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By N. L. Muench, J. S. Osba

Research conducted previously has demonstrated that spectral analysis of gamma radiation from the naturally radioactive elements present in earth materials permits detervination of the relative concentrations of these elements. This research suggested that spectral analysis of gamma radiation resulting from neutron bombardment of elements not nor-mally radioactive might serve to identify these non-radioactive elements, and might permit their quantitative determination. To investigate this possibility, laboratory experiments were conducted in which various earth materials were subjected to bombardment by neutrons from a polonium-beryllium source, and in which the spectra of the resultant gamma radiation were analyzed. The geometry of the lab-ortory system was designed to simulate wellbore conditions. The laboratory work demonstrated that some elements not only can be identified with relative ease, but also can be determined quantitatively. This finding indicates that the use of an intense source of more energetic neutrons may lead to the identification and measurement of additional elements of interest by means of induced nuclear reactions. INTRODUCTION In recent years the applications of nuclear physics to the producing branch of the petroleum industry have become increasingly numerous. One significant development, an outgrowth of nuclear science which is of potential importance in well logging, has been the analysis of gamma-ray spectra of naturally radioactive elements in earth strata. The work of Brannon and Osoba1 has demonstrated that presently available equipment and techniques may be used to determine the relative concentration of thorium, potassium, and uranium in underground strata by means of gamma-ray spectral analysis. Success of the research on spectral analysis of naturally radioactive elements suggested that spectral analysis of induced radioactivity might serve to identify, and perhaps measure quantitatively, those elements which normally are not radioactive, but which become radioactive on neutron bombardment. It was to investigate this possibility that the research described in the following sections was undertaken. THEORY OF INDUCED NUCLEAR REACTIONS Of fundamental importance is the fact that an element, when bom- barded with neutrons, emits gamma rays of energies characteristic of that element. Therefore, in theory, an element may be identified by analysis of the energy spectrum of the neutron-induced gamma radiation. If a neutron impinges upon the nucleus of an atom, any one of several reactions may occur. For identification of elements in earth formations the more important are listed below: 1. The neutron may be elastically scattered, as in a collision between two billiard balls. In this case the total kinetic energy is conserved, and no nuclear radiation is emitted. 2. The neutron may be inelast-ically scattered, as in a collision between two automobiles in which case the total kinetic energy is not conserved. The lost kinetic energy reappears in the form of gamma radiation. 3. The neutron may be captured, in which case the neutron becomes a part of the target nucleus, and a gamma ray is emitted. For example, if the target nucleus is H1, the pro-duced nucleus will be H3, and gamma radiation of a particular energy will be emitted. 4. The neutron may produce nuclear fission, or may enter into miscellaneous reactions which result in the emission of

Jan 1, 1958

By N. A. MacLeod

Ball wear in wet grinding mills has been the subject of considerable discussion in the last few years. Its importance to millmen is obvious in view of the fact that ball wear may cost from 2 to 4 per ton of ore for the more fortunate operators and many times this cost when a refractory ore must be reduced to a fine state of comminution. Consequently, any factual information that may be obtained on the nature of ball wear may be applied to introduce changes leading to lower ball consumption and therefore also to lower costs. In 1940, while employed with the Britannia Mining and Smelting Co., Britannia Beach, B.C., I had occasion to investigate factors that might affect ball consumption. We performed a number of tests, which will be briefly described. These tests originated as a result of changing from a 3½-in. ball to a 2-in. ball of different type of manufacture and were motivated by the desire to obtain the best possible type of 2-in. ball. Our testing was helped by the fact that the company operated a one-ton electric furnace, so that it was quite easy to make steel changes. It should be emphasized at the beginning that these tests produced results that in their general application to milling should be interpreted qualitatively rather than quantitatively. As will be evident in the description of the method used in testing, the balls were subjected to an intermittent batch grinding treatment, which may have produced results in rate of steel wear that may not have an accurate correlation with steel consumption in full scale mill operation. However, with this bed and rather arbitrary method of testing, results were obtained that may be of some interest and may stimulate further work on this subject. Unfortunately, owing to pressure of war work, our tests, which we had intended to repeat on a continuous grinding operation, had to be discontinued. Method of Testing Tests Were made in a Small cylindrical mill, rotating at 72 r.P.m. Internal dimensions of the mill were 10½-in. dia. by 9 in. The cylindrical inner surface was lined with rubber and the two ends were formed by steel plates. A charge of 2000 grams dry feed and 2000 C.C. of water was added evev 2 hr., the mill being drained of pulp before the addition of each charge, by tilting and sluicing with water. The mill was run On afternoon and night shift for daily periods of about 15 hr. total grinding time, and each test lasted from 60 to 150 hr. This batch method of testing involved a higher average pulp temperature in the mill, which undoubtedly affected comparative results in Some of the tests. Hardness oF Ball vs. Wear In these tests, special "eutectoid" steel balls were used, some of which were chill-Cut and quenched, some sand-cast and quenched, and some sand-cast and annealed to a dead soft condition. The results obtained, using as mill feed an ore containing considerable free quartz and

Jan 1, 1947

By N. A. MacLeod

Ball wear in wet grinding mills has been the subject of considerable discussion in the last few years. Its importance to millmen is obvious in view of the fact that ball wear may cost from 2 to 4 per ton of ore for the more fortunate operators and many times this cost when a refractory ore must be reduced to a fine state of comminution. Consequently, any factual information that may be obtained on the nature of ball wear may be applied to introduce changes leading to lower ball consumption and therefore also to lower costs. In 1940, while employed with the Britannia Mining and Smelting Co., Britannia Beach, B.C., I had occasion to investigate factors that might affect ball consumption. We performed a number of tests, which will be briefly described. These tests originated as a result of changing from a 3½-in. ball to a 2-in. ball of different type of manufacture and were motivated by the desire to obtain the best possible type of 2-in. ball. Our testing was helped by the fact that the company operated a one-ton electric furnace, so that it was quite easy to make steel changes. It should be emphasized at the beginning that these tests produced results that in their general application to milling should be interpreted qualitatively rather than quantitatively. As will be evident in the description of the method used in testing, the balls were subjected to an intermittent batch grinding treatment, which may have produced results in rate of steel wear that may not have an accurate correlation with steel consumption in full scale mill operation. However, with this bed and rather arbitrary method of testing, results were obtained that may be of some interest and may stimulate further work on this subject. Unfortunately, owing to pressure of war work, our tests, which we had intended to repeat on a continuous grinding operation, had to be discontinued. Method of Testing Tests Were made in a Small cylindrical mill, rotating at 72 r.P.m. Internal dimensions of the mill were 10½-in. dia. by 9 in. The cylindrical inner surface was lined with rubber and the two ends were formed by steel plates. A charge of 2000 grams dry feed and 2000 C.C. of water was added evev 2 hr., the mill being drained of pulp before the addition of each charge, by tilting and sluicing with water. The mill was run On afternoon and night shift for daily periods of about 15 hr. total grinding time, and each test lasted from 60 to 150 hr. This batch method of testing involved a higher average pulp temperature in the mill, which undoubtedly affected comparative results in Some of the tests. Hardness oF Ball vs. Wear In these tests, special "eutectoid" steel balls were used, some of which were chill-Cut and quenched, some sand-cast and quenched, and some sand-cast and annealed to a dead soft condition. The results obtained, using as mill feed an ore containing considerable free quartz and

Jan 1, 1947

By C. E. Westley, R. R. Beebe

Recent works by Plaksh et al.,1,2 Glembotsky,3 and others have renewed interest in the effects of oxidation on the surface activity of the sulfides. Since considerable supporting data are available on galena-potassium ethyl xanthate, this system is being studied at South Dakota School of Mines and Technology by contact angle measurement, using the technique of McGlashan and McLeod.4 The contact-angle method is well adapted to investigation of the influence of small amounts of oxygen on the establishment of a stable contact angle on galena in potassium ethyl xanthate solution. Samples of massive galena containing less than 0.001 pct Cu, 0.001 pct Ag, and 0.01 pct Zn are mounted in castable plastic and ground and polished manually in a glove box containing the desired proportions of oxygen and purified nitrogen. Oxygen and nitrogen contents of the test atmosphere are determined with an Orsatt analyzer. In this way a reproducible surface is created in contact with whatever oxygen concentration is desired. Water and all reagents are prepared and stored in the test atmosphere. An absorbent is used to control carbon dioxide that might be present. Final polishing is done with levigated alumina on a glass plate. The prepared sample is placed in the test solution and transferred to the contact angle apparatus in a sealed box, and the test is conducted while both sample and solution are maintained under a slight positive pressure of the test atmosphere. Table I gives the results of contact angle measurements made at various 02-Nz concentrations.5 Each value of contact angle is the average of at least six individual measurements made with different bubbles at different locations on the sample surface. A period of 20 to 25 min has been found by preliminary tests to be sufficient to permit develop- ment of maximum angle, and all measurements are made after at least this much time has elapsed. Exposure of prepared samples to pure water under the test atmosphere before exposure to the xanthate results in a small but measureable and consistent reduction in contact angle. This is particularly true in the oxygen-deficient atmospheres; for example, at 2.2 pct O2 such water contact reduces the average angle about 8" from that obtained by immediate testing in xanthate. The general trend of increasing contact angle with increasing oxygen concentration corresponds to the results of Plaksin et a12 The absence of diminish-ment of contact angle at very high oxygen concentration has been attributed to the high concentration of xanthate per unit of galena surface: At oxygen concentrations below 1 pct (the limit of accuracy of the Orsatt analyzer), no contact angle is obtained. Furthermore, no contact angle is obtained at any oxygen concentration in the absence of xanthate. This result seems to be in disagreement with those cited by Plaksin.1 Further work on the interaction of galena and potassium ethyl xanthate or a similar collector as influenced by oxygen is contemplated. The true nature of the interrelation is as yet unknown. For example, it is not known whether the governing oxygen reaction is with the mineral, with the reagent, or with both.

Jan 1, 1961

By J. P. Heller, H. B. Bradley, A. S. Odeh

It is an accepted procedure to represent oil field displacement problems in which the pressure is relatively constant by a potentiometric model. Variations in reservoir permeability thickness product are represented in the model by proportional variations in electrolyte depth. It is shown that significant errors are present wherever these variations are of such magnitude that the consequent differences in the electrolyte depth in the model or any regions therein are appreciable in comparison with their respective horizontal dimensions. To demonstrate the order of magnitude of this error, a hypothetical linear oil field in which permeability varies linearly with distance was treated both analytic.ally and by potentiometric model. The results obtained from the model are compared with the exact solution for various configurations of linear geometry. Deviations in flow times up to 11 per cent were observed. It is confirmed that these discrepancies can be reduced by increasing the areal scale and/or decreasing the vertical scale of the model. It is the purpose of this work to assist in the design of potentiometric models by indicating the relationship between this error and the chosen scale factors. INTRODUCTION The fundamental geometrical criterion which determines whether the pressure distribution in an oil or gas reservoir may be simulated in a conventional potentiometric model is the requirement that all reservoir parameters be constant along any vertical line between its upper and lower boundaries. This situation never obtains exactly; nevertheless, it is usually assumed that there is no permeability stratification within the section of interest, that all wells completely penetrate the sand, that there are no gravitational effects, and that variations in thickness of the sand are small compared to the horizontal extent of the field. In these ways the reservoir problem is reduced to two dimensions in which there is no variation of pressure in the vertical direction within the limits of the sand. Variations in sand thickness and/or horizontal pesmeability may be taken into account as described by Muskat, by considering the fluid conductivity of the reservoir in its horizontal plane to be proportional to the product of permeability and sand thickness. If the variations in sand thickness are small compared to the horizontal dimensions of the reservoir, then it is a good approximation to consider the reservoir problem to be essentially two dimensional. The same approximation, however, is made in the simulation of the assumed two-dimensional reservoir by the electrolytic model. The model, if it is to take into account variations of permeability-thickness product, must of necessity be made in three dimensions, that is, with variable depth. Most potentiometric model studies and theoretical treatments reported in the literature to date2,3,4,5,6,7,8 are those in which either an average permeability was used or a constant permeability was assumed. This is understandable since detailed permeability data are not usually available for the majority of reservoirs. Many investigators have recognized that the failure to incorporate permeability variations within a reservoir in model studies leads to serious error in predictions made

Jan 1, 1957

By L. Stone, H. Margolin

The Ti-C-N and Ti-C-O systems were investigated in the temperature range from 500° to 1400°C and in the composition range up to 2 pct C and 5 pct N or 0. Characteristic isothermal sections at 800°, 900°, 1000°, and 1300°C are presented. The Ti-N-0 system was studied in the temperature range from 900' to 1400°C with alloys containing up to 6 pct total alloying content. Characteristic isothermal sections at 1000° and 140O°C are presented. Melting-point data for all three systems are also included. THIS paper reports on one of a series of investi-gations which have been conducted on the phase diagrams resulting from interstitial alloying with iodide titanium. The other investigations involved delineation of the binary systems with carbon,' nitrogen and boron,h and oxygen. The Ti-0 binary system has also been investigated by Bumps et al.' In varying degrees, each of these interstitial elements has been shown to stabilize the low temperature a modification of titanium1-5 and each forms a face-centered cubic TiX compound (henceforth designated 6). In addition, the Ti-N and Ti-0 systems reveal a low temperature tetragonal phase (6) formed by a peritectoid reaction between a and TiX Experimental Procedure The development of experimental techniques for the study of titanium alloy systems has, to a large extent, become standardized. In this investigation, the equipment and procedures described in detail by Cadoff and Nielsenl have been used. Arc Melting: In general, binary alloys with carbon, nitrogen, and oxygen, prepared in the composition range of interest in this investigation, show negligible composition changes during arc melting. However, the possibility of the formation of some gaseous combination of alloying elements such as CO, CN, or NO during the preparation of these ternary alloys was considered. Calculations showed that the evolution of only 0.05 gram of such a gas would be detectable as a pressure change in the closed system used during preparation of these alloys. Such pressure changes were not observed. Consequently, nominal compositions have been used in plotting the data. The compositions of the materials used in the preparation of the alloys are shown in Table I. After melting for 3 to 5 min at 275 to 350 amp, the alloys were checked for homogeneity by microstruc-tural examination. Alloys containing up to 1 pct C were homogeneous in the presence of less than 3 pct N or 0. At higher alloying contents, some inhomo-geneities in the carbon distribution became evident. Alteration of the melting procedure toward longer times and higher currents did not improve the homogeneity of these alloys. Ti-N-0 alloys were homogeneous in the range to about 3 or 4 pct total alloying addition. Beyond this, almost all of the specimens showed as-cast microstructures consisting only of the phase. Consequently, inhomogene-ities could not be detected by examination of micro-structures. Ten alloys from each of the systems were analyzed for two of the elements present (oxygen being omitted in all cases and titanium being omitted in the Ti-C-N alloys). In all cases the analyses were found not to be sufficiently precise to serve as criteria for the total composition of these alloys. On the basis of phase distribution in heat-treated alloys, however, it appears that carbon is distributed throughout the alloys most uniformly, with oxygen and nitrogen following in that order. Heat Treatment: Specimens for heat treatment were wrapped in titanium sheet before sealing in the argon-filled quartz capsules. Heat-treatment times varied from 100 hr at 800°C to 0.5 hr at 1400 °C. After heat treatment the specimens were quenched by breaking the capsule in water. With the exception of alloys in the low composition region, heat treatment did not have an appreciable effect on the as-cast microstructures. Metallography: Following heat treatment, the specimens were prepared for metallographic examination by grinding on emery paper and electrolytic polishing. For the majority of the specimens a 10-sec etch with Remington "A" agent (25 pct HNO3, 25 pct Hf, and 50 pct glycerin) adequately

Jan 1, 1954

By D. D. Smith, D. P. Squier, E. L. Dougherty

A system of differential equations describing the temperature behavior of fluid injected at constant surface temperature in a well is derived and .solved analytically. A formula for the fluid temperature at any time and depth is given, as well us a special formula valid for very large times. These formulas are used to calculate temperatures for several typical cases. The results indicate that, initially, the temperature of the water entering the formation is considerably lower than the injection temperature. This condition lasts for only a short period— less than three days for most cases of practical interest. Following this highly transient period, during which the temperature of the fluid entering the formation builds up to about 50 to 75 per cent of the injection temperature. the system enters a quasi-steady state in which the temperature changes are very slow. After severl years, the bottom-hole temperature will still be 50" to 100°F lower than the injection temperature, hilt the heat losses may he tolerable. INTRODUCTION Predicting the behavior of a hot-water flood requires that the temperature of the water entering the injection interval be estimated. This report describes the development and solution of a system of equations which describes the temperature behavior of the injected water in the wellbore with certain simplifying assumptions. The only previous means known to the authors for describing such a process is that of Moss and White.' Their results appear to be close to those obtained by our method in the practical cases which were compared; this agreement is largely due to the fact that in our method temperature soon approaches a quasi-steady state, as was assumed in their method throughout. However, our model covers all times, is continuous (whereas the Moss-White model depends on breaking the depth into discrete intervals) and. we feel. more closely describes the physical problem. FORMULATION OF THE PROBLEM PHYSICAL SYSTEM AND ASSUMPTIONS The injection procedure consists of pumping water at a fixed surface temperature T., down an infinitely long cylindrical well or tubing of inner radius Any material exterior to the water column such as mud, casing, or cement is regarded as part of the formation. The general behavior of the system may be described qualitatively as follows. When the hot water is first introduced into the system, the temperature difference between the formation and the water is large, resulting in a high rate of heat transfer. As a result, the temperature adjacent to the wellbore rises very quickly. Because the segment of the formation adjacent to the wellbore largely controls the heat transfer rate, the heat transfer rate will become relatively constant when this portion has reached a temperature close to that of the water opposite it. The temperature of the water and formation then increase very slowly with time. The length of the initial highly transient period and the temperature of the water at its conclusion will be functions of depth, injection rate, injection-string radius, surface injection temperature and the physical properties associated with the water-formation system. The following additional assumptions were made. 1. There is no heat transfer by radiation in the system. 2. There is no heat transfer by conduction in the vertical direction in either the injection stream or the formation. 3. The linear volumetric and mass flow rate of the water is constant throughout the injection stream. 4. No horizontal temperature gradient exists in the injection stream. 5. The product of density and heat capacity is constant for both the water and the formation, and the formation thermal conductivity is constant. 6. Initially, both the water in the wellbore and the reservoir are at a temperature given by the (constant) ambient surface temperature plus the product of depth and geothermal gradient (assumed constant). At large distances for the wellbore (r m), the formation will remain at this temperature. 7. The water temperature and the formation temperature at r — r,, are equal for all depths D. DERIVATION OF EQUATIONS The differential equation satisfied by the fluid temperature T,(D, t), which is obtained by writing a heat balance on a cylindrical differential of volume dV of the injection string between the depths D and D i dD, is

By H. Sigurdson, T. V. Cherian, C. H. Moore

The phenomenon of recovery of cold-worked metals is interesting not only because of its practical importance but also because of its fundamental significance in solid state reactions. Although extensive investigations1,2 have already been made in an attempt to discover the mechanics of the recovery process, many of the observations have not yet been satisfactorily correlated to provide a completely consistent model for the process. The wide differences in the recovery rates of various properties can be cited as a typical example of one of the difficulties that are encountered. Frequently, for example, the electrical resistance will have almost completely recovered before any recovery in tensile strength can be detected. Of course, such differences in the recovery rates of different properties might be explained by assuming that each property is a unique function of the work-hardened state, and consequently each property exhibits its own unique recovery rate. The assumption that different properties are uniquely related to the work-hardened state cannot be denied. On the other hand, the properties that recover at different rates often exhibit more or less parallel changes upon work-hardening. This suggests that the microstructural changes attending recovery are not exactly the reverse of the changes attending work-hardening. Several types of imperfections must be postulated in order to account for this apparent anomaly. The different recovery rates for various properties, then, are due to the different recovery rales of the type of imperfection to which each property is most sensitive as well as the unique dependence of each property on the cold- worked state. This concept assumes that a simple model of the work-hardened state consisting only of one type of imperfection, such as Taylor's type of dislocation patterns, is inadequate to cope with the diversified phenomena attending work-hardening and recovery. Although current models for the work-hardened state are not useful for describing all aspects of the recovery process, the general trends of the recovery of each postulated type of imperfection as a function of time and temperature should be at least qualitatively deducible from the rather well developed laws of kinetics of reactions in the solid state. Consequently, recovery data might prove useful for elucidating some aspects of the complexities of the work-hardened state of metals. A preliminary attempt to study work-hardening by investigating recovery rates of cold-worked metals is outlined in the following pages of this report. Experimental Procedure Many properties recover when cold-worked metals are annealed below their recrystallization temperature. Therefore, electrical resistivity, thermal electromotive force, X ray diffraction line widths, X ray diffraction line intensities, elastic spring back, density and other physical and chemical properties have been used to study the recovery process. Major interest, however, has generally been directed toward the recovery of the mechanical properties such as hardness, yield strength, and tensile strength. But a search of the literature suggests that the effect of recovery on the true stress-true strain curve has been neglected, in spite of the current recognition of the fundamental importance of such an investigation. An investigation on the effect of recovery treatment on the true stress-true strain curves in tension, therefore, was undertaken in the present study. Commercially pure aluminum (99. + pet Al) in the form of 0.100 in. thick rolled sheet of 2S-O aluminum alloy was selected as the material for this investigation because rather extensive correlatable data are already available on the recovery of some of its properties. Tensile specimens having a 6 in. long gauge section and a uniform reduced section width of 0.500 in. were machined from the sheet in accordance with a design that has previously been reported.3 All specimens were selected with their axes aligned in the rolling direction. In order to eliminate the effects of previous work-hardening and the effects of machining, the specimens were annealed for 15 min. at 750°F before testing. During tensile testing the loads were measured by means of a proving ring (sensitive to 1/2 lb) in series with the specimen.4 Strains were determined from the extension of a rack and pinion strain gauge sensitive to a strain of + 0.0001. The stress was recorded as the true stress, namely

Jan 1, 1950

Theoretically mobile primary crushers at the mine working face can be considered the ideal comminution system. A crusher which follows the ore can reduce materials handling costs because it eliminates about one ton of truck deadweight per ton of ore hauled to the crusher. It also eliminates the backhaul of this same deadweight ton. Development of mobile primary crushers has centered in Germany where many soft iron ore and limestone deposits are flat-lying and thus readily adaptable to the use of shiftable conveyors which easily followed the working face. These ores were easily crushed in impact- type mills which had extremely large receiving openings and therefore large reduction ratios. The feeding of such a unit was done with a front-end loader which dumped its load to an inclined apron feeder, which in turn fed the impactor. Under the crusher was an inclined conveyor which transferred the crushed ore to a belt wagon for delivery to the shiftable overland conveyor. Low headroom overhead eccentric single-toggle jaw crushers and short-shaft gyratories were also used on these units, which generally travelled on tracks. While these early mobile primary crushers were versatile and served their purpose, they generally suffered from low capacities. Manufacturers have quickly responded with larger crusher, feeders, and moveable supports, however; and today mobile crusher s have capacities of up to 1500 metric tons per hour, a figure comparable to the capacity of some 54 in. by 74 in. gyratories. An example of a quarry portable crushing plant is at the Bath cement plant of Canada Cement Lafarge, Limited. Two 12 cu yd front-end loaders are digging the stone and hauling it to the portable crushing plant which feeds a field conveyor system. The crushing plant is moved and the field conveyors extended whenever the length of the haul exceeds 300 ft. At the crushing plant, the loaders discharge the stone onto a pan feeder which feeds into the hopper of a Weserhutte-Hazemag compound crusher which combines primary and secondary rotors in the same housing. These are driven at 1200 rpm by 800 hp and 1,000 hp motors (600 and 750 kw). The maximum 3 ft feed (914 mm) is reduced to 3/4 in. (19 mm) at 800 tph. The Weserhutte steered walking mechanism, operated by hydraulic cylinders, takes five -foot strides. Another example is at Alcoa of Australia's operation at Huntley in Western Australia. At the mine face, front-end loaders load 50 mt rear-dump trucks that transport the bauxite ore to the mobile crusher which follows the mine operation. The crusher can turn 360° within its own length, walk at a speed of 34. 5 ft per minute (10.5 m per

Jan 1, 1978

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,' Mc Quillan,' Van Thyne et dl.,' and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger' discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95' *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse's conclusions, Barrett's results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By J. Lindbo, B. Vigeholm

IN transmission electron microscopy, specimen thicknesses quoted are frequently based upon either traditionally familiar values or a few evaluations representing the whole material. Taking aluminum in 100 kv TEM as an example, average and maximum values are widely accepted as being 2000 to 2500 and 6000 to 7OOOÅ, respectively. It is the purpose of this note to revise these figures and to point out the importance of evaluating individual specimens carefully. All evaluations have been based upon slip trace widths and lattice orientations as determined from diffraction patterns. In many cases where two or more slip systems have been operating the geometrical method described by Crocker and Bevis1 has been applied as a check. The foils were usually oriented to within 2 deg from the exact Bragg angle. Kikuchi patterns were used as indications of correct orientations but not applied in the evaluations. The tilt of the foil surface relative to the beam normal may with certain geometrical relations between the tilt axis and the operating slip plane lead to substantial errors.2'3 Where these geometries were inevitable the samples were omitted in the investigations. Various measures were taken in order to overcome ambiguities, e.g., comparison with neighboring grains, tilts, evaluations based upon two or three slip systems,' and comparison with extinction contour evaluations where s = 0 conditions were obtained. Errors caused by misinterpretation of the slip traces on a micrograph are easily avoided by considering the bright-dark sequence on opposite surfaces and by taking into account the tapering of the foil usually leading to a distinguishable divergence of the pair of traces. In the investigations described here the interpretation was further facilitated as the slip trace formation was observed on the microscope screen and sketches taken down. In a few observations slipping was so violent that the distinction of pairs was considered dubious and consequently given up. To assess average values, thickness evaluations carried out in two independent investigations were analyzed: I) 99.998 pct A1 extruded, cold-drawn, and recrys-tallized to grain sizes between 35 and 500 um were deformed in tension at room temperature. In order to determine the dislocation densities as a function of strain,4 specimens prepared by spark machining and electropolishing in a PTFE holder were analyzed in the electron microscope at 100 kv. Thicknesses were evaluated for 569 selected areas. Histogram I in Fig. 1 shows the results, the average thickness being 4900Å. II) Electropolished specimens prepared from 99.9999 pct A1 with magnesium contents from 0.005 to 0.5 pct rolled to foil and annealed were subjected to fission fragment irradiationa2 For volumetric dose and defect concentration determinations thickness evaluations were performed on 123 areas. Histogram II in Fig. 1 shows the thicknesses of these areas averaging 4250Å. Whereas in investigation I no selection related to thickness has been made, some thin as well as thick areas have been omitted from I1 for experimental reasons. This and the application of two different microscopes although of the same type may account for the difference in average thickness. Assuming a mean error of 10 pct for a single evaluation, the error of the average should be negligible. In order to investigate the maximum transmissible foil thickness in aluminum, specimens were prepared from single crystals with (111) and (110) orientations parallel to the beam, and from polycrystalline material. Maximum values of thickness that could be measured were given by the stopping of the dislocations. The visibility often extended far beyond the end of the slip trace, but with no means of knowing the

Jan 1, 1970

By Robert T. Pring

IN addition to the humanitarian aspects of a dust-control program, certain economic benefits are becoming more fully recognized and now furnish a greater incentive to the mill operator to eliminate the dust from his plant. It is well known that a favorable working environment promotes increased efficiency and improves the morale of employees, with a consequent decrease in labor turnover rates. One progressive mining company1 estimates its direct and indirect labor turnover costs at from $40 to $50 per man; for skilled labor, such as machine operators, the cost may approach $100 per man. While these figures may not be typical of every plant, they do indicate a potential savings in operating costs. Dust signifies waste; its elimination decreases maintenance costs of mechanical and electrical equipment; its recovery is often justified from the standpoint of values contained in the collected material, although in large-scale milling operations handling low-grade ore this may not be an important factor. Perhaps the most significant trend in industrial sanitation is that dust-control equipment and procedures are becoming recognized as integral parts of the mill flowsheet. Exhaust ventilating systems are now afforded equal care in design and maintenance to that given other machinery more closely related to the process. METHODS OF DUST CONTROL "Dust control" is a general term descriptive of a number of methods used singly or together to prevent particulate atmospheric contamination. These methods are, in order of their desirability, as follows: I. Change of process. 2. Isolation of process. 3. Wet methods. 4. Ventilation. a. Local exhaust ventilation. b. General ventilation. 5. Personal respiratory protection. In ore-concentration plants it is seldom practical to change a process to eliminate the dust it creates It is possible in some cases to isolate a particular dust-producing operation from the rest of the plant, provided that constant attention on the part of the operators is not required. Frequently water is used in fine crushing and fine grinding, primarily to facilitate the processing of the ore and incidentally to allay the dust produced. Wet methods, however, are not feasible in coarse and secondary crushing operations, because of the relatively great volume of water required in instantly wetting each freshly fractured rock surface. Such quantities of water would entail conveying and storage difficulties. Local exhaust ventilation is the most effective and most commonly applied control measure, wherein directional air currents through the zone of dust production draw the contaminants into a duct system. Unfortunately, only a limited amount of reliable information on exhaust ventilation is available.2-5 Of necessity these publications are rather general, being primarily concerned with engineering fundamentals. While many organizations have successfully

Jan 1, 1940

By E. A. Gulbransen, W. S. Wysong, K. Andrew

INTRODUCTION THE reaction of carbon in solid solution in a metal with the surface oxide film on many metals may be inferred from thermodynamic calculations for high vacua and high temperature conditions. Holm1 has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. Considerable work has been described in the literature on the decarburization reaction. Several general references may be noted.2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides 0n strips of various types of chrome-nickel alloys. Some of the early experiments on the behavior of 13 pct chrome-iron in vacua of the order of 5 X 106 mm and at a temperature of 600°C have been reported.5 These experiments showed a slow reaction with the residual oxygen or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600°C pure enough to reduce Cr203 formed on the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome iron and Nichrome V has been investigated in the thin film range by Gulbransen, Phelps and Hickman,6 and shown to be Cr203. It was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pct nickel and 20 pct chromium was heated to 850°C in a high vacuum, the specimen' lost weight. The rate of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. TYPE REACTIONS Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature, of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type. They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: [I. Metal • (gas) ;--* metal + gas - degassing of the metal 2. xM(s) + y ½ 02(g) tom- M.0„ (s) – oxidation]

Jan 1, 1948

By J. H. Jackson, P. D. Frost, C. H. Lorig, L. W. Eastwood, A. C. Loonam

R. S. BUSK*—I wish first to congratulate the authors of this paper both for the work done and the presentation of that work. We have also been working on this type of alloy development, but any technical contribution I might have is better reserved for a separate paper which is planned in the near future. However, I would like to insert a word of caution. The alloys described in this paper are still very much in the laboratory stage. There still remains the quite vexing problem of property stability at slightly elevated temperatures which must be solved before the properties quoted can be effectively utilized. These alloys are extremely interesting and I am confident that the problems can be solved. However, the present existence of those problems must not be overlooked. I have one question with regard to the work-hardening test. If the work harden-ability of magnesium is compared to aluminum using a more standard test such as the Meyer Analysis the magnesium is found to work harden the more rapidly. Is the test developed for this work truly a work-hardening test or a measure of something else ? J. H. JACKSON (authors' reply)—I am sure we appreciate the comments of Mr. Busk and we are pleased that the Dow Chemical Co. has also undertaken work in this field. It is a big field. We, of course, are continuing our research for the Navy Bureau of Aeronautics, since, as clearly shown in the paper, the alloys are not completely developed. With regard to Mr. Busk's comments on the relative work-hardenability of aluminum and magnesium, the comparison we cited in the paper was intended merely to show that the results obtained by our method of testing were independent of the yield strength of the materials. We believe that this test method afforded a rough indication of the work-hardenability of the magnesium-lithium base alloys. It is not known whether this method affords greater or less accuracy than the Meyer Process, which is based upon a hardness-test impression. It is quite possible, since work-hardenability is a function of metal purity, that our results, obtained for commercial aluminum and magnesium, would be different if high-purity metals had been used. A. C. LOONAM—Lithium has some very interesting effects on magnesium. The paper showed that even small percentages increased ductility. These small amounts changed the axial ratio of the hexagonal magnesium from 1.624 in the pure metal to 1.606 in the saturated alpha solution, a value close to that of titanium, which has a ratio of 1.601. You will recall an article in the January, 1949, issue of the Journal of Metals where it was stated that titanium can be cold-rolled over 90 pct without any significant edge cracking. At 4.9 or 5 pct lithium, a change begins in crystal structure—from a hexagonal close packed to body centered cubic. There are two phases over a short range of lithium content, but at 10 pct the structure becomes completely cubic. The melting points of alloys in this range of lithium content are relatively high. Alloys even up to the six ratio have melting points above 500°C; this represents a relatively small reduction in melting point from pure magnesium itself. The magnesium-lithium system has a number of very interesting characteristics. This is only a very small part of the story. J. H. JACKSON—I would like to remind you that Mr. Loonam is one of the authors of this paper, and the fact is that this work is based on many of his ideas. I am sure we appreciate his additional comments in this discussion. R. LEITER*—I am interested in Fig 19 in which Mr. Jackson compares

Jan 1, 1950

By B. H. Caudle, R. E. Watson, I. H. Silberberg

The production history of an inverted nine-spot injection pattern was studied with a porous plate model similar to Habermann's. Colored fluids were used so the boundary movements could be photographed. By varying the production rates of the side and corner producing wells, the optimum pattern sweep efficiency can be obtained. Results of the laboratory tests indicate that interpolation of the pattern sweep and conductivity ratio data will permit application of the data to predicting fluid injection operations with mobility ratios between 0.1 and 10 and production rate ratios between I and the optimum values. INTRODUCTION The inverted nine-spot injection pattern in Fig. 1 has some unique advantages over other regular injection patterns (five spot, line drive, etc.) used in secondary recovery operations. It has three producing wells for each injection well, while the five-spot and line-drive patterns require an equal number of injectors and producers. Futher-more, of the eight producing wells surrounding each injection well, four are of the "side well" type which lie nearer the injection well than the remaining four "corner wells". This allows the production rates of these two types of wells to be adjusted independently of each other to obtain better pattern sweep efficiency. This latter advantage may well be the reason why the nine-spot patterns have not been studied as extensively as the patterns containing only one type of injection or producing well. The pattern sweep efficiency of the inverted nine spot is affected almost as much by operating with different producing rates of the comer and side wells as by differing mobility ratios. Possibly because of this added operating parameter, published studies of nine-spot systems have been limited in their coverage of the pertinent variables.'-' The model studies reported here covered the mobility-ratio range normally found in waterflood operations, as well as the variation in well production rates necessary to achieve optimum pattern sweep efficiency. Conductivity ratios — a measure of the change in total flow at constant pressure difference — were obtained during each model run. A porous-plate model with miscible fluids representing the in-place and injected fluids was used in this study. This model technique is the same as that used in both X-ray shadowgraph" and visual techniques4 described in the literature. Using miscible fluids eliminates residual oil in the model, and the permeability to the injected fluid is the same as to the in-place fluid. Thus the mobility ratio in the model is given by the ratio of the viscosity of the displaced fluid to the viscosity of the injected fluid. Because of the non-linear nature of the viscosity vs composition curve for two miscible liquids, the mobility change across the boundary between the two fluids is reasonably sharp. This technique thus represents the displacement of a region of one fluid mobility by a region of possibly different mobility in an isotropic system under steady-state flow conditions. Table 1 shows the dimensionless similarity groups used to scale the model conditions and results to

Jan 1, 1965

By C. S. Smith, K. K. Ikeuye

In an earlier paper1 one of the authors called attention to the significance of the relative free energies of grain boundaries and interphase boundaries in alloys in determining the shape and distribution of micro-constituents. The ratio of the interphase and inter-crystalline boundary energies (that is, —?12, where ?12 is the energy of the interface between a crystal of phase 1 and a crystal of phase 2, and ?11 is the energy of the boundary between two crystals of phase 1) will be denoted by F. It is this ratio that determines, by the simple triangle of forces relation, the dihedral angle, ?, of phase 2 where it adjoins a boundary between two grains of phase 1. On a metallographic sample various angles are actually obtained because of the random orientation of the plane of observation, but the statistically most frequent angle is the true one. These basic principles were discussed in detail in the earlier paper. The experiments described below show the effect of both composition and temperature on ? and T for some alloys containing a liquid phase, and provide data on the rate of approach to the equilibrium angles in both solid and liquid phases. All the alloys were melted in a graphite crucible and cast into ingots 3/4 by 11/8 in. cross-section. Some of the aluminum alloys consisted of two immiscible liquids from which uniform castings could not be obtained. The amount of liquid phase varied locally to a considerable extent and the analyses were meaningless. Nevertheless, the composition of the liquid would not differ from that in an alloy of the intended gross composition, and the synthetic composition of the alloys was therefore used in considering the surface energy results. The ingots were given initial deformation by cold-rolling to 50 pct reduction, annealed, and given a second 50 pct reduction prior to cutting into small samples for heat treatment at the times and temperatures subsequently reported. The resulting micro-samples were carefully prepared metallographically and examined at magnifications of 650, 1280, or 2500. The objectives used were 21X, 0.40 NA (dry); 41X, 0.65 NA (dry); and 80X, 1.40 NA (oil emulsion). The appropriate angles were measured by rotation of the stage of a Bausch and Lomb metallograph to align the appropriate boundaries successively with a cross-hair in a micrometer eyepiece. About 250 angles were measured on each phase. Though the angles were read to 1°, the accuracy is probably not above 3°, because of uncertainty in setting the cross-hair tangent to the sometimes curved boundary. The corners of very small particles, particularly in early stages of adjustment after cold-rolling, were difficult to measure and the results were slightly dependent on the magnification used (compare Fig 1-C and 1-D). With particles of larger size and more nearly equilibrium shape, magnification made no difference (vide Fig 1-F and 1-G). The measured angles were grouped in 10° intervals (5° if ? was less than 20°) and plotted in bar

Jan 1, 1950

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

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,' fractional crystallization,' 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' 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' 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

By J. H. Kittel

THE properties of the metal molybdenum have been the subject of recent investigations1,2 = which have included studies of the changes that occur in the metal when it is annealed after having been cold worked. Most of the data which have been reported have pertained to only one aspect of annealing, that is, the conditions under which recrys-tallization has been observecl. The process of recovery which may precede recrystallization docs not appear to have been investigated, and it is the purpose of this note to report observations on the recovery process in cold-worked molybdenum as determined by changes ill the thermoelectric power which occur as the metal is annealed. The measurements were made on commercially pure molybdenum wires which, after annealing at 1035°C in dried hydrogen for 1 hr, were swaged to give a series of reductions up to a maximum of 84.5 pct. The variously cold-worked wires were then annea1c.d in dried hydrogen for periods of 16 hr at progrc:ssively highel. temperatures from 200" to 1000 c with a final annealing treatment of 70 hr at. 1100°C. After each annealing treatment the ther.ma1 emf's were determined against a length of original unwo~,ked material that had received the initial hydrogen anrit,aling treatment. The difference in temperature between the hot and cold junctions was maintained at about 75'C. and. the thermal emf's were measured with a potentiometer that could be read. to 0.01 microvolt. Fig. 1 shows the thermoelectric power. (dE/dT) in microvolts per C between annclalcd and cold-worked molybdenum as a function of the degree of cold work. The effect of annealing is shown in Fig. 2. The general shape of the curves in both figures is similar to results which have been obtained for copper." It was observed that after annealing at temperatures as low as 200°C recovery was well under way. The rapid changes irt thermoelectric power observed near 900 C are probably associated with recrystallization, since such a relation has been observed with copper. Beyond 900°C the thermal emf's changed in polarity. indicating that from this point or1 the specimens were more highly annealed than the standard. Annealing treatments could not be given at temperatures higher than 1100°C due to limitations of the furnace, and it is evident that, since equilibrium values of thermoelectric powers were far from having been attained, temperatures considerably higher are required to fully anneal molybdenum. References Robert M. Parke: Molybdenum, A New High-Temperature Material. Metal Progress (1951) 60, pp. 81-96. * R. A. Long, K. C. Dike, and H. R. Bear: Some Properties of High-Purity Sintered Wrought Molybdenum Metal at Temperatures up to 2400 °F. NACA TN 2319 (March 1951): G. W. Brindley: A Thern-io-Electric Study of the Cold-Rolling and Heat-Treatment of Copper, Report of a Conference on the Strength of Solids. Physical Society, London (1948) pp. 95-106.

Jan 1, 1953