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By T. D. Tiemann

The extraction of iron oxide from several types of siliceous iron ore by digestion in sulfuric acid solutions was investigated in the temperature range from 80 to 258°F at concentrations from 10-60% H2SO4. Degree and rate of extraction were found to be critical with respect to both temperature and acid concentration, requiring temperatures in excess of 250° F and acid concentrations of 50% to effect 80-90% extraction of iron oxide in 60 min. Rate of extraction is directly related to surface area and apparently controlled by the rate of chemical reaction. The activation energy was found to be approximately 25,000 cal per g mol. Extraction characteristics of the several ores were found to be similar. The Department of Minerals and Metals Engineering at the University of Wisconsin conducts a continuing research program to develop processes for the utilization of low-grade iron ore deposits such as the nonmagnetic taconites of the Wisconsin Gogebic range. Methods under study include high-intensity magnetic and high-tension electrical concentration, flotation, direct reduction and chemical extraction. Concentration of a number of low-grade siliceous iron ores by the extraction of silica in sodium hydroxide solutions has been reported by the writer and others in the literature.1,2,3,4 Residual concentrates containing as much as 65% iron have been obtained from taconites containing less than 30%. Currently an alternative approach is under study, namely the dissolution of iron oxides from siliceous gangue by extraction in acid, with subsequent recovery of the iron from solution. Such a process for extracting iron oxide from the low-grade oclitic deposits of Alberta with hydrochloric acid was investigated and described by Gravenor, Govett and Rigg.5 The current investigation, which is entirely devoted to extraction with sulfuric acid, is the subject of this paper. In part, the objective of this research was to determine the possibility of leaching iron ores in situ with sulfuric acid. The investigation of a recovery method is left to later research. The ores investigated contained hematite (Fe2O3) as the principal iron-bearing mineral and minor amounts of goethite (Fe2O3 .H2O), magnetite (Fe3O4), and iron-bearing silicates. The gangue was essentially quartz occurring as single crystals and microcrystalline aggregates. Detailed description of the ores may be found in the literature.1,2,4,6 A comparison of the specific ores used in this investigation is shown in the partial analyses of Table I. EXPERIMENTAL METHODS All extractions were made at atmospheric pressure using beakers with a mechanical stirrer for those tests run below the boiling point, and Erlenmeyer flasks for those at the boiling point. A thermostatically controlled hot plate was used for heating, and this maintained the mean temperature within the solution to within ±3°F during extraction. The sample of ore for extraction was weighed to + 0.02 g. For tests below the boiling point, the sample was added to the beaker containing the sulfuric acid solution at the desired temperature. For the boiling-point tests, the sample was added to the Erlenmeyer flask followed by distilled water and the

Jan 1, 1968

By Harvey Cline, Donald P. Ferriss

THE violent outgassing of commercial tungsten and other refractory metals when melted in an electron beam zone refining apparatus1"3 is dealt with experimentally by one or both of two approaches. One is to provide a suitable emission current control1,2 the other is to purify the metal in the solid state before melting.4 The first of these is usually sufficient, but the authors chose also to investigate the source of the troublesome gases and to devise means of solid-state purification. Some further insights into the use of tungsten as a structural material at temperatures near its melting point were also revealed in the course of the work. One may speculate on the causes of gas formation in tungsten at high temperature by inferences from the literature and an examination of the impurities in commercial wire. Davenport5 observed microporosity in both tungsten and molybdenum filaments heated to several hundred degrees below their melting points. Studying the function of oxygen in molybdenum welds, Perry, Spacil, and wulff8 attributed similar porosity to the disproportionation of Moo2 to molybdenum metal and Moo3. Tungsten dioxide also disproportionates7 above 2000oC to yield WO3 vapor at considerable pressure. Commercial tungsten contains some 5 to 20 wt ppm O and a similar concentration of carbon depending on the details and precautions of processing. Therefore, evolution of CO is also a strong possibility as a source of gas at high temperatures. Furthermore, even for activities in the order of 0.01, it may be calculated that the pressure of CO at 3000°C would be over 4000 psi, which is in excess of the tensile strength of tungsten at this temperature.9,10 Powder metallurgy tungsten contains some 0.02 pet Fe and 0.002 to 0.005 pet of the elements Ni, Si, Al, Ca, Mn, Mg, and Mo; at temperatures over 2800°c, therefore, these elements will exhibit appreciable vapor pressure, though small compared to that of WO3 and CO. Some of these impurities may react to form high-pressure monoxides such as SiO and A10. Finally, dissolved and occluded nitrogen is an ever-present source of high-pressure gas. Commercial Type 218, General Electric filament wires, 0.025 in. diam, were heated by resistance in 10 -4 mm of Hg and in argon or hydrogen at pressures from 50 µ to atmospheric. For temperature determinations in vacuo, the Jones - Langmuir8 current-temperature relationship was employed. For gaseous atmospheres, the burn-out temperature was assumed to be the same as in vacuo so that a small, constant correction could be made for temperatures below burn-out conditions (i.e., local heating to failure). Several dozen experiments may be summarized by pointing out some structural observations. At 3050oC in 1 atm of A, porosity is very evident after 30 min, as shown in Fig. 1. For the section in Fig. 2, failure occurred 200°C below the melting point and many voids have grown in the grain bound-

Jan 1, 1962

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 C. S. Matthews, W. R. Strickler, M. Prats

To gain an insight into the deviations from normal behavior caused by dip. a mathematical study has been made of single-fluid five-spot floods in dipping reservoirs for flooding techniques likely to be employed in such cases. Streamline patterns and sweep eficiencies are computed for a number of different cases, and the results, where possible, are presented in graphical form. An increase in sweep efficiency can be obtained by moving the central injection well updip, and the opti~num position is found for several cases. The applicnhility of the results is discussed. INTRODUCTION Because of the growing importance of water flooding in California and in other locations where large angles of dip are quite common, it is important to know at least some of the effects of dip on the performance characteristics of water floods in such instances. In the past, only reservoirs having relatively mild dips have been wateflooded. Consequently, little is known today as to the effect of dip on the performance characteristics of a flooding operation from the point of view of field experience; and because of the complexity of the problem, little, if anything, has been done on the problem from the point of view of theory. There are two distinct aspects of the role played by gravity in a flooding operation. The first is that of the preferential segregation of the reservoir fluids at the time when the flood is to commence. The second is the role that it may play in affecting the performance of the reservoir during the course of the flooding operation. In this paper the reservoir is assumed to be filled with only one fluid, so that there is no preferential segregation of reservoir fluids at the commencement of the flood. Moreover, the injected and in-place fluids are assumed to have the same characteristics, so that in effect we consider only a single-fluid problem. Single-fluid results have been used as a guide in the past for predicting and interpreting the behavior of regular five-spot floods in horizontal reservoirs. It is thought that single-fluid results might likewise be used for five-spot patterns in dipping reservoirs as a norm to which the effects of the multifluid problems might he referred.* In confining our attention to the single-fluid case, we therefore do not consider the preferential segregation of injected water in the oil bank, or of the oil bank in the unflooded zone. Instead we consider the deviation from the behavior of a horizontal five-spot which is caused by use of flooding techniques (i.e., the flow potential pattern at injection and production wells) likely to be employed during flooding operations in dipping reservoirs. In other words, we consider effects which are caused by the pattern of injection and production well pressures which we choose to apply. Performance characteristics are given for the five-spot spacing pattern as a function of two parameters; one is the ratio of gravity head to potential difference bctwccn the high updip injection well and the low downdip producer of the same five-spot, denoted by Rg; the second is the orientation of the five-spot pat-

Jan 1, 1956

By Reed W. Hyde

SOME information has been published on the sulphur dioxide concentration of gases from Dwight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide flotation concentrates mixed with minus 20-mesh oxide ore, the mixture carrying 16.8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO2 might be utilized, a series of runs was made to determine the concentration of SO2 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1) 2 to 1 3/4 in., (2) 4 to 3 1/2 in. and (3) 6 to 5 1/8 in. The averages of the determinations from each series are platted on the graph (Fig. I). The vertical scale shows the percentage by volume of SO2 (as determined by the Reich method), and the horizontal scale shows the time expressed as percentage of the total sintering time. Sintering was considered to be complete when no SO2 could be detected in the gases. In all cases the depth of bed was 4 1/2 in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which SO2 determinations were made could not be measured, but has been calculated from the SO2 content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume will usually drop slightly toward the middle of the period and increase toward the end. However, this assumption is a reasonable approximation. Several interesting features are brought out by these data. In general, the published data on SO2 concentration in sintering under ordinary conditions show a high SO2 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SO2 in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum SO2 concentration is obtained 2 ½ min. after

Jan 1, 1942

By C. S. Yust, C. S. Morgan

ThIS note reports the observation of masses of dislocation etch pits around the weld necks of small single-crystal particles of calcium fluoride sintered to a cleaved face of a larger CaFz crystal. Crystal particles in the -50 +I00 mesh size range were placed on freshly cleaved CaFz surfaces and heated at 1250°C for 30 min in a tantalum container in an argon atmosphere. The sintered specimens were then etched at room temperature for 40 to 50 min in a 2 pct sulfamic acid solution which is a selective etch for dislocations in caF2.' Figs. 1 through 3 show the masses of dislocation etch pits observed around weld necks after etching. In some cases, particles were gone after removal of the specimens from the furnace although weld necks were readily visible. In other instances, no etch pits formed around a weld neck. A possible cause of concentrations of dislocations on the crystal surface is mechanical deformation of the base crystal when particles are dropped on it. If such a deformation does occur, it would be much smaller than that caused by the light punching of a crystal with a sharp instrument which results in large concentrations of etch pits. However, crystals deformed by punching with the sharp instrument and annealed at the conditions of these experiments (1250°C for 30 min) before etching showed no concentrations of dislocation etch pits. It is obvious that dislocations from the much smaller deformations, possibly created when particles are placed on the surface, would also anneal out. Etching of large crystals which had particles placed on them in the usual manner but which were not heated showed no dislocation concentrations such as shown in Fig. 1. The magnitude of dislocation etch-pit concentrations did not vary with extensive variation of the cooling rate. The appearance of many of the etch-pit clusters is typical of a well-annealed condition, indicating that the dislocation concentrations formed before the specimen temperature was lowered. Therefore, it is evident that thermal stresses in the neck area did not create the deformation indicated by the presence of the dislocations. The possibility exists that the etch-pit concentrations at places where particles had been removed may be the result of deformation accompanying the fracture of the sintered bond. That this is not so was demonstrated by breaking off particles around which no etch pits occurred. Re-etching never resulted in the large concentrations observed at sintering sites. The stress available to effect material movement during sintering of two particles will depend on the geometry at the contact point but can easily exceed the macroscopic yield stress in CaFz systems. It appears that the plastic deformation observed results from sintering or simply from the weight of the small particles. It has been previously argued that plastic flow makes an important contribution to the initial densification of oxides having the fluorite crystal structure.2p3 If plastic deformation occurs, it would begin as soon as the temperature is sufficiently high

Jan 1, 1967

By Thomas P. Bispham

INTRODUCTION From the lender's point of view, the greatest period of risk in a project financing occurs during the construction phase. Therefore, most projects are supported during this phase by completion guarantees supplied by some credit-worthy entity; for example, the project sponsors in the case of a joint venture, such as that of W.R. Grace, Hanna Mining, and Liberty Capital; or by a strong contract with a utility or foreign importer/investor, such as the way North American Coal Corporation has structured many of its transactions. THE PROJECT LOAN REQUEST A project financing is a more complex form of term loan than one using an ongoing corporation's balance sheet as a credit base and, therefore, a potential lender will subject the loan request to a more rigorous analysis. To support this effort, the financial institution will require a more detailed information memorandum to evaluate the credit and technical risks of a project - especially since much of the necessary information is not otherwise available. (See also Gibbs and Sroka paper above in this Chapter) A well-prepared information memorandum will impress prospective lenders with the planning ability and general competence of management. Also, the process of preparing the memorandum will help management understand the true extent of the opportunities and limitations of its venture. Appendix A outlines the topics which comprise a complete information memorandum for a loan request. Of some interest to those seeking to sell a currently-operating mining venture, a similar information memorandum should be prepared i.e., covering the same topics discussed here, for the investment banker to use with potential purchasers. For that purpose, though, one might not want to prepare quite as much detail as for a lender. Appendix B outlines the elements of a reserve evaluation and feasibility study, often called the "Bankable Document." Usually, these studies are prepared by independent engineering consultants for use by potential borrowers and sellers. (Potential purchasers will often contract for a similar study for their use in evaluating an acquisition.) ELEMENTS OF A LOAN INFORMATION MEMORANDUM 1. Outline: The information memorandum should begin with a one-page outline covering such topics as: a. The borrower's name, address, and phone number. b. Principal contact at the borrower. c. Amount of the proposed financing. d. Desired pricing and structure of the proposed financing. This should include a description of the amount and source of equity in the proposed financing. e. Use of the proceeds and timing. 2. Summary: The most important information contained in the memorandum should be summarized in two pages. Note - If the borrower is a recently-formed single-purpose company, then elements 3, 4, and 5 will apply to the guarantors of completion and to the project sponsors. 3. The Borrower: This section is a brief biography of the borrower including such topics as date and state of incorporation, founder(s), lines of business, etc. 4. Capitalization: The borrower's current debt and equity position, including leases and trade debt, with amounts, terms, names, and addresses enumerated. Equity owners, and percentage ownership, should be identified. 5. Historical Financial Statements: If available, a minimum of five year's worth of complete historical financial statements

Jan 1, 1985

By D. F. Kaufman, E. D. Levine, L. R. Aronin

ThE primary slip plane in hcp metal crystals can usually be inferred from the c/a ratio. Basal slip is the primary system at room temperature for zinc, cadmium, magnesium, cobalt, and rhenium, all of which have a c/a ratio greater than 1.60. Zirconium and titanium, on the other hand, each with a c/a ratio of 1.59, deform primarily by (1010) [ll20] prismatic slip. The increasing tendency toward prismatic slip in these materials is generally thought to be associated with the increase in atomic density on (10i0) as c/a is reduced. Beryllium, with a c/a ratio of 1.57, would, according to the above scheme, be expected to exhibit prismatic slip. However, in beryllium of commercial purity, the primary deformation mode at room temperature is basal slip.' The ratio of critical shear stress for prismatic to that for basal slip at room temperature is approximately 5:l. The critical shear stress for prismatic slip decreases quite rapidly with increasing temperature, however, and at 500°C the ratio is approximately unity. The apparently anomalous behavior of beryllium has led to speculation that prismatic slip in this material may be restricted by an anisotropic effect of impurities,' and that, if beryllium could be purified to a sufficient extent, prismatic slip might predominate at room temperature. In such a case, the conditions under which basal cleavage can occur would be suppressed, and enhanced low-temperature ductility might result. With the advent of the floating-zone method for purification of beryllium,3 it has become possible to determine experimentally the effects of purification on basal and prismatic slip. Tensile tests were performed at room temperature on single crystals oriented favorably either for basal or prismatic slip. The crystals had been purified to various extents by zone-refining, employing procedures that have been described elsewhere.4 Relative purities of the crystals were estimated by measuring the ratio of electrical resistance at 4.2"K to that at 298°K. Typical values ranged from 0.40 for commercial-purity material to 7.7 X 10"4 for crystals prepared from vacuum-distilled beryllium and subjected to six zone-refining passes. The purity dependence of the critical shear stresses for basal and prismatic slip is shown in Fig. 1. In the purity range studied, the critical shear stress for basal slip is decreased from 1.4 to 0.14 kg per sq mm. The critical shear stress for prismatic slip is decreased from 6.7 to 5.3 kg per sq mm. The decreases in critical shear stress for each deformation mode, therefore, are approximately equivalent. No purification anisotropy is observed. Because of the absolute magnitudes of the critical stresses, the ratio of the critical shear stress for prismatic slip to that for basal slip actually increases from 5:l to 38:l at the highest purity level studied. It is evident, therefore, that basal slip is the primary deformation mode in high-purity beryllium. This fact must be accounted for in any rationalization of the deformation behavior of hcp metals. This work was performed at Nuclear Metals, Inc., under the sponsorship of the U.S. Atomic Energy Commission.

Jan 1, 1964

By Reed W. Hyde

SOME information has been published on the sulphur dioxide concentration of gases from Dwight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide flotation concentrates mixed with minus 20-mesh oxide ore, the mixture carrying 16.8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO2 might be utilized, a series of runs was made to determine the concentration of S02 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1) 2 to 1 1/3 in., (2) 4 to 3 1/2 in. and (3) 6 to 5 1/8 in. The averages of the determinations from each series are platted on the graph (Fig. I). The vertical scale shows the percentage by volume of SO2 (as determined by the Reich method), and the horizontal scale shows the time expressed as percentage of the total sintering time. Sintering was considered to be complete when no S02 could be detected in the gases. In all cases the depth of bed was 4 ½ in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which S02 determinations were made could not be measured, but has been calculated from the S02 content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume will usually drop slightly toward the middle of the period and increase toward the end. However, this assumption is a reasonable approximation. Several interesting features are brought out by these data. In general, the published data on S02 concentration in sintering under ordinary conditions show a high S02 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SO2 in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum S02 concentration is obtained 2 ½ min. after

Jan 1, 1942

By M. S. Seltzer

In a previous paper1 it was shown that activation energies for steady-state creep in lead sulfide single crystals varied with the concentration of electronic defects. For n-type lead-excess crystals, values for the creep activation energy, Qc, decreased from 2.9 to 2.2 ev as the carrier concentration increased from 1017 to 1017 electrons per cu cm, while Q, increased from 1.6 to 2.3 ev for p-type sulfur-excess crystals as the concentration of holes increased from 6 X 1017 to 1018 per cu cm. It was also shown in Ref. 1 that the Q, values could best be correlated with the sum of the self-diffusion activation energies in PbS, i.e., for a given concentration of electrons or holes Q, = QPb + Qs, where Qpb and QS are the activation energies for diffusion of pb210 and s35 in PbS. This result suggests that creep rates are controlled by at least two atomic defects, one for lead migration and one controlling sulfur transport. It would be most desirable to interpret these creep energies in terms of an atomic defect disorder model for lead sulfide. Studies of creep rates as a function of sulfur pressure2 indicate that the defects controlling creep rates are singly ionized lead and sulfur vacancies, VPb and Vs. This hypothesis can be more firmly established by determination of Q, under conditions of constant atomic defect concentration rather than constant electronic defect concentration as has been previously done. Therefore, several measurements have been made of Q, on crystals whose con- centration of lead vacancies or sulfur vacancies has been fixed by equilibration under appropriate sulfur pressure and temperature. It was indicated in Ref. 2 that high-temperature isotherms are available which show how the concentrations of various atomic point defects in PbS vary with composition over the entire homogeneity range for the compound. Two such isotherms are shown in Fig. 1 for 900" and 1000°K. Utilizing these isotherms the concentration of a given defect, say Vbb, may be held constant over a particular temperature range by adjusting the sulfur pressure as the temperature is changed. Thus the concentration of one defect suspected of controlling creep rates may be held constant while other defect concentrations vary. The apparent activation energy for formation of these defects can be obtained from the isotherms giving their concentration as a function of sulfur pressure. Activation energies for creep obtained under conditions of constant defect concentration can then be compared with defect formation energies and certain possible atomic defects can be eliminated as creep-controlling species. We have performed creep experiments as a function of temperature at a stress of 244 g per sq mm under conditions which fixed the lead vacancy concentration, V', at 1016, 3.2 x 1016, and 3.2 x 1017 cm-3, and one were the sulfur vacancy concentration, Vs, was held at lo17 cm-3. The results are presented in Fig. 2 as creep rate, k, vs reciprocal of absolute temperature, 1/T. Specimens 34, 35, and 36 were deformed under constant lead vacancy concentration while specimen

Jan 1, 1969

By A. C. Losekamp, R. M. Fincel, J. B. Conway

TANTALUM like several other metals exhibits a great affinity for or reactivity with certain gases. Tested in atmospheres which are not completely pure this metal becomes contaminated by certain impurities (notably nitrogen, oxygen, and hydrogen) with a resultant change in various properties. Well-known are the drastic changes in hardness, ductility, and electrical resistivity. Also previously recorded are the distortions of the lattice1,2 accompanying the increased content of oxygen and nitrogen in tantalum. This pronounced affinity for certain gases along with the significant property variations thereby produced makes it necessary to observe additional experimental precautions in making various property determinations with tantalum. Some recent measurements of the linear thermal-expansion characteristics of tantalum have made this point quite emphatically. Failure to observe the greatest precautions in reducing the contaminating influence has led to some extremely distorted results. Not only does such operation lead to different heating and cooling curves during the thermal-expansion measurements, but upon cooling to room temperature the sample is found to have suffered a permanent (actually semipermanent since the specimen can be returned to its original length by a 3-hr degassing treatment in vacuum at 2300°C) elongation. In addition, subsequent heatings will not follow the initial heating curve unless the expansion measurements are based on the actual specimen length at the beginning of the heating cycle. These thermal-expansion measurements were made by positioning the specimen horizontally at the longitudinal midpoint of a 20-in.-long, 4-in.-diam resistively heated tungsten tube furnace. The specimens were in the form of 20-mil sheet formed into a sharp U-shape about 0.3 in. in width and 0.3 in. in depth. Fiducial marks in the form of 0.010-in. holes drilled at either end of the 2.5-in.-long sheet specimens were viewed by a paired filar micrometer telescope system mounted on an Invar bar on the top of the furnace. Tests were made in helium with temperatures measured by a Pt/Pt-lORh thermocouple to 1000°C; above 1000°C temperature was measured by means of an optical pyrometer sighted into a black-body hole drilled into the specimen-holding fixture in the vicinity of the specimen. Previous tests with black-body holes drilled in a 0.25-in.-diam rod specimen had confirmed the temperature uniformity between specimens and specimen-holding fixture in this furnace. A typical thermal-expansion curve for arc-cast tantalum in helium is shown in Fig. 1 for the case where no attempt is made to remove all the impurities from the cover-gas atmosphere. The initial heating curve appears smooth and has a shape characteristic of all metals. However, it is known that the sample begins absorbing impurities at temperatures above 1000°C which are sufficient to distort the lattice and lead to specimen lengths which are somewhat larger than would be obtained in the absence of contamination. During the cooling cycle the expansion curve is seen to be significantly different from the heating curve. This is due to the impurity content causing a semipermanent (i.e., permanent until the impurities are removed by vacuum degassing) deformation which will not allow the speci-

Jan 1, 1965

By C. E. Sims

In some experimental work conducted several years ago, it was noted that sulphur seemed to have a distinct influence on grain size of carbon steels. 111 order to check this observation, a series of S..A.E. 1040 steels was made with the normal composition held as nearly constant as possible. The steels were made with three sulphur levels, which were 0.012, 0.024 and 0.038 per cent sulphur, respectively. For each of the sulphur levels, steels were made with only silicon deoxidization and with aluminum additions of 0.1015, 0.025, 0.050 and 0.10 per cent. The melting medium was an acid-lined high-frequency induction furnace. These steels were forged and rolled and differentiall!. quenched from temperaturcs in the range of 1500O to 1800°F. After this, the A.S.T.M. grain size was determined and plotted as in Fig. I. It will be noted, first of all, that the aluminum-free steels had filler grain size with higher sulphur when heated to 1500, but that this condition was reversed at 1700°. When aluminum was added to produce fine grain size, the steels in the lowest sulphur level were fine-grained only to 1600°. and then only with an addition of one pound of aluminum per ton. The medium sulphur steels werc fine-grained to 1600' with a wider range of aluminum addition. The steels in the highest sulphur level were fine-grained at 1600° over a still wider range of aluminum additions and fine- grained at 1700° with an addition of one pound per ton. Fig. 2 shows curves of the grain-coarsening temperature for these steels and illustrates how sulphur and aluminum combine to give greater inhibition to grain growth than aluminum alone. Only the highest sulphur steels have a grain-coarsening temperaturc above 1700°.. At 1650°, the low sulphur steel is fine-grained only at its peak, while the highest sulphur steel is fine-grained over a wide range. In these tests, one pound of aluminum per ton gave the best results; this is equivalent to about 1 1/2 lb. per ton for commercial condition. IllcQuaid-Ehn tests made on these steels showed the same trend but to a lesser degree. The tests were repeated on a series of S.A.E:. 1015 steels with sulphur levels of 0.02 and 0.03j per cent. Aluminum additions were made in the range from 0.025 to 0.15 per cent. These steels were forged and rolled, normalized at 2000°F. to put them all in the same starting condition, then reheated to various temperatures from 1600" to 1800" and cooled at rates that would allow ferrite precipitation in the austenitic grain boundaries. The results of these tests arc shown in Fig. 3. It will be noted that. up to the temperature of 1650°, there is very little difference in the grain size obtained from the two levels of sulphur. .At temperatures of 1700° and 1750°, however, the lower sulphur steel was fine-grained only with an aluminum addition of 1 1/2 lb, per ton;

Jan 1, 1945

By T. W. Healy, P. Somasundaran, D. W. Fuerstenau

The flotation behavior of quartz in the presence of alkyl ammonium acetates as a function of alkyl chain length has been interpreted in terms of hemi-micelle formation at the solid-liquid interface. The van der Waals cohesive free energy that is responsible for hemi-micelle formation has been found from these results to be 1.0 kT per CH2 group. This is in excellent agreement with literature values obtained from research on the properties of micelles in bulk systems. Collectors of the type CH3(CH2)n-2CH2-P, where P is a polar group and n is the number of carbon atoms in the straight alkyl chain, will induce flotation of an appropriate mineral at lower concentrations as n increases. This reduction in collector concentration with increasing n has been reported for such systems as xanthates on sulfides1,2 and amines on quartz.' The effect of chain length of alkyl surfactants on such solution properties as conductivity,' surface tension,' and solubility6 and such interfacial properties of solids as contact angle7 and electrokinetic potential8 have received considerable attention, but only limited quantitative descriptions of the effects have been given. The electrokinetic studies of alkyl amine salts on quartz indicated that the solution concentration of collector at which the marked change in electrokinetic potential of quartz occurs decreases systematically as the length of the alkyl chain increases. The aim of the present work was to obtain a quantitative description in terms of current theories of flotation of the effect of the hydrocarbon chain of alkyl ammonium acetates on the flotation behavior of quartz. BASIC PRINCIPLES The marked changes in electrokinetic potentials of quartz in dodecylammonium acetate (DAA) solutions were postulated to result from the association of adsorbed collector ions into two-dimensional aggregates, called hemi-micelles.9 Subsequently, the rapid increase in flotation rate of quartz was shown to coincide with hemi-micelle formation." We would like to discuss briefly the concept of hemi-micelles in terms of recent interpretations of micelles in bulk solution. Micelle hypothesis: In dilute solutions, alkyl ammonium and related salts behave as ordinary strong electrolytes, but at a certain concentration there is a marked change in physical properties of the solutions, e.g., in equivalent conductance, transport number, freezing point lowering and viscosity. To account for these phenomena, McBainl1 introduced the concept of micelles, which are aggregates of long-chain ions. It is believed that the ionic heads of the constituent ions of the micelle are in contact with water, whereas the nonpolar groups turn away from it and are in contact with each other. Work must be done to bring these charged polar groups together, but energy is gained (i.e., so called van der Waals cohesive energy) when hydrocarbon chains are expelled from the water and allowed to associate. For a given polar group, the tendency to form micelles will therefore strongly depend on the hydrocarbon chain length. Theoretical treatments of micelle formation by Shinoda12 and Phillips13 and others lead to the following expression for the concentration at which micelles form (the critical micelle concentration or cmc) in aqueous solutions of long- chain electrolytes

Jan 1, 1964

By Franz Fohr

On July 27, 1919, there passed away a simple, unassuming gentle-man, who, throughout his life, allowed his intense modesty to keep him-self in the background and during his later years effaced himself so thoroughly that but few of his acquaintances knew aught of him. Yet he was one of our accomplished metallurgists, who did good work in the practice of his profession and lived an upright life. Now that he is no longer with us Franz Fohr cannot plead to be overlooked, and those who fondly remember him will be gratified by his receiving his due. Franz Fohr was born, Sept. 7, 1838, in Mannheim, Germany. Of his ancestry, education, and early career we know scarcely anything. We do not even know just when he came to America, or. what led him hither. The first record of his professional work in this country, found among his papers, shows that from July, 1870, to Jan. 1, 1872, he was superin-tendent of the Newark Smelting & Refining Works, then owned by Ed-ward Balbach & Son. At that time the Balbach works at Newark, established in 1850, and the Selby works at San Francisco, established about 1866, were the only important silver-lead refineries in the United States. Mr. Fohr may have been associated with the Balbachs for some time before he became superintendent of their plant or he may have come from Germany but a short time previously. At all events, it is certain that he was at that time an experienced and accomplished metallurgist. After leaving Newark and going to San Francisco, he soon formed a connection with Thomas H. Selby & Co. Early in 1874-this firm sent him to New York to procure information respecting the manufacture of white lead. His engagement in New York terminated on-Jan. 31, 1875. During 1875, Mr Fohr spent some time at Silver Islet and in the Lake Superior copper region, but of his work there no record remains. In the latter part of 1875, or early in 1876, he associated himself as metallur-gist with the Boston Silver Co., operating at Saint John's, Summit County, in which William L. Candler, of Boston, was the moving spirit. That company was developing its mine in 1875. At the end of that year it "had about 800 tons of ore on hand, about three-fourths of which is dress-ing ore, to be concentrated in its very systematic establishment and to be smelted into pig lead." Evidently Mr. Fohr was engaged for the latter purpose. Henry A. Vezin, erudite and painstaking, was the mechanical engineer for the company. In the fall of 1876, Anton Eilers took his family for the first time so far West as Denver and Mr. Fohr went with them. I do not think that Mr. Eilers had any connection with the Boston Silver Co., save possibly in a consulting capacity, but he visited Saint John's and the enduring friendship among Eilers, Fohr, and Vezin, which terminated only with their deaths, dated from that time.

Jan 12, 1919

By L. D. Jaffe

IN 1945-1946, the author measured temper brittle-ness in ingots of varying composition prepared by remelting SAE 3135 bar stock under vacuum. Since other investigators1-" have been referring to this hitherto unpublished work, belated publication seems worthwhile. Steel in 7 lb batches&apos; was induction melted with nickel additions in a magnesia crucible under a pressure of 10 microns of Hg or less and cast into a 2 in. diam chill mold. The compositions of ingots A, B, and C prepared in this way are shown in Table I; the vacuum melting lowered carbon, manganese, sulphur, and nitrogen content. Ingot B was homogenized 24 hr at 1095°C; ingots A and C were not homogenized. Blanks, M in. square, were cut from each ingot, austenitized 1 hr at 870°C, water quenched, tempered 1 hr at 595"C, and water quenched. Half the blanks from each ingot were given an embrittling treatment of 50 hr at 455°C and water quenched. A few specimens, embrittled and unembrittled, were finally heated 1 hr at 580°C and water quenched. Charpy specimens machined from the blanks were V-notched on the side closest to ingot mid-radius and paired as to radial position in the ingot, one of each pair having received the embrittling treatment and the other not. Specimens were broken in a standard impact machine at various temperatures, the same temperature, in general, being used for both bars of a pair. Fig. 1 shows the results. It is evident that temper brittleness, as measured by the increase in temperature of transition from brittle to tough failure introduced by the 455°C treatment, was decreased but not eliminated by reducing carbon to 0.006 pct, manganese to < 0.004 pct, and nitrogen to 0.001 pct. In another study," temper brittleness was apparently eliminated by -reducing carbon to 0.003 pct, with 0.80 pct Mn and 0.0015 pct N (ingot D)." • Analyses given for carbon below 0.02 pct were made by Jensen method; for nitrogen, by Kjehldahl method. Values quoted else-where&apos;-&apos;." for carbon content of ingot C and for nitrogen content of ingot D were obtained by conventional combustlon and by vacuum fusion methods, respectively, and are considered much less accurate. The 580°C final treatment removed previous em-brittlement (ingot B particularly), indicating that this was "reversible embrittlement."" Metallographic examination of ingot C with 1 pct nital etch revealed only ferrite; ingot A had carbide spheroids uniformly distributed in a ferrite matrix. With ethereal picric acid plus zephiran chloride etchant.&apos; no differences between embrittled and un- embrittled specimens of ingots A, B, or C were noted. Fracture of C and D below the transition temperature was predominantly transcrystalline, with traces of intercrystalline, in both embrittled and unembrittled conditions. The corresponding fracture of unembrittled B was mixed transcrystalline and intercrystalline; of embrittled B, predominantly intercrystalline with some transcrystalline areas. . . . Acknowledgment The efforts of J. C. Leschen, formerly of National Research CO~P., in preparing the ingots are acknowledged with thanks.

Jan 1, 1956

By G. R. Love

i\ program has been written which allows fully automatic conversion of data for X-ray intensity, as a function of time, to finished conventional pole figures. The program accepts input data in the serial order in which they are taken and is therefore immediately compatible with automatic data-acquisition devices. From these data taped instructions are prepared for the Calcomp plotter to construct ink-on-paper drawings. Because both Siemens and Norelco pole figure goniometers are used in this laboratory, the program was written for pole figure data obtained from one or more interpenetrating spiral scans during which both the polar angle, @, and the equatorial angle, a, are varied simultaneously and continuously. The reference direction for a scan, that is the point @ = 0 deg, may be chosen coincident with either the normal direction (N.D. figures) or the rolling direction (R.D. figures). In either case the plotted figures are drawn with the transverse direction (a = 0 deg) at the right and the rolling direction at the top. The full, circular, pole figure is drawn as two semicircular figures labeled "front side" and "back side". As presently constituted, the program will also accept data from circular scans taken at constant values of @. In every case the angular coordinates of each intensity entry are generated in the computer from a relatively small number of auxiliary data. The X-ray intensity data are corrected for background scattering by direct subtraction of the intensity measured with 28 set appropriately "off" the Bragg angle. It is possible to enter this correction as an additional spiral scan through the a, @ space; because the background correction does not normally vary rapidly enough to warrant this detailed a determination, the background corrections are entered as one or more auxiliary data. All data are normalized to a multiple of random intensity. The data taken in this laboratory for N.D. figures are normally taken in a reflection geometry from from sheet samples and do not extend beyond <p = 75 deg; for these data random intensity must be determined from separate experiments and entered as auxiliary information. When the auxiliary information is not available, a number is chosen to give intensity values normalized to a scale of 1 to 10. In this laboratory, R.D. figures are based upon hemispherical samples for which data are taken out to @ = 90 deg; for these data random intensity is calculated by direct numerical integration of . sin @ d@ using the trapezoidal rule and the background-corrected values of the input data. Points necessary to the construction of the pole figure are identified by simple linear interpolation between adjacent data points to determine the loci of contour lines. Points lying on a given contour are connected to one another with straight-line segments and the search-calculation-drawing sequence is patterned to assure that different contour lines do not cross, that a single line does not branch, and that lines do not end in space. However, so that there be no ambiguity in the data presentation, all contour lines end at the limits of the input data. Since the curves are constructed of straight-line segments, they are not continuous in their derivatives. However,

Jan 1, 1969

By P. Niessen, S. J. Bercovici

RECENTLY Aust et al.&apos; proposed a model of non-equilibrium grain boundary segregation based on a vacancy gradient induced uphill diffusion process of solute to grain boundaries. According to their proposal, solute atoms which are attracted to vacancies would, during the cooling of a sample, migrate with vacancies toward grain boundaries (vacancy sinks) and thereby enhance the solute concentration in boundary regions. For solute atoms which are not attracted to vacancies no such boundary solute enrichment would be expected. These concepts were given experimental support by boundary and bulk mi-crohardness measurements of various thermally treated dilute zinc and lead alloys and also doped aluminum oxide. The underlying assumption in their work was that solute enrichment in boundary regions is indicated by higher microhardness values. From thermodynamic considerations1&apos;2 it appears that the solid-liquid solute distribution coefficient (K), defined as the concentration of solute in the solid to the concentration of solute in the liquid at equilibrium, indicates whether attractive or repulsive forces exist between vacancies and solute atoms. K < 1 indicates a solute-vacancy attractions, K > 1 indicates no, or a repulsive, vacancy-solute interaction. This note is to report on observations of different grain boundary etching phenomena in high purity zinc alloys. These phenomena appear to depend on whether a K < 1 or K > 1 solute is present. In experiments designed to measure directly the solute enrichment in grain boundary regions, samples of zone refined zinc with 0.1 at. pct solute additions were cooled from 380°C at a rate of 3°C per min. A surface layer of approximately 50 was then removed from the samples by chemical polishing. The samples&apos; surfaces were then protected by a chromating treatment such that in a subsequent etch only grain boundary regions were dissolved. The dissolved regions were approximately semicircular troughs, 10 µ in width. The grain boundaries were usually in the middle, i.e., at the bottom, of this trough. For zinc containing the K < 1 solutes cadmium and aluminum, the grain boundary was always indicated by a ridge as shown in Fig. 1. For pure zinc, and zinc containing the K > 1 solutes copper and gold, a groove at the bottom of the trough indicated the boundary position, Fig. 2., To test if these different grain boundary etching behaviors were possibly connected with the segregation process discussed above, the Zn-Cd alloy was again heated to 380°C and quenched into brine. After surface protection and etching it was found that this specimen no longer exhibited the grain boundary ridges but rather grain boundary grooves as shown in Fig. 2. It would appear, therefore, that the boundary ridge is a consequence of a process occurring during the slow cooling of the samples. From absorption spectrophotometric analysis it was found that for slowly cooled samples containing K < 1 solutes, the solute/zinc ratios of the material from the boundary trough were consistently considerably higher than the solute/zinc ratios of the bulk alloys. This boundary region solute enrichment was not observed in quenched samples. It is concluded therefore, that the boundary ridge shown in Fig. 1 is directly or indirectly connected with nonequilibrium solute segregation.

Jan 1, 1970

By R. D. Longyear

[Some Problems Involved in the Interpretation of Diamond-drill-hole Sampling and Surve ing (paper by J. J. Collins, Mining Tech., Jan. 1946). ............... I Geologic Interpretation of Magnetic Exploration on the Mesabi Range, Minnesota (paper by R. H. B. Jones, Mining Tech., July 1946) ................... 2] DISCUSSION R. D. LONGYEAR.*-Mr. Collins is to be commended very highly for the brief summary he has made of the currently used methods of taking diamond-drill sludge samples and the principles involved in evaluating the results. This paper should stimulate further discussion and research on this vitally important problem. It is particularly imperative that geologists and engineers know when assay results on sludge recovery can be accepted quantitatively and when they must be considered only qualitatively. In most cases where the sludge recovery is less than 95 per cent or more than 125 per cent, it is safest to consider the assays as of qualitative value only. Certain cases, however, are known where a relatively small proportion of the sludge sampling will give a reasonably accurate measure of the value of the total sample. One such case is ore in which the valuable mineral is of approximately the same specific gravity as the waste mineral, such as chalcopyrite in a massive pyrite body. The essential point is to determine the degree of accuracy of sludge sampling in any given drilling project and to weigh the results accordingly. It should be emphasized, however, that sludge sampling can be made reliable in many localities where careless practice produces unreliable results. In many instances, it is desirable to empty the core barrel in the core shack instead of at the drill, so that the engineer can examine the core as it first comes from the core barrel. It should be pointed out, however, that the drill * E. J. Longyear Co., Minneapolis, Minnesota. runner should be permitted to study the core to guide his future drilling. It is hoped that with the return of more normal conditions after the war geologists, engineers, contractors, and manufacturers will be able to carry on more research along the lines of improved core-barrel design and drilling technique with the objective of increasing core recovery so as to eliminate as far as possible the necessity of relying upon sludge samples. H. M. ROBERTS.*-Whoever in the future will have to do with the search for ore bodies and their exploration will have frequent occasion to refer to the clear and comprehensive summary on diamond-drilling methods by John Collins. His review of the experience of the last 40 years in this technique is invaluable. As Dr. L. D. Ricketts wrote in 1932, "The principles on which an art is founded are usually few and necessarily basic in nature, but he who wishes to achieve the power to select his aides and give success to important undertakings that may be intrusted to him in the future must ordinarily undergo years of drudgery in order to gain the experience that will enable him to distinguish such fundamentals through the haze of reinforcing detail that clothes and tends to disguise them."[t] Ricketts went on to say that since the beginning of the century there has been much

Jan 1, 1946

By C. E. Birchenall, W. Batz, H. W. Mean

AT temperatures between 1095&apos; and 1347ºC, 13 runs have been made on the diffusion of silicon in iron. In two of the runs the couple compositions were entirely within the loop of the Fe-Si system; the base alloys contained 0.0 and 1.0 wt pct Si. The other runs in which the couples consisted of a 2.3 wt pct Si alloy welded to a 3.7 pct Si alloy were a phase throughout. The alloys were made by melting electrolytic iron and commercially pure silicon. Trace impurities were not determined. The butt welded couples were diffused in an inert atmosphere of argon or hydrogen. After cooling, cuts of two mils or greater thickness were machined parallel to the weld interface. The chips were analyzed for silicon. When the concentration and distance data were examined on the conventional probability plot,&apos; no marked variation of the diffusion coefficient with concentration was indicated over the narrow composition ranges employed. Therefore, a single diffusion coefficient is recorded for each run in Table I. The temperatures and atmospheres of the diffusion anneal are listed along with the compositions of the base alloys. For a iron the silicon diffusion coefficient is given by the equation: D = 0.44 e-48,000/RT where R is the gas Constant and T, the absolute temperature. However, since the scatter in the data is fairly large, the activation energy may be in error by as much as 6000 cal per g-atom. The two ? iron points do not permit estimation of the activation energy with any reasonable certainty. They do indicate that the coefficients reported by Smithells2 and Jost,3 based on the work of Fry,4 are much too high. Although very dilute solutions in iron of manganese,5 nickel,8 cobalt,7 and molybdenum8 give dif- fusion coefficients quite close to those obtained for self-diffusion in iron, the silicon values are considerably higher, though of the same order of magnitude. This seems to be consistent with the fact that the silicon atom is the only one of those listed here which is appreciably smaller than iron. The authors are grateful to the Office of Naval Research for their support of this work under Contract N6ori-47, Task order IV, Project NR 031-184, to J. K. Stanley and the Westinghouse Research Laboratories for the silicon alloys used, to several steel companies for the silicon analyses, and to C. Wells, of the Metals Research Laboratory, Carnegie Institute of Technology, for numerous suggestions during the course of the work. References &apos;C. Wells: Atom Movements (1951) Chapter 2. A.S.M. 2C. J. Smithells: Metals Reference Book (1949) p. 405. Interscience. Pub. Co. 3W. Jost: Diffusion (1952) p. 223. Academic Press. 4 A. Fry: Stahl und Eisen (1923) 43, p. 1039. T. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 315. "C. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 329. 7M. F. Hawkes and R. F. Mehl: Trans. AIME (1947) 172, p. 467; Metals Technology (August 1947). .J. L. Ham: Trans. A.S.M. (1945) 35, p. 331.

Jan 1, 1953

By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,&apos; fractional crystallization,&apos; and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported&apos; to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman&apos; in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956