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By Jr. Ensign C. O., J. W. Trammell

The two principal methods of room-and-pillar mining practiced at White Pine make it important to predict variations in the thickness and rock types of a stratum called the upper sandstone. In full column mining, the nearly barren upper sandstone occurs between two ore horizons (called upper shale and parting shale, respectively), and is mined as a part of the ore column. In general, full column mining is not practiced where excessive upper sandstone thickness causes full column ore grade to be substantially lower than parting shale ore. In parting shale mining, the upper sandstone forms the mine roof. Difficulty in predicting upper sandstone character arose because the extent and directions of its variations were not apparent in the property's diamond drilling, in which holes are spaced on 1000-ft centers. A study of sedimentary features, undertaken to improve the predictability of trends in the upper sandstone, led to an interpretation of the sedimentary environment in which the sandstone was deposited. Ripple marks, mud cracks, and cross-bedding, as well as other, less well known features, such as channel casts, flute casts, and current crescent casts, were mapped or recorded. These data, coupled with the knowledge of regional facies changes gained from studying drill core, show that the upper sandstone was deposited by a series of streams flowing northeastward over the underlying parting shale. Deposition of the lowermost bed of the upper sandstone, near the ancient shoreline, was locally preceded by erosion of the parting shale, and the greatest thicknesses of sandstone are found in channels scoured out of the parting shale. Awareness of the rather strong linear trends in the upper sandstone makes it possible to project continuous areas of thick upper sandstone through apparently isolated "highs" in the upper sandstone thickness contour map, which is based on drill-hole information. Since local exceptions to general stratigraphic trends exist, a method was also needed for esti- mating, in detail, the thickness and degree of shali-ness of upper sandstone forming the roof in active parting shale mining areas. Because locally the parting shale was thinned by erosion during the deposition of upper sandstone, parting shale thickness is inversely proportional to upper sandstone thickness. Utilizing information taken from short drill holes into the roof, curves were constructed for the correlation of parting shale thickness (measurable in the mine) with the upper sandstone total thickness, as well as the thickness of its basal member. The White Pine mine is situated in Ontonagon County, approximately 6 miles south of Lake Superior, in the Upper Peninsula of Michigan (Fig. 1). The orebody mined by White Pine Copper Co. occurs in the lowermost 20 to 25 ft of the Nonesuch formation, a series of middle- to upper-Keweenawan shales, siltstones, and sandstones. This paper discusses the solution of problems in ore grade control and mine planning arising from the presence of an essentially barren sandstone stratum within the orebody. THE OREBODY AND MINING TYPES A brief description of the orebody and mining methods is necessary to show how the upper sandstone affects mine planning and grade control. In the mine, the cupriferous zone of the Nonesuch shale is divided into three major portions, as shown in Fig. 2. Lying conformably on top of the Copper Harbor formation (or "lower sandstone") is the lower part of the orebody, the parting shale. The parting shale is overlain by the upper sandstone. On top of the upper sandstone, the basal portion (8 ft) of the upper shale is quite similar to the parting shale. Both the upper shale and parting shale are divided into a number of smaller stratigraphic units, each having a characteristic copper content, as shown by the histogram of Fig. 2. Other authors1'3 have dealt in detail with the stratigraphy and mineralogy of the orebody. However, in this article, we are concerned with the major subdivisions only, and it will suffice to note the low copper content of the upper sandstone, shown in Fig. 2. At present, two types of room-and-pillar openings are created in the orebody. In one type, called parting

Jan 1, 1964

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By W. A. Tiller, S. O’Hara

Grain refinement in stirred melts has previously been shown to arise from dendrite segmentation. The present work discusses experiments capable of distinguishing between remelting and mechanical effects which result from fluid motion. Nucleation of still un-dercooled Sn-1 pct Pb melts with a single-crystal seed shows that the grain size of the resulting ingots decreases as the undercooling at nucleation increases up to about 1Z0C, then increases again for larger undercoolings. Pure melts exhibit little refinement as a result of nucleation at any undercooling up to 12°C. The presence of fluid motion gives rise to grain multiplication in pure melts, but the magnitude of this effect is partly obscured by solid-state pain growth. The results indicate that two grain-multiplication pvocesses can operate, one which involves dendrite remelt ing, and another associated with fluid motion. Small ingot experiments indicated that an equiaxed transition can be caused by fluid motion. THE presence of forced convection during recales-cence of undercooled Sn-1.3 pct Pb melts has been shown to give rise to extensive grain refinement during solidification of small ingots of this alloy.&apos;&apos;2 In Ref. 2, this refining was shown to result entirely from dendrite fragmentation and not from any nucleation mechanism. The purpose of the present work is to establish what processes lead to dendrite segmentation. Experiments were therefore carried out to determine the resulting structure of both pure tin and Sn-1 pct Pb melts, nucleated at various undercoolings by single-crystal seeds in the absence of forced or natural convection. By comparing the information obtained from these experiments with the results of Refs. 1 and 2, the effects of fluid motion on the ingot structure, and the details of the segmentation mechanisms, should become clear. The results of these experiments should also be helpful in understanding the solidification structures of larger ingots since natural convection, which is known to play an important role in determining ingot structure13 differs only in degree from the fluid-motion effects studied here. I) EXPERIMENTAL PROCEDURE The apparatus shown in Fig. 1 was constructed to permit controlled nucleation of stirred or unstirred supercooled melts using a seed oriented in the tin dendrite growth direction. Because the melts, in all cases, were capable of larger supercoolings than the one used in each experiment, the structure observed always resulted from a single nucleation event at the surface. The sequential procedure was as follows: Tin was melted under purified hydrogen and the oxide removed at a temperature of 450°C . Electromagnetic stirring was then used to clear the surface completely and during this time the guide tube was lowered underneath the melt surface. A pointed Czochralski-like crystal was then propagated from a specially prepared tin dendrite seed4 inside the guide tube while the temperature of the bulk melt was held just above the melting point, ensuring a perfectly clean seed which was epitaxial with the original dendrite. The dendrite and epitaxial seed, still in the guide tube, were withdrawn from the melt which, in turn, was undercooled to 2C° below the temperature at which the nucleation experiment was to be performed. The melt was held there for several minutes, both in stirred and in still-melt experiments. The temperature was next raised to the required value and the melt nucleated by the carrot seed inside the guide tube, the heater power being shut off just after nucleation. In experiments where quenching after nucleation was required, a high-density graphite crucible was used, but otherwise the procedure was as described above. The temperature gradient in the melt before nucleation was kept below 1C° per cm by carrying the experiment out just below the center of the heater shown in Fig. 1.

Jan 1, 1968

By Robin O. Williams

AN investigation has been made of the Ni-Cr system for the purpose of elucidating certain points, namely the nature of aging in both terminal solid solutions and the nature of the phase diagram. Information pertaining to solubilities and precipitation has been obtained. Experimentation Five alloys, Table I, were arc melted in a cold copper crucible using electrolytic chromium and car-bony1 nickel, both dry hydrogen treated. These 100 g buttons were homogenized 24 hr at 1300°C in dry hydrogen and air cooled. Powders were prepared by filing or pulverizing and subsequent heat treatment was done in vacuum or helium using titanium chips as a getter. Powder of —80 mesh was filed from the 60 pct Ni alloy quenched from 1000°C and was sealed in silica under vacuum using a 250 °C outgassing. After aging as indicated in Table I1 the lattice parameters were measured on the quenched samples using the standard cos" 6 extrapolation. These parameters are considered accurate to roughly 0.0001A. In all cases chromium lines of 2.8812 ± 0.0005Å at 30°C were found. Drastic quenching from sufficiently high temperatures produced very sharp body-centered-cubic lines in the first four alloys without indications of transformations. Temperatures to 1250°C were used. Solid samples less than 1/16 in. thick were quenched in water without transformation and the powders could be adequately quenched in small helium filled thin wall silica tubing using a water quench. For those powder samples which were quenched from the two phase field the relative intensity of the body-centered-cubic lines and the face-centered-cubic lines were estimated and extrapolated to give the indicated solubility data in Fig. 1. The data for the two higher alloys were somewhat limited, the plotted points being the lowest temperature where no nickel phase was found. Neither filing, abrading, pulverizing, nor cooling to —190°C produced any new diffraction lines for solid samples quenched from the single phase region, nor did the character of the body-centered-cubic lines change Single phase body-centered-cubic powders likewise did not change on cooling to —190°C. Also, samples which had some precipitation due to inadequate quenching showed no additional changes under these conditions. The first change apparent by X-ray diffraction form samples quenched almost fast enough to prevent precipitation was the diffuseness of the body-centered-cubic lines, particularly on the low angle side, For slower cooling rates the diffuse face-centered-cubic lines appeared. Work on the large grained castings showed profuse streaking through some of the Laue spots while oscillating patterns showed broad body-centered-cubic and face-cen-tered-cubic lines as well as some new lines. For the 23.6 pct Ni alloy the new lines corresponded to 2.16, 1.96, and 1.86A and were more similar in character to the face-centered-cubic lines than the body-centered-cubic lines. Samples which were air cooled gave only face-centered-cubic and body-centered-cubic lines which were still broad. One pattern indicated that face-centered-cubic (111) plane was parallel to a body-centered-cubic (110) plane. For those samples which were examined by light microscopy there were details which were not resolved. However, varied and beautiful structures were obtained. Fig. 2 is of an alloy quenched in a helium filled silica tube from the single phase region and shows particles associated apparently with dislocations which are arranged in low angle boundaries. Finer, general precipitation has also taken place within the grains. Figs. 3 to 5 show the variety of structures produced in these alloys on continuous cooling. It appears that there are four distinct modes of precipitation as evidenced by these, figures. Annealing these structures at higher tem-peratures in the two phase field gives structures as shown in Fig. 6, which shows nickel plates in the chromium matrix which reprecipitated nickel on a much finer scale of the final quench. Lower annealing temperatures and shorter times naturally give finer plates of the nickel-rich phase. Samples of the first four alloys were annealed for appreciable times between 900º and 1250°C and gave structures like Fig. 6. The relative amounts of the two phases were measured and extrapolated to give solubility data as indicated in Fig. 1. The point at 1250°C was deduced from data of Oxx.1 These and most of the other samples were checked for ferromagnetism but none was apparent. In fact, it appeared that the magnetic susceptibilities were not more than three times that for paramagnetic chromium. Discussion In Fig. 1 it is seen that the solubility of nickel in chromium can be represented by a slightly curved line on the usual log X vs 1/T plot, These data are believed to be accurate to roughly 5 to 10º. There is only fair agreement with the data of Taylor and

Jan 1, 1958

By C. L. Prokop

A laboratory investigation has been made of the effects of mud hydraulics upon the formation and erosion of mud filter cakes. The tests were conducted to simulate drilling conditions as nearly as possible. The formation of mud filter cake in a drilling well does not proceed at a uniform and unbroken rate. Instead, the rate of cake accumulation depends upon whether or not the mud is being circulated. If the mud column is quiescent, filter cake formation is a smooth function of the filtration characteristics of the system. If the mud is being circulated filter cake formation depends not only upon the filtration characteristics of the mud but also upon the erosive action of the flowing mud column Filter cakes formed during continuous mud circulation were observed to reach an equilibrium thickness after several hours&apos; circulation. Mud circulation was maintained at a constant volumetric rate throughout each experiment. The fluid velocity at equilibrium cake thickness was dependent upon the thickness of the filter cake. Muds having exceptionally high water loss deposited thick filter cakes in spite of very high eroding velocities. The muds having good filtration characteristics deposited thin filter cakes at equilibrium circulating velocities well within tile range of those in a drilling well. It was observed that filter cakes deposited during stagnant filtration were quite difficult to erode by mud circulation. The - rate of crosion computed from the rate of filtrate accumulation after equilibrium cake thickness had been reached was in reasonable agreement with the rate of erosion obtained by direct observation. Continuous mud circulation usually caused the permeability of the filter cake to decrease with time. INTRODUCTION Many of the difficulties encountered during tile drilling of a well have been attributed to the loss of water from the mud and the attendant deposition of solids upon the walls of the hole. Past experience has shown that a reduction of the filtration rate of the drilling fluid eliminates or greatly reduces these difficulties. Definite filtration requirements, however, are hard to establish for a given set of conditions. This is due. in part, to the fact that the usual filtration test performed upon mud doe? not simulate well conditions as closely as desirable. The filtration characteristics of a mud are customarily determined by means of the standard low-pressure API wall-building tester.&apos; In this instrument a filter cake is deposited upon a horizontal bed under a pressure differential of 100 psi. The rnud is quiescent during the filtration period. In actual practice. mud filtration occurs within a well under quite different conditions. One of the major differences is that mud flows upward across the filter bed as the filter cake forms. This undoubtedly produces a change in the filter cake which cannot be reflected in the results of the API test. The laboratory work described in this paper had as its primary objective a better understanding of the influence of mud circulation upon the thickness and ,characteristics of the filter cakes deposited under conditions similar to those existing in a drilling well. ANALYSIS OF PROBLEM Once a permeable formation is penetrated by the bit, filtrate from the mud flows into the formation. &apos;he mud solids plaster against the walls of the hole, forming a filter cake. If the mud column is stagnant, that is, if it is not being circulated. the filter cake will increase in thickness until the hole is filled. Prior to the time that the hole is filled, the thickness of filter cake existing at any given time will be a function of the filtration characteristics of the mud, the temperature, and the pressure differential. The effects of these variables have been investigated in the past for both flat bed filtration2&apos;3 and for radial filtration.&apos; When the mud is circulated in a hole in which a filter cake i. being deposited. some of the solids that would ordinarily deposit in the filter cake will be carried away by the eroding action of the mud. This will limit. filter cake thickness. Some work has been done to determine the effect of flow upon the filtration rate in a circulating mud system&apos; but little work has been done upon the factors which determine the filter cake thickness existing in a circulating system. On first sight it would appear that the major factors controlling filter cake formation in a circulating system should be: 1. The rate of deposition of solids from the mud. 2. The erosive force that the flowing mud exerts upon the filter cake. &apos;A. The erodabilitv of the filter cake. 4. Any change in filter cake characteristics attributable to the scouring action of the mud. The rate at which solids are deposited from the mud will be controlled to a large degree by the filtration characteristics of the mud, the pressure differential. the temperature under

Jan 1, 1952

By Y. C. Liu

The orientation relationship between the dejormation and recrystallization textztres of binary Cu-P alloys of high phosphorus content was observed to he a ± 14-deg (110) rotation. According to the ori-ented-gvowth hypothesis, the same relationship should exist between a successfully flowing pain and the strained single-crystal matrix of alloys of corresponding composition. The orientations of thirty successfully growing grains were obtained in a Cu-1.0 at. pct P alloy. Both a conventional analysis and the more detailed analysis advanced in the present study demonstrate that the observed orientation relationship is not comparahle to that predicted by the oriented growth hypothesis. IT has been shown experimentally that the formation of recrystallization textures in metals may be explained on the basis of the oriented-growth hypothesis. This conclusion is based primarily on the results of cooperative experiments carried out by various investigators in aluminum. Beck and HU&apos; suggested that the orientation relationship between the recrystallization and deformation textures of aluminum is a 38-deg(111) rotation. A similar relationship, i.e., a 40-deg(111) rotation, was observed between the primary and secondary recrys-tallization textures.&apos; Since the secondary grains result from a process of selective growth, this naturally implies that the same mechanism is also responsible for the formation of the primary re-crystallization texture from the deformed matrix. Further evidence was provided by the experiments of Liebmann, Liicke, and Massing3 and Yoshida, Liebmann, and Lucke.4 They observed that grains which could successfully grow into strained aluminum single crystals invariably exhibited the same orientation relationships with their matrix. Thus, regardless of other opinions,5&apos;9 these results offered good evidence in favor of the oriented-growth hypothesis. In order to examine broader applications of this oriented-growth hypothesis, experiments should be carried out in metals other than aluminum. In a recent investigation on the recrystallization textures of binary copper alloys with phosphorus, arsenic, and antimony,7 it was found that the predominant recrystallization components were related to the deformation textures by a (110) rotation. The (110) rotational relationship is different from the (111) relationship generally proposed between the recrystallization and deformation components of other binary copper alloys. 1,8,9 Applying the observations made for aluminum, the oriented-growth hypothesis predicts that the orientation relationship of grains successfully growing into the strained single crystals of either one of these copper alloys should correspond to that observed in the textural study. Verification of this prediction would provide a critical test of general applicability of the oriented-growth hypothesis to the formation of recrystallization textures in fcc metals other than aluminum. The Cu-1.0 at. pct P alloy was selected in the

Jan 1, 1964

By A. E. Powers

YEARS of experience and research have shown that molybdenum, tungsten, and vanadium are among the most useful and effective elements in augmenting the high-temperature strength of heat-treatable, ferritic steels. Grün, for example, in conducting an early survey of the strengthening effects of various elements in annealed, low-carbon steel at 750° and 930°F (400° and 500°C), found molybdenum and vanadium to be the most effective.&apos; Holtmann comprehensively studied the strengthening effects of molybdenum and vanadium in quenched and tempered steels at 930°F as a function of microstructure and carbon content.&apos; He found creep strength to be related to the saturation of the austenite at the austenitizing temperature, such that strength is increased by alloying until the y loop is reached—the terminus of complete austenitization. Beyond this degree of alloying, the inability to heat treat will result in lower strength, at least for low and moderate creep temperatures. Tungsten, owing to higher cost than molybdenum, has been little used in ferritic high-temperature steels. As a result, very few investigations have been made of its high-temperature strengthening ability, and reliable data on its effectiveness are not available. Grün rated tungsten far less effective than molybdenum at 930°F (500°C) on a weight-percentage basis.&apos; However, Tammann has found that tungsten is as effective as molybdenum in raising the recrystallization temperature of iron. For this reason Smith, in a review of the subject, has advocated a re-examination of the influence of tungsten on the high-temperature strength of steel.&apos; In any study of the effects of alloying additions on high-temperature properties, recognition must be made of the many variables involved, some of which can be controlled but have been ignored in innumerable investigations of the past, and some of which are difficult or even impossible to control. One cannot, for example, assign a definite strengthening index to any one alloying element, for this will be dependent upon the microstructure (heat treatment and mechanical treatment), testing con- ditions (temperature, time, and stress), and the complete composition of the steel (accompanying alloying elements, impurities, etc.). One ever-appear ing variable, hardness or tensile strength at room temperature, may be eliminated by heat treating all of the alloys to a single hardness level. An attempt may be made to control the variable of primary quenched structure by oil or water quenching the test specimen. The control of such variables may not be possible in cases of widely varying compositions, but at least such deviations should be recognized. Material and Procedure The alloys, made as 30-lb ingots in an induction furnace, all had the same base composition of about 0.18 pct C, 0.85 pct Mn, and 0.48 pct Si. They were grouped as follows: Mo Group—Containing up to 5.2 pct Mo. W Group-Containing up to 6.0 pct W. V Group—Containing up to 3.3 pct V. Mo-V Group—Containing up to 2.7 pct Mo and up to 1.4 pct V. Mo-W Group—Containing up to 2.5 pct Mo and up to 2.5 pct W. The steels, listed in Table I, were forged to ¾ in. sq bars and the material for the high-temperature, rupture-test specimens was further swaged to %-in. round bars.

Jan 1, 1957

By R. W. Guard, M. E. Fine

By treating the dislocation like a surface and ap-plying the usual thermodynamic treatment to the adsorption process a Gibbs adsorption equation for dislocations was derived. For extended dislocations in binary solutions the adsorbed concentration on the fault, X2a, may be computed from (jo/da2b) where a2b is the activity of the solute in the bulk material and s is the stacking-fault energy. Using the data of Howie and Swann for s the adsorption concentration goes through a maximum at 2 at. pct Al in Ag-Al, 10 at. pct Zn in Cu-Zn, and 8 at. pct A1 in Cu-Al. The pinning stress calculated from this concentration difference goes Ihrough a maximum at the same concentration us the peak in X2 a. The computed pinning stress thus does not vary with composition in the manner predicted by Suzuki, as was also pointed out by Hendrickson. The results are compared with the stress increment which can be attributed to Suzuki locking in Cu-Zn and Cu-Al stress-strain curves. They both agree in magnitude and in the location of the maximum. The predicted and observed maximum values for the Cu-Zn system (where activity data are available) are 700 g per sq mm (predicted) and 1000 g per sq mm (measured, laking into account the orientation factor of 2.2 to convert poly-crystalline to single-crystal data). CERTAIN simple internal surfaces may be regarded as dislocation grids. This fact suggested that it might be profitable to consider certain phenomena related to segregation of solute atoms at dislocations from the point of view of the thermodynamics of surfaces and surface adsorption. A general treatment of this type is given and then the results are applied to Suzuki segregation and pinning. Confirmation of the results is obtained from comparison of stress-strain behavior for copper and copper-base alloys. Two kinds of dislocations need be treated: perfect and extended dislocations. In either case the line tension of a dislocation, ?. the work which must be done to increase the length of dislocation by a unit length, is analogous to the surface tension. For an undissociated dislocation ? is the self-energy of a unit length of dislocation; for an extended dislocation where is the self-energy per unit length of a pair of partials far enough apart so that there is no interaction energy, is the interaction energy per unit length, is the stacking fault energy per unit area, and w is the equilibrium separation of the paired partials. In the absence of an applied stress the force pushing the dislocation partials apart in a close-packed structure is Gb2/12p where G is the shear modulus, b is the Burgers&apos; vector of the complete dislocation, and is the separation of the partials. At the equilibrium separation, w this force equals s. Thus

Jan 1, 1965

By W. B. Nelligam, J. Tittman

Refinements in radiation logging techniques during recent years have involved increasing usage of scintillation ditectors. These detectors produce voltage pulses whose heights are related to the energies of the gamma rays which initiate them. Analysis of the gamma-ray spectrum, as indicated by the pulse heights, yields information about the chemical elements composing the formations surveyed. Refined scintillation counter techniques can furnish chemical information concerning earth formations in situ, from a study of the gamma-ray spectra emitted by the formation either naturally or as a result of neutron bombardment."&apos; Accompanying the rising interest in gamma-ray scintillation spectroscopy, there has been increased activity in the development of accelerator-type neutron sources (in contrast to encapsulated chemical-mixture sources). Such neutron generators are attractive for several reasons: (1) they greatly reduce radiation hazards to personnel; (2) there is a great reduction in contamination danger if they are lost in the hole; (3) they can produce larger neutron intensities than can conveniently available encapsulated sources; and (4) they are capable of being pulsed, thus permitting new techniques in logging. In the past, both accelerator and encapsulated neutron sources have been used by others in conjunction with scintillation-detector pulse-height analysis. The results have not been too encouraging, due to the interference among different gamma-ray spectral lines and to the fact that the gamma-ray peaks were not too clearly distinguishable above the large and ill-defined background "noise".&apos;.&apos; This paper is a status report on laboratory studies of a technique using a borehole accelerator as a neutron source, which gives an improved scintillation spectrum, thus permitting more accurate chemical analyses of the formations penetrated. The Schlumberger-accelerator neutron source&apos; is presented; the origins of inelastic and of thermal-neutron, capture gamma rays are dis- cussed, and results are given for some laboratory measurements performed in borehole geometry. THE NEUTRON GENERATOR-TUBE ACCELERATOR In the attempt to develop an accelerator neutron source which would have the desirable properties outlined in the "Introduction" and which would operate satisfactorily under borehole logging conditions, a small-diameter, cylindrical, neutron generator tube has been developed. This tube utilizes the principle of accelerating deuterons (heavy hydrogen nuclei) by a high voltage so that they bombard a tritium (heavy, heavy hydrogen) target. The resulting reactions produce large numbers of neutrons of 14 Mev energy. Furthermore, the tube is permanently sealed and, thus, the use of pumping techniques in the sonde is avoided. The tube consists of a pressure control, an ion source in which the deuterons are stripped of their electrons, an accelerating gap down which the deuterons are sped by the high voltage, a secondary electron suppressor and a tritium-loaded target. Obviously, the tube requires auxiliary circuitry in a sonde for the control of the ion source, tube pressure, high voltage and other operating variables. Neutron yields, both continuous and pulsed, have been produced under simulated field conditions in the range between 1 and 10 times those conventionally used in neutron logging applications. For the experiments discussed in this paper, neutron-pulse repetition rates in the range between 500 and 5,000 pulses/sec are adequate. Furthermore, by making suitable adjustments in operating conditions, one can vary the pulse width from a minimum of several microseconds up to dc. As will be seen later, the present application to well logging does not require that one have available pulses of neutrons which are appreciably shorter than the time it takes for fast neutrons to slow down to thermal energy in water. As a consequence, much of our interest has been directed towards the operating characteristics of the tube with pulses longer than about 10 microseconds in duration. Our experience to date shows that tubes can be operated in this manner with reasonably constant, average neutron outputs.

By E. W. Johnson, M. L. Hill

Equilibrium concentrations of hydrogen in iron were measured at H2 pressures up to 136 atm and temperatures down to 145°C. Residual hydrogen was prominent near 600°C in air-melted but not in vacuum-melted iron. The diffusible hydrogen solubility is abnormally high below 390°C, confirming the hypothesis of hydrogen trapping.&apos; It appears that the traps for hydrogen in iron form suddenly on cooling. The estimated H2 pressure in equilibrium with 5 ppm hydrogen in steel at room temperature is less than 1000 atm. It was shown previously1 that the diffusivity of hydrogen in a-Fe below 200°C is anomalously low, a behavior attributed to the presence in the metal structure of hydrogen "traps." The energy of the trapped hydrogen was computed as 4.8 kcal Per g-atom below that of the interstitially dissolved hydrogen. The strongest confirmation of the trap hypothesis should be obtainable from measurements of the hydrogen solubility at low temperatures. such measurements have been performed and are reported in this paper. The "residual hydrogen" effect1&apos;&apos; must be carefully controlled if valid measurements of the solubility are to be obtained, and such an effort was made in the present work. Previous data for the solubility of hydrogen in iron have been summarized by Geller and Sun.3 Their equation for the most probable solubility at 1 atm in a-Fe above 400°C is

Jan 1, 1962

By W. G. Pfann

In zone-melting, a small molten zone or zones traverse a long charge of alloy or impure metal. Consequences of this manner of freezing are examined with impurerespect to solute distribution in the ingot, with particular reference to purification and to prevention of segregation. Results are expressed in terms of the number, size, and direction of travel of the zones, the initial intermsofsolute distribution, and the distribution coefficient. IF a charge of binary solid-solution alloy is melted and then frozen slowly from one end, as for example in the Bridgman method of making single crystals,&apos; coring usually occurs, with a resulting end-to-end variation in concentration. Such coring, or normal segregation, is undesirable where uniformity is an object. On the other hand, for certain systems, it can be utilized to refine a material by concentrating impurities at one end of the ingot.&apos;. &apos; In the present paper a different manner of freezing will be examined with respect to the distribution of solute in the ingot. A number of procedures will be indicated which have in common the traversal of a relatively long charge of solid alloy by a small molten zone. Such methods will be denoted by the general term zone-,melting, while the process described in the preceding paragraph will be called normal freezing. It will be shown that, in contrast to normal freezing, zone-melting affords wide latitude in possible distributions of solute. Segregation can either be almost entirely eliminated or it can be enhanced so as to provide a high degree of sttparation of solute and solvent. A number of simplifying assumptions will be invoked which, while not entirely realizable in practice, nevertheless provide a suitable point of departure for more refined treatments. Moreover, our own experience with zone-melting has shown that, for certain systems at least, the analysis holds quite well. The present paper will be confined to a discussion of principles and a general description of procedures. Comparison with experiment is planned for later publication. Normal Freezing Before considering zone-melting, segregation during normal freezing will be reviewed briefly. If a cylinder of molten binary alloy is made to freeze from one end as in Fig. 1, there usually will be a segregating action which will concentrate the solute in one or the other end of the ingot. If the constitutional diagram for the system is like that of Fig. 2, then the distribution coefficient k, defined as the ratio of the concentration in the solid to that in the liquid at equilibrium, will be less than one and the solute will be concentrated in the last regions to freeze. If the solute raises the freezing point, then k will be greater than one and the solute will be concentrated in the first regions to freeze. The concentration in the solid as a function of g, the fraction which has solidified, can be expressed by the relation: C = kC0 (1-g)k-1 [I] where C, is the initial solute concentration in the melt. Eq 1 is based on the following assumptions: 1—Diffusion in the solid is negligible. 2—Diffusion in the liquid is complete (i.e., concentration in the liquid is uniform). 3—k is constant. Concentration curves representing eq 1 for k&apos;s from 0.01 to 5.0 are plotted in Fig. 3. This equation, in one form or another, has been treated by Gulliver,³ Scheuer,4 Hayes and Chipman5 for alloys and by McFee2 for NaCl crystals. It is derived in Appendix I. It should be pointed out that the k which is calculated from the phase diagram will be valid only in the ideal case for which the stated assumptions are correct. In all actual cases, the effective k will be larger than this value for solutes which lower the melting point, smaller for solutes which raise the melting point, and will probably vary during the beginning of the freezing process. For simplification it will be assumed that the ideal k is valid. Zone-Leveling Processes The processes of this part are designed to produce a uniform, or level, distribution of solute in the ingot. Single Pass: Consider a rod or charge of alloy whose cross-section is constant and whose composition, C2, is constant, although permissibly varying on a microscopic scale." Such a charge might be a rapidly frozen casting or a mixture of crushed or powdered constituents. Cause a molten zone of

Jan 1, 1953

By B. J. Kochanowsky

The idea of a portable crusher is not new. Many such crushers are available but they are small and designed for construction work. For many years the author has suggested, both in this country and in Europe, the building of larger portable crushers intended expressly for use in quarries or open pits. Although not applicable under all conditions, there are mining operations where a mobile crusher arrangement could be more profitable than the facilities now used. The primary use of a portable crusher, i.e., a crusher mounted on crawlers or tires, in the rock and mining industries is to reduce costs by permitting the substitution of conveyor belt haulage for truck or track haulage. The usual sequence of operations in surface mining is drilling, blasting, loading, haulage, and crushing. Haulage is normally accomplished by truck or track-mounted cars, the latter method being used for the longer distances. However, by using a portable crusher in the pit, the sequence of operations would be changed so that the crushing stage would occur before haulage (Fig. 1). Such a sequence would permit the use of conveyors to replace the more expensive truck or track haulage methods. Since most quarry and open pit operations normally require a crushing stage, the only additional costs incurred will be due to the investment required to purchase or construct a mobile arrangement for a crusher. But this factor has to be weighed against the advantages to be gained by conveyor haulage. As shown in Fig. 2, transportation of material by belt conveyor over short distances is less expensive than by truck. The inclination of the belt has no effect on belt speed; consequently, the hourly tonnage moved remains the same. Conversely, the output rate of trucks as expressed in tons or ton-miles per shift decreases proportionally to the haulage speed, which is considerably slowed by the steepness of the road (Fig. 3, left). Although maximum possible grades and maximum economic grades of haulage are greater for a belt than for a truck (over the same total lift), the longer haulage distances favor the use of trucks. Although power consumption for hauling on a grade increases for both conveyances, the rate of power consumption increases faster for trucks than for conveyor belts (Fig. 3, right). Since the output rate and related fixed costs are affected by the travel speed, total haulage costs with trucks would increase with the grade more rapidly than the similar costs of conveyor belts (Fig. 4). Travel distance, road grade, speed, size and number of pieces of equipment, efficiency of operation, and many other factors affect such haulage costs. In general terms it can be said that the shorter the distance, the steeper the grade, and the greater the output, the more advantageous the belt becomes in comparison to truck or track haulage. In addition to potential cost savings in haulage procedures, a portable crusher would allow better utilization and performance of shovels. Loading operations would not be interrupted as often by the necessity of waiting for cars or trucks. Unfortunately, the application of belts in open pits for haulage from bench sites is generally not practical under existing conditions because a belt fed directly by a mechanical shovel can be torn, damaged, or worn out quickly by the large rock fragments falling on it during loading. However, by using a mobile crusher this situation can be avoided. As shown in Fig. 1 (b), the shovel feeds rock into the crusher located behind it. The crushed material is initially transported by an extensible and/or movable belt, thence by a longer stationary conveyor to the plant where the material is subjected to further treatment by secondary crushing, screening, etc. The first-mentioned conveyor, needed to bridge the distance between the shovel and the stationary conveyor, is necessarily variable in length owing to the continuous movement of the shovel and the desire to keep the stationary belt at a safe distance from the bench during blasting operations. The remarkable part of mobile crusher operations is the extra-ordinarily high output per man-shift, the low maintenance and power requirements for haulage, and the increased output of the loading shovel. A cement quarry which has been using a portable crusher and conveyor since 1956 requires only three men to operate the shovel and crusher and to transport the crushed rock by belt from the quarry face to the screening plant. If truck haulage

Jan 1, 1961

By N. K. Chen, R. B. Pond

IN the study of slip band* formation, there have been many examples to show that they do not always appear as lines traversing the entire crystal, but as segments whose ends seem to vanish in their path through the crystal. This characteristic appearance of slip bands has been witnessed under the optical microscope at various magnifications&apos;-&apos; and also under the electron microscope.&apos; A typical example of this behavior seen with the optical microscope is shown in Fig. 1. However, the slip band studies were generally conducted on polished surfaces of single or poly-crystalline metals which had been previously deformed; i.e., the load was generally released so that the observation could be made. Any picture of slip bands so obtained can represent the surface phenomenon only in a static state of the strained material. The conditions prior to their formation cannot be definitely and clearly assigned. Thus, while a segmented slip band may suggest that slip is a growth process as supposed by the theory of the nucleation of slip,V he usual appearance of suddenly and fully developed slip bands around the crystal has generally been considered as a consequence of uniform shear of the entire slip plane akin to a cataclysmic process. Little clear-cut information is available with regard to the speed at which a slip band forms, its direction of motion, the geometry of its position with regard to its neighbors, and its dependence on orientation. A description is given in this paper of experimental apparatus by which the progressive formation of slip bands can be recorded while the specimen is undergoing deformation. Qualitative and quantitative data on the dynamic formation of slip bands will be presented with special interest concerning the propagation of slip bands, the spacing of slip bands, and their relations to strain hardening. Views on the formation of slip bands are discussed and a mechanism of the unit process involved in the formation of a slip band is proposed. Preparation of Specimens Single-crystal specimens of high purity aluminum (99.997 pct), 1/8 in. square in cross-section and 1% in. long in gage length, were made by the method of gradual solidification from the liquid state. Since no machining work could be introduced in preparation of crystals of such small size, a special mold was designed for casting them to final shape. The mold consisted of two, separate, high purity graphite blocks. Generally, 20 molds were packed together in one container so that 20 specimens could be obtained by one casting operation. This was desirable since it was possible by this method to obtain groups of crystals with similar orientations. The as-cast crystals were carefully clipped from the gate, etched, and homogenized for 24 hr at 600°C. They were then very gently polished using a 4/0 paper, re-etched, and finally electrolytically polished after the method previously described by Chen and Mathewson.6 The crystallographic orientations were determined using a back-reflection, Laue method. Tensile Testing and Photographic Method The tensile testing equipment for these tests was composed of a specially designed microtensile machine, microload cell and microclip gage with necessary appurtenances. The members of the microtensile machine consisted of three parts, as shown in Fig. 2. The chassis is equipped with an oil cylinder, A, and piston, the piston being part of the movable cross-head, B. Pressure in the oil cylinder is controlled and regulated by an external pneumatic-hydraulic cell, C, which is connected to the cylinder by a Vs in. high pressure copper tube. This cell is half filled with hydraulic oil and has a needle valve, D, on the oil exit side as well as a needle valve, E, on the gas inlet side. A quick-acting valve, F, as well as a pressure gage is provided for the gas side. The oil exits into the load piston on the microtensile machine. By connecting a tank of inert gas to the gas inlet, regulated pressures were provided over the oil so that the oil would leave the cell at a rate determined by the setting of the exit needle valve, the gas pressure, and the pressure of the oil in the load piston of the microtensile machine. With this pneumatic-hydraulic appurtenance it was possible to

Jan 1, 1953

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1&apos;2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O&apos;s. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO&apos;s are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.&apos; At 900°C noticeable decomposition takes

Jan 1, 1964

By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th&apos;vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1&apos;2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS&apos; and on GaAs doped with oxygen,5&apos;" manganese,&apos; and copper.&apos; The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968

By Benny J. Nelson

AS a part of the fundamental research program of Aluminum Research Laboratories, some data were obtained on the ternary system Mg-Al-Mn. As very little information on the magnesium corner of this diagram has heretofore been published, it seems desirable to make available the values found for the liquidus and solidus surfaces of this system. Procedure The settling procedure was used for the determination of the liquidus compositions. Metallo-graphic examination of quenched samples, and stress-rupture upon incipient melting, were used for the solidus determinations. The settling procedure has been described in a previous paper.&apos; Briefly, this method involved saturating the alloy with manganese at a temperature substantially above that at which the sohbility was to be determined, then cooling the melt to the latter temperature, and holding it at that temperature for a substantial period of time. Samples for analysis .were carefully ladled from the upper portion of the melt at hourly intervals during the holding period. After the ladling of each sample, the melt was stirred to redistribute some of the manganese that had already settled, because it appeared that when the latter particles of manganese again settled, they aided in carrying down more of the manganese and thus hastened the attainment of equilibrium. The melts were prepared and held in a No. 8 Tercod crucible holding approximately 4 lb of metal. The manganese was added either in the form of a prealloyed ingot (Dow M) containing about 1.5 pct Mn or by the use of a flux (Dow 250) containing manganese chloride. In calculating the flux additions, it was assumed that the manganese introduced would be equal to 22 pct of the total weight of the flux. Temperatures were measured with an iron-constantan thermocouple enclosed in a seamless steel tube, the lower end of which was welded shut. This protection tube also served as a stirring rod. The samples ladled from the upper portions of the melts at the various intervals were analyzed for aluminum, manganese, and iron. When making the alloys which were to be used for the determination of the solidus, 2½ in. diam tilt mold ingots were cast, scalped to 2.0 in. in diam, and extruded into ? in. diam wire. The principal impurities in the melts for this investigation were iron and silicon; their total not exceeding 0.03 pct. Portions of the wire, approximately 2 in. in length, were enclosed in stainless steel capsules for protection from the atmosphere. Bundles of these capsules, with a dummy capsule containing an iron-constantan thermocouple, were heated inside a large steel block (acting as a heat reservoir) in a closed circulating-air type electric furnace. At ap- propriate times, the capsules were removed and quenched in water. The wires were examined metallographically to determine the temperature of initial melting. Short times at temperature were used at the beginning for wire specimens of all alloys to obtain quickly the approximate temperatures at which melting could be first observed. When approximate solidus temperatures had thus been determined, equilibrium heating was attempted. This equilibrium heating consisted of an 8 or 16 hr period at a temperature, about 50 °F below the lowest temperature at which melting occurred when short heating cycles were used, followed by further heating for 1 hr periods at consecutive 10" higher temperatures. The theory for the method of stress-rupture at incipient melting has been well covereda and its limitations are recognized. Thus, if the interfacial tensions are such that the first minute quantity of liquid is "bunched up" at the grain boundary junctions instead of spreading out along the grain boundaries,³ temperatures higher than the solidus are required before melting will be manifested by rupture of the specimen. This point will be elaborated later. Specimens of the wires with a reduced section (approximately 1/16 in. diam) were suspended vertically in a tubular furnace. The setup used is shown in Fig. 1. The clamp holding the specimen was made from alumel thermocouple wire and the thermocouple was thus completed across the specimen by attaching a chrome1 wire to its lower end. Temperatures were read from a Speedomax recorder used in conjunction with a calibrated thermocouple. The small weight attached to the specimen and a vibrator attached to the furnace tube, to aid in distributing the molten constituent along the grain boundaries, were used to bring about rupture at a temperature closely approximating the solidus. The specimens were heated at a rate of about 5°C per min. The rupture of the specimens was indicated both by sound and by the action of the recorder. An argon atmosphere containing a small amount of SO² was used for protection of the specimen. The assembly was taken out of the furnace immediately following rupture and the specimen removed. Some of the broken specimens were examined metallographically and will be referred to later. Results and Discussion Fig. 2 shows a set of typical time-composition curves for liquid samples of the Mg-Al-Mn alloys used for the settling tests. The data as presented

Jan 1, 1952

By L. D. Hall, D. R. Mash

The paper presents the results of experiments on the anelastic. behavior of gold, as manifested by grain boundary relaxation. Two grain boundary internal friction peaks are found for 99.9998 pct Au. It is found that the peaks are associated with primary and secondary recrystallization. However, the existence of two discrete peaks cannot be explained on the basis of grain size and shape alone. It is suggested that grain boundary stability, as determined by orientation, plays a role in the observed effects. EVIDENCE for the viscous behavior of grain boundaries in metals has been presented in recent years by several investigators, based upon studies of various anelastic effects, especially internal friction. KG1 has contributed greatly to this field, having put forward a coherent body of evidence for stress relaxation by the viscous intercrystalline flow mechanism. In this connection, he has made extensive use of pure aluminum (99.991 pct) as the test material, although he has also studied other metals and alloys, including pure iron (Puron).² Rotherham, Smith, and Greenough³ have studied the internal friction of pure tin, interpreting their results in a manner similar to that of KG. In view of the importance of such studies in shedding light upon the fundamental structure and behavior of the grain boundaries in pure metals, it appears that the use of a very pure test material which is inert to its environment should provide useful information on anelastic properties and the source of such behavior in pure metals. The present work was carried out on spectrograph-ically pure, 99.9998 pct Au, free of all impurities except for a trace of silver, estimated to be present to the extent of about 0.0002 pct. The term "pure gold" will hereafter refer to this very pure material. Gold of commercial purity, 99.98 pct, was also studied to observe the effects of small amounts of impurities. A pure gold "single crystal" specimen was also tested for comparison. The variation of the internal friction and rigidity modulus as a function of temperature was determined by means of a torsion pendulum apparatus employing extremely low stress amplitudes and a frequency of vibration of the order of 1 cycle per sec. A 12 in. length of 0.031 in. (20 gage) gold wire formed the suspension element. The apparatus was similar to that described by Ke.l The test procedure and the basic requirements to be met for obtaining useful experimental data by this method have been given elsewhere.1,2 It should be made clear that in all of the experiments to be described, the internal friction and rigidity were independent of the amplitude of torsional vibration. The semilog plot of amplitude of vibration vs ordinal number of vibration was a straight line. This was carefully verified for each internal friction measurement. The linear variation shows that the internal friction was independent of stress; i.e., that the specimens were not being cold-worked during testing. The reproducibility of the internal friction curves, which were obtained by cyclic heating and cooling, indicates that the gold was unaffected by its environment during the tests. The measure of internal friction adopted in the present study is the conventional "logarithmic decrement," defined as follows: log. dec. = l/n In A0/An [I] where n is the number of cycles or vibrations; A,, the initial amplitude of vibration; and An, the amplitude after the nth cycle. When the logarithmic decrement is small, the shear modulus, G, of the wire is proportional to the square of the frequency of vibration provided the length and radius of the wire are kept constant. A plot of frequency squared vs temperature gives the following ratio:&apos; This expresses the fraction of the stress which has not been relaxed at a given temperature. Gr and Gv are the relaxed and unrelaxed moduli, respectively. The frequency of vibration in the polycrys-talline specimen is fp, and the frequency of vibration of a single crystal is f8. This latter quantity is obtained simply by extrapolating the linear, low temperature portion of the curve of frequency squared vs temperature for the polycrystalline specimens. The theory of viscous grain boundary stress relaxation as demonstrated by the anelastic behavior of metals has been discussed in detail by Zener4 and need not be reproduced here. Experimental Results Initial measurements of the internal friction of pure gold were carried out on specimens which had been drawn with no intermediate annealing, resulting in a material which had undergone approximately 99 pct reduction of area in final processing. Annealing was then carried out at successively higher temperatures starting at 400°F for 1 hr and proceeding in this manner to as high as 1600°F in 100°F intervals. After each annealing treatment an internal friction and rigidity vs temperature curve was obtained over the range from room temperature to the particular annealing temperature. The resulting internal friction curves did not exhibit well defined maxima (peaks), but rather several fairly flat

Jan 1, 1954

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.&apos; Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By H. E. Cline

Calculations of the formation and growth of faults caused by a variation in lumellar widths were made for a two-dimensioml three-plate problem. The angle between the a-ß boundary and the growth direction was allowed to vary and the time evolution was studied using a quasisteady state approach. At spacings smaller than a critical spacing given by X V = AO variations in the larrlellar widths grow in time to produce faults that coarsen the structure, while at spac-ings larger than this critical spacing, variations in the lamellar widths decay in time. If small plates are introduced into the structure they may grow only at large spacings to refine the structure. The time evolution and shape of faults were calculated for the three plate-problem and then the three dimensional problem and rod-like eutectic were qualitatively discussed. UNDERSTANDING of the mechanism by which the spacing of directionally solidified eutectics is determined may allow one to control their structure better. Steady state solutions for the growth of lamellar structures have been found for a range of lamellar spacings A and growth velocities V. To obtain a unique solution for the isothermal growth of pearlite, Zener1 assumed that growth occurs at a maximum velocity, while Tiller2 assumed that a eutectic alloy, grown under an imposed velocity, will choose a spacing corresponding to minimum undercooling. These assumptions are equivalent and have been referred to as "extremum growth". The extremum condition predicts the observed relation between velocity and spacing as given by V = constant [I] but does not provide a mechanism for changing the lamellar spacing. Jackson and Hunt3 calculated the interface shape by using solutions to the diffusion equation for a planar interface and a relation of the interface composition to the local curvature. If the spacing is much larger than the extremum spacing, the interface breaks down catastrophically to form forked plates. However, the catastrophic breakdown cannot account for the small adjustments in spacing that must occur in practice..3 Direct observations during the growth of organic eutectics4 and the Pb-Sn eutectic5 show that spacing changes occur by the formation of faults. A fault in a plate-like eutectic is the edge of a plate. Once the faults form, they may move to make small adjustments in the spacing.6,3 The motion of faults intersecting the growing interface was shown by an approximate analysis to give Eq. [I].6 A perfectly regular lamellar structure should be able to persist over a range of lamellar spacings. However, during growth small perturbations in the structure may occur. If the amplitude of the perturbation increases in time the structure is unstable, while if all possible perturbations decrease in time the structure is stable. In a previous paper7 variations in the shape of the solid-liquid interface were considered, while this paper considers only variations in lamellar widths while maintaining a macroscopically planar solid-liquid interface. Previously, theories of lamellar growth1"3 have artificially contrained the growth to give a regular periodic structure. To allow for a variation in spacing, the three phase intersections and groove angles were allowed to change with time as determined by assuming local equilibrium. THREE-PLATE PROBLEM Since the spacing changes in eutectics by local formation of faults,4&apos;5 it is suggested that local variations in spacing are responsible. The interaction between neighboring plates will be greatest because they have the smallest diffusion distance. For simplicity, as a nearest neighbor approximation, a three-plate problem will be considered, as illustrated in Fig. 1. The structure consists of a periodic array in which all the plates are allowed to vary in width. As in steady state growth it is assumed that the average composition in the solid remains constant. A variation in plate widths, that maintains the composition in the solid, was introduced by making the first a-phase plate thinner by an amount A, keeping the width of the second B-phase plate constant, and increasing the width of the third a-phase plate. If the structure were not perturbed, as in the regular two-plate problem previously described,&apos; then the groove angles at the three-phase junctions are the equilibrium angles, 0, and ? B, and the solid-solid boundary is normal to the interface. In the three-plate problem with a variation in plate widths the phase boundaries are assumed to be related to the three-phase junction by equilibrium angles, but the a/B boundaries may be rotated by an angle 0 from the growth direction. The angle H be-tween the tangent to the a/B boundary and the growth direction may vary during growth and determine the —> — — —.A_ Q-0 / 0 x, X2 Fig. 1—Schematic of the three-plate problem showing a variation in the spacing and the effect on the angles at the three phase intersections.

Jan 1, 1970

By E. H. Snow, B. E. Deal

Instability effects in semicanductor devices have long been attributed to the motion of charges on or within oxide layers on the surface. These effects are of critical importance in metal-insulator-semiconductor MIS) field-effect devices. For this reason, the capacitance-voltage or the conductance-voltage characteristic of these devices can be used as a sensitive detector to study charge transport and polarization effects in the oxide or insulator. A review is given of the results of such studies of thermally grown SiO2 as well as of other insulating films of importance in silicon technology. Three types of effects are distinguished. The first of these is the drift of mobile cations within the dielectric, examples being thermally grown SiO, which is often contaminated with sodium ions, and a variety of other glasses in which the mobile ions are a part of the glass composition. The second effect is a dipole-type polarization which occurs in phosphosilicate glass films obtained by reacting P2O5 with thermally grown SiO2. The third effect involves the transfer of charges between the dielectric and the silicon electrode. This occurs in silicon nitride and other deposited dielectrics. It is concluded that MIS studies have provided a powerful technique joy the study of charge transport and polarization effects in insulating films. The knowledge gained from these studies has led to an understanding of surface effects on conventional transistors and diodes as well as making possible stable MIS transistors. THE metal-insulator-semiconductor field-effect transistor is conceptually the oldest type of active semiconductor device.&apos; The earliest attempts at making this device were frustrated because of high surface state densities at the interface between the semiconductor and the gate insulation.&apos; However, by using a silicon substrate with thermally produced silicon dioxide as the gate insulation, this problem was solved and metal-silicon dioxide-silicon devices with good characteristics were made as early as 1960. 3 Yet it was still over 5 years before these devices became a commercial reality. This delay was largly due, not to surface states, but to stability problems associated with polarization effects within the insulating layer which caused the threshold voltage of the device to drift under temperature and bias treatments. The solution to these problems has not only made possible stable MIS devices, but it has added immensely to our understanding of failure mechanisms in conventional bipolar transistors and has added to the reliability of ali types of planar devices. In this review, we shall first describe the effects of various types of polarization phenomena on MIS device characteristics. Then, since thermally grown SiO, is by far the most important insulator used in these devices, we shall review historically the type of instabilities which have been observed in thermal oxides, the attempts at understanding and eliminating them, and the present status of the problem. We shall then turn our attention to the various deposited insulators which have been used, including lead glasses, phosphosilicate glass, vapor-deposited silicon oxide, and silicon nitride. Interestingly enough, many of these materials show polarization effects which are quite different from those generally observed in thermally grown SiO2. THE EFFECTS OF POLARIZATION PHENOMENA ON MIS CHARACTERISTICS The simplest MIS device and the one which has been most frequently used in the study of polarization effects is the MIS capacitor. Two modifications of this structure with single- and double-layer dielectrics are illustrated in Figs. l(a) and (b), respectively. The capacitance of this structure as a function of voltage applied to the metal gate electrode is plotted in Fig. 2 for the case of an n-type silicon substrate. When the silicon surface is accumulated (positive bias) the measured capacitance is just that of the insulating layer C. When the surface is inverted (negative bias), the capacitance is that of the insulator and a silicon depletion layer in series CoCs/(Co + Cs). Indicated on the horizontal axis of Fig. 2 is the voltage VT at which the silicon surface becomes strongly inverted. This voltage corresponds to the threshold or turn-on

Jan 1, 1969