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By B. F. Oliver

A levitation zone melter is described which has the necessary characteristics for processing metals of controlled purity. No crucible is required; control of the solidification variables is stable; the environment of the charge is chenzically controlled. Rotation of the solidifying interface and mixing in the liquid by the magnetohydrodynamic stirring produce an eight-fold increase in freezing velocity over former melting units with better resulting solute redistributions. The smooth appearance of processed specimens, resistivity ratios as a hnction of position, as well as a segregation curve, are presented as evidence of smooth continuous solute fransport over distances in excess of ten zone lengths. THE difficulties of the floating zone-purification of higher density metals in large quantities under conditions of lowered surface tension are well known and have hindered fundamental research programs for some time. The inordinate amount of time required to obtain a small reproducible yield of high-quality metal has excluded the use of such material for many important material research programs. However, with the use of controllable induction levitation forces' to accomplish stable liquid zones with nearly flat solidifying interfaces, and with good physical and chemical control of the processes involved, these difficulties can be overcome. A zone melter that is to be used for both high-purity and controlled composition work in metal systems must have the following three characteristics: 1) The process must avoid the use of containers. 2) Physical control of the solid-liquid interface and of the mixing within the liquid phase must be stable. 3) The chemical environment of the melt chamber must be controllable. A description of an apparatus that accomplishes these objectives follows.* APPARATUS One of the basic features that is necessary for good process control of large sections is that the charge, the coil, and the motion mechanisms be within the same chamber. This arrangement permits a close coupling between the work coil and the load, which then provides a good flexibility for adjustments of coil dimensions, for controlling the amount of levitation needed for stable operation at a given power level. An overall view of the melter is shown, with the melt-chamber door open, in Fig. 1. The radiation shields surrounding the single-turn induction coil are of water-cooled copper. The chamber is stainless steel, as are most of the components within the chamber. The control panel for the scanner is located at the immediate lower right of the melt chamber. This panel controls the operation of the scanner. The operations controlled are the interface rotation rate, the stretch-squeeze or diameter control, the up and down scanning speeds, and the induction power. All of the drive motors are constant-torque variable-speed motors. The scanning speeds are set with precision helipots and continuously observed with the voltmeter on the control panel and checked with a mechanical indicator within the melt chamber. The rotation rate is also set with a precision helipot. The up-scanning speeds are 2 to 300 in. per hr.

Jan 1, 1963

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1'2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult's law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By E. D. Hummer, J. A. Younkins. J. P. Proctor

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By J. A. Younkins. J. P. Proctor, E. D. Hummer

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

By R. C. Hall

The magnetic anisotropy and magnetostriction of single crystals of alloys between 25 and 59 wt pct Co in Fe have been determined in the disordered and ordered states. The magrzetostriction is large and positive for all alloys in both states of order (up to 150 x 10-6 for A,, and 40 x 10-6 for 111). The magnetic anisotropy becomes zero rzear 41 pct Co for the disordered state. Ordering shifts the zero-anisotropy composition to about 50 pct Co. COBALT-iron alloys have for many years been of interest as magnetic materials because they have unusually high magnetic saturation values.' This interest was increased recently by the development of Supermendur.' Supermendur is an alloy of 49 pct Co-49 pct Fe-2 pct V* which was found by suitable purification and heat treatments, including a magnetic anneal, to possess excellent magnetic properties. These included a square hysteresis loop with a low coercive force and a high magnetization, and a low total loss. Two factors which are important in determining the magnetic hysteresis properties are the basic magnetic properties of magnetostriction and anisotropy. Alloys having zero anisotropy and zero magnetostriction show improved hysteresis properties.3 Since very meager data4-' are available in the literature on the single-crystal anisotropy and magnetostriction of the cobalt-iron alloys, the present program was undertaken to determine these two properties in the disordered and ordered states. EXPERIMENTAL TECHNIQUES Ingots of the cobalt-iron alloys containing from 25 pct to 59 pct Co in iron were vacuum melted from electrolytic iron and cobalt of 99.9 pct purity. The ingots were cooled at a rate of about 1°C per hr through the transformation temperature (950" to 980°C dependent on the alloy content) for the growth of large grains. From these grains, single-crystal disks were fabricated with either the (110) or (100) plane parallel to the faces of the disk. The crystals were given two heat treatments to produce either the ordered state (cooling rate of 20°C per hr from 850 "C) or the disordered state (water quench from 850 °C). Since the iron-cobalt alloys order very rapidly, the water quench may not have produced complete disorder in all cases. Due to the method of growth, the crystals were not perfect. Most of the samples had low-angle boundaries and a few had some small included grains. These imperfections could and probably did affect the accuracy of both the magnetic anisotropy and magnetostriction measurements. Much of the scatter in the data may be attributed to the crystal imperfections. The methods of determining the spontaneous saturation magnetostriction and the anisotropy have been previously described.419110 MAGNETOSTRICTION The magnetostriction in the [loo] and [Ill] directions (hO0 and ?111 respectively) is illustrated in Fig. 1 for the disordered state. Both ?100 and ?111i became large positive values as cobalt was added to iron. The state of order did not have a large effect on the magnetostriction. The effect of order did not appear too consistent in these data. Tentative curves are shown in Fig. 1 for the ordered magnetostriction near the FeCo composition; here ?100 appeared to be lowered and ?111 raised as the degree of order was increased. These results agree qualitatively with the

Jan 1, 1961

By Alfred Siegel

Mineral pigments give color, opacity, or body to paint, stucco, plaster, mortar, cement, linoleum, rubber, and similar materials. They must be finely divided, substantially insoluble, and generally inert for such uses. Inorganic pigments may be grouped somewhat arbitrarily as follows: A. Natural mineral pigments dug from the earth. 1. Those consisting mostly of iron oxides, such as hematite and limonite. 2. Those containing large amounts of clay or noncoloring matter, such as ocher, sienna, umber, and colored shales. 3. Those whose color is not due to iron oxide, such as Vandyke brown (including sap brown, an alkali extract of Vandyke brown), graphite, and terre verte. B. Synthetic pigments. 1. Those containing iron oxide as the essential coloring matter, such as "pure" reds, yellows, and blacks, and Venetian reds. 2. Those not containing iron oxide, but rather such compounds as lithopone, zinc white, titanium white, ultramarine, Prussian blue, and the like. Only groups A and B-1 are discussed here. All the pigments in those two categories, except Vandyke brown, sap brown, and some of the carbonaceous slates, contain, as their essential color constituents, one or more compounds of iron; namely, an oxide-limonite (2Fe2O3.H2O to Fe2O3.4H20), hematite (Fe2O3), or magnetite (Fe2O3.FeO). Man's first permanent coloring materials were earth pigments-the ochers, iron oxides, and various iron-stained clays. The caves occupied by prehistoric man and the arts of the ancient Chaldean, Egyptian, and Cretan civilizations bear mute witness to this and also testify to the beauty and permanence of earth colors. As the Roman era developed, earth pigments were pushed from their pre-eminent position by white lead and red lead and in the Middle Ages by zinc oxide. Today, of course, the number of acceptable pigments is very large and on a value basis the group of natural and synthetic earth pigments stands forth with $16,000,000 per year; it is surpassed by titanium, lead and zinc pigments. Of this sum,21 natural pigments supplied 31 pct of the tonnage and 16 pct of the value of the total finished pigment in 1957, the remainder representing the tonnage and value of sales of the synthetic iron oxide colors. The average value of finished natural pigments in 1958 was $80.62 per ton. The average value of manufactured pigments in the same year was $202 per ton. Of the 60,000 tons of manufactured colored pigments sold in 1958, the reds comprised 76 pct of the market and the yellows 20 pct. The reds furnished 68 pct of the value and the yellows 24 pct. Of the finished iron oxide pigments (natural and manufactured) sold in 1958, the reds dominated the market with 66 pct of the quantity and 63 pct of the value; yellows supplied 17 pct of the quantity and 20 pct of the value, and browns furnished 11 pct of the quantity and 10 pct of the value. The average value of the reds was approximately $152, and the average value of the yellows $190 per ton. The highest valued pigment in 1958, with almost 12 pct of the total tonnage and 21 pct of the value of the iron oxide pigment market, was manufactured red from calcined copperas valued at $286 per ton.

Jan 1, 1960

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963

By T. J. Fabiniak, R. A. Dodd, R. Balow

ALTHOUGH the (111) slip direction in pure bcc metals is well established, the information on operative slip planes is less unambiguously interpreted. So far, (110) {112), and (123) slip planes have been identified, but it is not certain whether glide on (112) and (123) really occurs or if it is composite slip on non-parallel (110) planes. The second of these possibilities is supported by the work of Chen and Maddin on niobium and molybdenum, and a subsequent analysis by these same workers of slip in bcc metals generally.3 The alternative possibility is exemplified by the work of Opinsky and smoluchowsky4 who concluded that slip in Fe-Si crystals can occur on any one of the systems {110}(111), {112}(111), and {123)(111), depending on which system the resolved shear stress is highest. Allen et alS5 also found that glide in ar iron could occur on any of these three systems, the operative system being determined principally by orientation. By an analysis of crystal rotation, slip lines, and X-ray asterism Harris6 concluded that niobium also deforms on these same systems, but if one of these glide planes does not coincide with the plane of maximum resolved shear stress, composite slip on nonparallel (110) planes may occur giving a macroscopic high indices slip plane. Earlier work on iron by Vogel and Brick reached the same conclusion.7 The analysis of slip in bcc metals is made more difficult by the fact that the slip lines may be quite wavy. In fact, the generality of wavy slip lines suggests that screw dislocations slip readily from one plane to another in the (111) zone ("pencil glide") although, as noted, it is not certain whether planes other than (110) really contribute to the slip. If planes of higher indices than {110} do operate, there is a possibility they may do so more readily at higher temperature Argon and Maloof9 observed {100}{211}(111) slip in tungsten single crystals plastically strained at low temperatures, but the results were interpreted in terms of an orientation-dependence rather than temperature-dependence. Therefore, at the present time corroborative evidence for the operation of higher indices slip planes at higher temperatures is lacking. The present results were obtained during the course of an investigation into the effect of cathode and anode surface crystallography on the prebreakdown currents of vacuum insulated devices. In the experiment of particular interest, the 1/8-in.-diam anode and the in.-diam cathode were tungsten crystals (total impurities -230 ppm) with (110) and (100) faces respectively. The faces were electrolytically planed and examined for initial perfection by plastic/carbon replicas and a study of Kikuchi lines in reflection electron diffraction patterns. They were aligned precisely parallel in an insulating holder incorporated into the electron microscope, the measured microscope vacuum being 2 x 10-5 torr, and the electrode spacing 0.01524 cm. The anode structure shown in Fig. 1 was obtained

Jan 1, 1970

By J. T. Raleigh, D. L. Flock

This study investigated the nature of formation plugging with bacteria and attempted to relate its characteristics to physical rock properties. Fifteen core samples of four specific formation types were defined and plugged using a commonly occurring, uniform sized dead bacteria, Bacillus subtilis. Two of the formation types were fairly uniform-grained sandstones and two were heterogeneous carbonates. The injection rate and concentration of solids in the brine were held constant during the test runs. The pore geometry factor G was a significant petro-physical rock characteristic for correlation with depth of plugging, but lacked importance as a parameter for rate of plugging. Although the G factor may not completely describe porous rock geometry for plugging predictions, for reservoirs with multi-pore systems, there is evidence that the pore geometry factor might form a basis for establishing injection water specification in more llornogeneous reservoirs with only primary porosity development. INTRODUCTION GENERAL PURPOSE Injecting water into oil-bearing formations to increase recovery is common practice in the petroleum industry. One of the most serious operational problems involved with water injection wells is the tendency of the porous rock immediately adjacent to the injection wellbore to plug partially. This results in increased injection pressures and/or a decrease in the rate of injection. This plugging in injection wells can result from a number of causes, including bacteria contained in the injected water.1 The purpose of this work was to investigate the nature of injection plugging with bacteria and to attempt to relate its characteristics to physical rock properties. Many variables exist in research of this type, so, to reduce them, injection rate and concentration of bacteria in brine were held constant. The bacteria used for plugging was a uniform-sized, dead bacteria, Bacillus subtilis, a micro-organism commonly found in water, air and soils. Four specific porous rock types were plugged—two consolidated sandstones and two heterogeneous carbonates. The experimental work involved two distinct phases. The first concerned determining the physical rock properties and the second was the experimental work of actually plugging the selected core samples. PORE GEOMETRY FACTOR Capillary pressure is necessary to displace a wetting fluid from a capillary opening with a nonwetting fluid. The factors which govern capillary pressure are the surface or interfacial tension of the fluids involved, the system wettability and the equivalent pore radius. Thus: P,= 2ucososrd..........(1) Thomeer used the idea that the location and shape of the capillary pressure curve reflect characteristics of the pore structure of any porous media sample.' He presented the mathematical description of capillary pressure curves and of indicated differences in pore geometry of samples. where G = pore geometry factor PC = capillary pressure Pi = displacement pressure (V,)p, = fractional bulk volume occupied by the displacing fluid at any capillary pressure (V,), = fractional bulk volume occupied by the displacing fluid at infinite pressure or total interconnected pore volumes. The shape of the curve is defined by the pore geometry factor G. The curve shape is related directly to the sorting and interconnection of the pores of the sample. The location of an infinite number of curves can be defined by the same asymptotes. However, these curves differ in shape, each curve being described by a specific value of G. Thus, the description of a curve is unique when, in addition to the position of its asymptotes, its shape is defined. These curves can be used graphically to determine the characteristic parameters of any arbitrarily located curve. Those parameters that can be approximated from any capillary pressure curve are: (1) total interconnected pore volume, represented by (V,),- ; (2) extrapolated displacement pressure, the abscissa axis; and (3) pore geometry factor, by the curve shape. PROPERTIES OF BRINE AND BACTERIA The fluid used throughout this study was an aqueous solution of sodium chloride, 25,000 ppm by weight. The addition of salt to fresh water was intended to eliminate clay swelling in the sandstone cores and to retard leaching in the limestone cores. The viscosity of the brine solution at 100F, the temp-

Jan 1, 1966

By W. F. Domis, F. von Gemmingen, R. W. Whitmore, F. Garofalo

Constant-load creep-rupture tests at 1100°, 1300° and 1500°F were made on a Type-316, 18 Cr-8 Ni-ZMo, austenitic stainless steel to determine the relationship between ruptzire life and other aspects of creep behavior, The test program was designed on a statistical basis to check the variability of various creep properties and to determine emprically the dependence of minimutn creep rate and ruptzire life on initial stress, The dependence of the rupture life, tn, on the initial stress, a,, is found to be related to the stress dependence of the wrinimum creep rate, i,, and secondary creep strain, The instabilities or breaks found in the conventionual log - logt, plots can be traced to either a change in the linear dependence of log i, on log a, or to a change in secondary creep strain. In the alloy tested, rupture is found to be predowmanantly of the inter crystalline type, For this material, the secondary creep strain is -found to depend on the nature of the grain boundary precipitate, which affects grain boundary migration. It has been shown for a variety of metals and al tested at elevated temperatures under creep conditions that the empirical relationship exists between rupture life, tr, and minimum creep rate, i,. This relationship, in which C and a are in some cases independent of stress or temperature, shows in a general way that creep rupture depends on creep behavior prior to tertiary creep stage. To determine more fully the factors which control creep rupture requires, therefore, more knowledge of the relationship between rupture and creep behavior. To obtain such information, constant-load creep-rupture tests have been made on a Type-316, 18 Cr-8 Ni-2 Mo, austenitic stainless steel at 11000, 1300°, and 1500°F. These tests were designed on a statistical basis to determine the variability of the various creep properties measured and to determine empirically the stress dependence of minimum creep rate and rupture life. As a result of this work, various empirical relations have been established defining more closely the factor, C, in the relation between rupture life and minimum creep rate. This factor is found to be proportional to the amount of strain during secondary creep. The variation of secondary creep strain with rupture life and temperature is determined and its effect on rupture behavior discussed. The variability in minimum creep rate and rupture life is also dis- cussed and the dependence of these quantities on initial stress is interpreted. TEST MATERIAL AND TEST PROCEDURES The material tested is an austenitic stainless steel, AISI Type 316, of the following composition: C, 0.07 pct; Mn, 1.94 pct; P, 0.01 pct; S, 0.021 pct; Si, 0.38 pct; Cr, 18 pct; Ni, 11.4 pct; Mo, 2.15 pct; All 0.003 pct and N, 0.043 pct. The material was received as a hot-rolled 0.5-in. diam bar which was sectioned into 3.25 in. long blanks. Each blank was heat treated by holding 1/2 hr at 2000° F followed by water quenching. A 3/8-in. coupon was removed from each heat-treated blank and the microstructure was examined, the grain size determined, and the hardness measured. The microstructure was found to be uniform from blank to blank and the grain size was found to range from 4 to 6 ASTM numbers. Hardness, measured using a 20-kg load, varied between 127 and 148 Vpn. Tensile creep-rupture specimens having a 0.25 in. diam within a 1.5-in. reduced section were machined from the heat-treated blanks. Constant-load tests were made on these specimens at 1100°, 1300°, and 1500 F. Six specimens were tested at each stress level. Three creep-rupture machines were employed for tests at each temperature, two specimens being tested in each machine for each stress level. To minimize any effect due to local inhomogeneities along the length of the as-received bar the specimens were randomized before test. Each specimen was tested to rupture and in most cases an autographic extension-time curve was obtained. For very low stress levels at 1500°F no auto-

Jan 1, 1962

By Richard M. Foose

Most of the roofing granules produced in Pennsylvania are made by two companies at three plants. The Advance Industrial Supply Co. has three quarries and a mill at Gladhill Station, in southern Adams County. The Funkhouser Company is actively engaged in mining, quarrying and milling at Charmian, about one mile west of Gladhill Station, and at Delta, in southern York County. These three plants produced approximately 100,000 short tons of granules in 1943. The production of rooling granules in 1937 for the whole country was only about 500,000 tons, generally indicating the large growth of the industry since that time. The fundamentals of producing roofing granules were discussed comprehensively by G. W. Josephson in a paper before the Industrial Minerals Division in October 1943 (TP 1725, this volume page 460). The purpose of this paper is to describe the actual methods of mining the rock and milling it to make roofing granules, as practiced by the three Pennsylvania plants. Mining and Milling Funkhouser Company (Delta) The Funkhouser Company, near Delta, in southern York County, Pennsylvania, operates three joined quarries and a mine in the Peach Bottom slate. The joined quarries extend 1200 ft. in a northeast-southwest direction along the strike of the slate cleavage and are about 200 ft. .wide. The working face is about 45 ft. high. The quarrying operation is rather simple: Ingersoll-Rand Jackhamers, I-in. and 1 1/4-in., with hollow drill steel, are used to undercut the quarry face with 10-ft. holes. The face is "blown" and allowed to slump on the quarry floor. Loaded by a Marion electric shovel into trucks, the shattered rock is taken to the primary crusher 2500 ft. away. In addition to the normal quarrying operations, a drift into the northeast wall of the middle quarry was begun about 1935, and has advanced about 2000 ft. since then. Rooms have been driven at angles to the drift along choice beds of slate. The drifts and rooms have a roof more than 35 ft. high and the main drift and rooms are all more than 40 ft. wide. There is no cribbing at any place in the mine. Several of the rooms were driven upward on a 5' slope and in some of them there was stop-ing. Ingersoll-Rand Jackhamers are used, and only wet drilling is practiced. When visited in January 1940, an electric shovel was operating at the head of the drift, scooping up the slate blasted out of the working face. This, too, is trucked to the primary crusher. Some of the better quality slate is saved for making slate shingles. The primary crusher, which is a No. 30 McCulley gyratory, receives the slate from the trucks and crushes it to about a-in. size (Fig. I). This product travels by a 30-in. belt conveyor to Niagara vibrating screens with 2-in. holes. The minus a-in. product moves to a storage silo by bucket

Jan 1, 1948

By Richard M. Foose

Most of the roofing granules produced in Pennsylvania are made by two companies at three plants. The Advance Industrial Supply Co. has three quarries and a mill at Gladhill Station, in southern Adams County. The Funkhouser Company is actively engaged in mining, quarrying and milling at Charmian, about one mile west of Gladhill Station, and at Delta, in southern York County. These three plants produced approximately 100,000 short tons of granules in 1943. The production of rooling granules in 1937 for the whole country was only about 500,000 tons, generally indicating the large growth of the industry since that time. The fundamentals of producing roofing granules were discussed comprehensively by G. W. Josephson in a paper before the Industrial Minerals Division in October 1943 (TP 1725, this volume page 460). The purpose of this paper is to describe the actual methods of mining the rock and milling it to make roofing granules, as practiced by the three Pennsylvania plants. Mining and Milling Funkhouser Company (Delta) The Funkhouser Company, near Delta, in southern York County, Pennsylvania, operates three joined quarries and a mine in the Peach Bottom slate. The joined quarries extend 1200 ft. in a northeast-southwest direction along the strike of the slate cleavage and are about 200 ft. .wide. The working face is about 45 ft. high. The quarrying operation is rather simple: Ingersoll-Rand Jackhamers, I-in. and 1 1/4-in., with hollow drill steel, are used to undercut the quarry face with 10-ft. holes. The face is "blown" and allowed to slump on the quarry floor. Loaded by a Marion electric shovel into trucks, the shattered rock is taken to the primary crusher 2500 ft. away. In addition to the normal quarrying operations, a drift into the northeast wall of the middle quarry was begun about 1935, and has advanced about 2000 ft. since then. Rooms have been driven at angles to the drift along choice beds of slate. The drifts and rooms have a roof more than 35 ft. high and the main drift and rooms are all more than 40 ft. wide. There is no cribbing at any place in the mine. Several of the rooms were driven upward on a 5' slope and in some of them there was stop-ing. Ingersoll-Rand Jackhamers are used, and only wet drilling is practiced. When visited in January 1940, an electric shovel was operating at the head of the drift, scooping up the slate blasted out of the working face. This, too, is trucked to the primary crusher. Some of the better quality slate is saved for making slate shingles. The primary crusher, which is a No. 30 McCulley gyratory, receives the slate from the trucks and crushes it to about a-in. size (Fig. I). This product travels by a 30-in. belt conveyor to Niagara vibrating screens with 2-in. holes. The minus a-in. product moves to a storage silo by bucket

Jan 1, 1948

By G. Britsianes, T. L. Joseph

THE reduction of a lump of iron ore is a complicated sequence of up to three reactions proceeding simultaneously in a gas-solid system. As the ore moves down the blast furnace into zones of higher temperature and higher reducing power, it is successively reduced through the three oxides of iron into metallic iron. The reduction process involves much more than chemical problems. Physical factors add to the complexity of the overall process. Under optimum conditions, reduction of the ore is completed at a level about one-half way down the blast furnace stock column. At this point, the ore undergoing reduction has attained a temperature of about 1000°C and has been in the furnace for about 6 hr. On the practical side, the behavior of the ore during smelting has been of great interest to operators. Unsatisfactory blast furnace operation on burdens containing magnetite ore or badly slagged sinter has often been attributed to poor re-ducibility. The question of reducibility has also been raised in formulating quality standards for agglomerates such as nodules, briquettes, and pellets. In the present investigation, the solid phases formed during reduction were studied as a step toward a better understanding of the overall process. Equilibrium Studies The iron-oxygen equilibrium diagram shown in Fig. 1 reveal; a number of facts pertinent to the gaseous reduction of iron ores. This diagram is from the work of Darken and Gurryl, 2 and represents a correlation of the best available data. Four solid phases may exist during the complete reduction of hematite to metallic iron. These are hematite (Fe2O3), magnetite (Fe3O4), wustite (FeO), and iron (Fe). The wustite phase is a solid solution which is not stable below 570°C. At this temperature the solid solution undergoes a eutectoid-type of decomposition into the phases, magnetite and iron. Thus above 570°C, the diagram dictates that a hematitic ore should pass through a four-phase sequence on reduction to metallic iron. Below 570°C, only hematite, magnetite, and iron should appear. Information on the iron-oxygen system has been derived largely from CO and H2 reduction equilibria. The Fe-C-0 relationships have been studied extensively by R. Schenck and his coworkers and well summarized by H. Schenck.3 More recent studies have been made by Darken and Gurry.1, 2 Data from these sources have been combined and plotted in Fig. 2. With respect to the Fe-H-O system, the works of Emmett and Schultz4 seem the most reliable, and these data have also been included in Fig. 2. Certain physical properties of the solid phases of the iron-oxygen system are summarized in Table I. The crystallographic information is of special interest as much of the present work has been concerned with the X-ray analysis of the products of reduction. Reduction with Hydrogen The reduction of ore with hydrogen is the net result of two or more gas-solid reactions. Above 570°C, the reaction sequence may be represented by stoichiometric stages as follows: 3Fe203+ H2e2Fe,O, + H20 [1] 2Fe3O, + 2H2 6FeOw + 2H2O [2] 6FeOw + 6H3 ^ 6Fe + 6H=O [3] Fe2O3 + 3H2 ^ 2Fe + 3H,O. [4] These reduction reactions follow the general form: A (solid) + B (gas) e C (solid) + D (gas). This type of gas-solid reaction has been investigated by Langmuirl' who has shown that such reactions can occur only at the boundary between the two solid phases. Furthermore, a nucleus of the second phase must initiate the reaction. Once such an interface exists, the reaction proceeds through a layer of the solid reaction product (C). The specific mechanisms involved will depend a great deal on the properties and condition of this particular layer. A number of heterogeneous reactions such as the dehydration of single crystals of copper penta-hydrate and the calcination of limestone follow this type of process. It should be noted that the inter-facial type of reaction also occurs even in dense polycrystalline material which simulates a mono-crystalline behavior.

Jan 1, 1954

By W. R. Wilcox

The camphor-anthracene system was chosen as a transparent low-melting analog of the zirconium carbide -graphite system. Camphor and zirconium car -bide both grow nonfaceted, while casting of mixtures yields platelets of both anthracene and graphite. Zone melting of thin layers of organic was observed under the microscope. Irregular lamellar structures were produced at high values of the ratio of the temperature gradient G to the zoning rate V. The anthracene invariably led the camphor, indicating lower kinetic undercooling for the anthracene. The lamellar spacing was an order of magnitude greater than typical spacings for metal eutectic systems. Exact behavior depended on orientation of the anthracene. Oriented dendritic structures were produced at low values of G/V. Transient and oscillatory behavior were also observed—much of it unexpected. A.RC-CAST refractory carbide-graphite mixtures are promising thermal-shock resistant materials. Oriented structures of these materials would be superior to arc-cast materials for many applications. Mollard and Flemings1 and Cline2 have shown that aligned structures can be obtained for a wide range of Pb-Sn alloys. However, these metals both solidify in a nonfaceted manner while graphite yields platelets or flakes. In addition only small diameter samples of Pb-Sn alloys were produced because it was necessary to avoid free convection and to have high temperature gradients. The purpose of the present work was twofold: 1) To observe the solidification of a transparent low-melting analog of carbide-graphite systems and 2) to see if larger diameter samples can be produced. EXPERIMENTAL PROCEDURE When zirconium carbide-graphite mixtures are cast, the resulting structure naturally depends on composition. Carbide-rich mixtures yield metal-like nonfaceted carbide dendrites in a eutectic matrix. Graphite-rich alloys have graphite platelets in a eutectic matrix. Empirically it was found that camphor-anthracene mixtures produce similar structures with camphor being nonfaceted and anthracene forming plates. The organic eutectic melted at 116°C and was composed of 78 wt pet camphor.3 The camphor used was U.S.P. grade from Fisher Scientific Company; the anthracene was 98+ pet fro Aldrich Chemical Co. The impurity content is judged to be on the order of 1 pet. Mixtures ranging from 50 to 88 wt pet camphor were employed for the experiments. All but one of the experiments were performed on the microscope-stage zone melting apparatus described in detail elsewhere.4 The organic mixtures were contained in horizontal cells made of microscope slides or cover glasses. In most of the cells the organic was present as a very thin layer, thus giving almost two-dimensional growth behavior. The cells were moved slowly under a heated wire, which caused a molten zone to move through the solid at rates ranging from 0.01 to 5.4 cm per hr. The temperature gradient was estimated before moving the zone by measuring the distance between the line where all solid was melted (freezing point) and that where solid first began to melt (eutectic temperature). The temperature gradient was found to be 465°C per cm in the thinnest cells used, which were made by pressing together two microscope cover slips in the organic melt and then rapidly withdrawing them. RESULTS The experimental results are described in four parts: simultaneous growth, dendritic growth, irregular growth, and transients and erratic phenomena. Steady state data are summarized in Fig. 1. Except where noted all comments are for the cells containing a thin layer of organic. A) Simultaneous Growth. Simultaneous and roughly parallel growth of anthracene and camphor was obtained over the full range of compositions investi-

Jan 1, 1970

By A. Heim, M. Gondouin

Invasion experiments were run on Berea sandstone cores to get laboratory measurements of resistivity and saturation profiles characteristic of water and oil sands invaded by mud filtrate. Injection rates were as low as 1.13 cm/D, and the cores were 30 to 36 in. long, cut parallel to the bedding planes. In the water-sand case, the resistivity profiles revealed the existence of an extensive transition zone between flushed and uncontaminated zones. In the linear geometry of the experiment, the width of the transition zone increased as the square root of the injected fluid volume. For the oil-sand case the core was prepared by displacing the formation water with kerosene to minimum water saturation. During the subsequent invasion experiment. oil saturation was measured directly by means of an oil-soluble radioactive tracer, and resistivity profiles along the core were taken at the same time. These data were interpreted in terms of an oil-water front, followed by a formation water bank, a zone of mixed waters, and finally, invaded mud filtrate near the borehole. Micro-fingering and capillarity seemed to affect considerably the resistivity profiles observed in the invaded oil-sand experiment. Beyond the regular conductive annulus or "low zone", it was found that a resistive "anti-annulus" could also be formed. As a result of these experiments, some simplified invasion profiles have been accepted and are being used in Grand Slam* interpretations. INTRODUCTION The importance of the mud filtrate-invaded zone in interpreting electrical logs has long been recognized.',* In trying to account for its effect, only very simple models of the resistivity profiles in the radial direction from the borehole have been used. In fact, most log interpretation charts have been based on resistivity models consisiting of two media of uniform resistivity (R, and R,) abruptly separated at the diameter of invasion. Such a clean separation of the media of different resistivities seems unrealistic, since flushing may not be perfect and may vary with radial distance into the formation.3** The nature of the transition zone, when it is within the radius of investigation of the surveying devices, may affect the log readings. Campbell and Martin' verified that a conductive annulus containing a high percentage of formation water may be formed when mud filtrate invades an oil-bearing sand. Interpretations which are to include the effect of such an annulus require the addition to the model of a conductive zone located at the outer rim of the invaded zone.' Using the Buckley-Leverett relations,6 aturation profiles may be derived, from which resistivity profiles can be calculated. Results of such computations by K. S. Kunz and J. H. Moran were given in a paper by Dumanoir. Tixier and Martin,7 and led to the construction of log interpretation charts which were based on a representation with three media of resistivities R, R0 and R1. Fig. 1 shows a schematic representation of a resistivity profile which includes an annulus. Campbell and Martin realized that, during the invasion of an oil sand, both capillarity and mixing would contribute to rounding of the profile shown in Fig. 1. Capillarity tends to draw some of the formation water from the annulus into the uncontaminated (Rt) zone, whereas mixing of the mud filtrate with formation water of the

Jan 1, 1965

By Nicholas J. Grant, Hanna Ibach, Bill C. Giessen

The system Ta-Rh was investigated over the entire comnposition range using metallogvaphic and X-ray techniques as well as thermal analysis. Terminal solubility limits, solidus temperatures, and the crystal structures of two new intermediate phases were determined. There are five intermediate phases: o, tetragonal, isostructural with o(Fe-Cr); a1, orthorhomnbic : a2, orthorhombic, isostructural with CozSi; 0 3, a high -temperature phase of unknozun structure; and a TaRh3, cubic, AuCu3 structure. a, aL, a,, and a melt peritectically; and a TaRh, has a maximum melting point. Five peritectic and one eutectic reactions occur. THE Ta-Rh phase diagram has not been fully treated in the literature; however, two inter metallic phases have been described.&apos;-&apos; This study attempts to work out the diagram covering the details of phase boundaries as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by National Research Corp., Cambridge, Mass., and rhodium powder of 99.9 pct purity, supplied by Bishop Co., Malvern, Pa. Analyses as given by the manufacturers are presented in Table I. In addition to the spectroscopic analysis, an oxygen analysis has been made of the tantalum powder. After preliminary trials, the standard procedure employed in making the alloys was as follows (see Ref. 4 for further details). The powders were weighed, mixed manually, compacted under 16,000 psi, and arc-melted at not more than 500 amp under thoroughly titanium gettered welding-grade argon of 400 mm Hg pressure. The gettering process was repeated after each melt. It had been shown previously5 that under these conditions no oxygen pick-up exceeding 0.001 pct in a hafnium button could be detected. The buttons, ranging from 5 to 10 g in weight, were inverted or, if possible, crushed and remelted three times. Melting presented no difficulty, except for tantalum-rich al- loys, which showed considerable spashing during melting. The average weight loss of 1 wt pct rose to 2.5 wt pct in these cases. Subsequent melting, however, resulted in losses of less than 0.1 wt pct. The melts obtained frequently showed small in-homogeneities, mostly in the tantalum-rich part of the system below 25 at. pct Rh. This was not due to insufficient blending of the elements, but to crystallization taking place from the cooled bottom. This condition was not improved by further re-melting; therefore the following precautions were taken. Cross sections of as-cast buttons were made. For the investigation only buttons were used where these inhomogeneities did not exceed 1 at. pct (estimated from the amounts of haSeS resent). In addition, only the center portions of such buttdns were utilized to minimize errors. Smaller buttons showed smaller concentration gradients and were used as a check. Finally, all alloys were homogenized to eliminate coring (see below). After this, the error in alloy composition due to inhomogeneity was cl at. pct. In order to confirm the concentrations of the alloys and to provide an impurity check, wet-chemical analyses and oxygen-fusion analyses of four key alloys were carried out. The results, together with the concentrations as calculated with the weight balance method, are presented in Table 11. It was found that for three alloys the agreement is very good (< 0.2

Jan 1, 1964

By R. T. Torgerson, W. A. Baginski

Alloying studies were conducted on modifications of Cb-10W-1OHf (C-129) alloy as part of a cooperative alloy development effort between The Boeing Co. and the Wah Chang Corp. The purpose of these studies was to develop a fabricable, high- strength columbium alloy with superior melding properties. The initial investigations of alloy modifications were conducted using laboratory-melted button ingots. An alloy with the composition exhibited excellent veld ductility, elevated-ternpevature strength, and fabricability. The yttrium-modified alloy was desigrzated C-129Y and was selected for further developrnetzt. Three prodziction heats of C-129Y weve processed into sheet. Welding, forming, and tensile proper-lies are presented for this material. Tungsten-are welds of. C-129Y exhibited a minimum bend radius of 1/2T in the as-welded conditioti compared to 8T for C-129 alloy. An investigation was conducted on Disil coating of C-129Y and test data are presented on oxidation resistance and effects of re-entry environments. The excellent combination of strength, fabricability, weldability, and low transition temperature of C-129Y alloy offers potential design advantages for use of this alloy in structures of aerospace vehicles. It is atiticipated that C-129Y will rapidly supplant C-129 and similar alloys clue to the versatility provided by its impvoved welditzg properties. COLUMBIUM alloys with improved properties are required to achieve better performance and efficiency of radiation-cooled structures for re-entry vehicles and recoverable launch systems. Cooperative work by The Boeing Co. and the Wah Chang Corp. resulted in the development several years ago of C-129 alloy, a high-strength Cb-W-Hf alloy.&apos; This alloy has received favorable consideration for many advanced designs of high-temperature structures due to its excellent combination of properties. However, this alloy exhibits low weld ductility unless given a high-temperature stress-relief treatment. For this reason the development effort was directed towards modification of the C-129 alloy composition (Cb-1OW-1OHf) to eliminate the need for post-weld heat treatment. This paper describes the successful development of an alloy meeting this requirement. This new alloy was designated C-129Y and has a nominal composition of EXPERIMENTAL PROCEDURES Alloying Studies. Various Cb-W-Hf compositions were investigated using are-melted button ingots. These buttons were hot-forged using a protective glass coating and rolled into sheet specimens. Metal-lographic examination: tensile testing, and welding studies were conducted to evaluate properties of the experimental alloys. Sheet Fabrication. Three pilot production heats of C-129Y were fabricated into sheet to establish processing techniques and to determine sheet properties. The three heats consisted of 6-in.-diam ingots weighing from 140 to 250 lb. The ingots were prepared by electron-be am melting followed by vacuum-arc melting. The hafnium and yttrium additions were made during the are-melting operation by tack welding alloy strip additions to the Cb-W master-alloy electrode. The final ingots were machined into billets with samples of the machine turnings collected for chemical analysis. Ingot breakdown methods for the three heats are as follows: Ingot Ingot Heat Size Weiaht___Breakdown Method A 6 in. 250 lb Hot extrusion B 6 in. 140 lb Hot forging C 6 in. 250 lb Hot extrusion Sheet bars from the extrusion and forging operations were conditioned, recrystallized, and rolled into sheet. Initial rolling was conducted at elevated temperatures and final rolling was conducted at room temperature.

Jan 1, 1967

By A. D. Schwope, L. R. Jackson, A. M. Hall

IN the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of recrystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. MATERIALS USED IN THE INVESTIGATION Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table 1. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871°C in air and hot rolled to 3/8 in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hrs. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pct reduction) in 6 passes and annealing at 427°C for 4 hrs. This annealed wire was then drawn to 0.081 in. wire, (37.1 pct reduction) in 2 passes. Square rod was made by hot rolling wire bars to 9/16 in, rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 3 1/2 hrs at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°C for 3 1/2 hrs. Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 X 0.268 in. square, annealing for 332 hrs at 538°C and cold rolling to 0.257 X 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hrs in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from 0.015-0.025 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. EFFECT OF COLD DRAWING AND TENSILE STRAIN ON STRENGTH OF COPPER Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are

Jan 1, 1947