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By L. E. Mannion

Sodium carbonate or soda ash is one of the two principal alkalis of commerce, the other being sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines or solid salts were the source of impure soda for glass manufacture. In early modern times until the 19th century, soda ash, as well as potash, was recovered mainly by leaching the ashes of plants. In Europe, during the 18th century, a brown lye for laundering was produced by pouring hot water over burned seaweed. One of the better grades of this kind of material was a product from Spain termed "barilla," which analyzed 24 to 30% Na2CO3 (Hou, 1942). The birth of the modern chemical industry may be said to start with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. Although invented in France in 1691, England made the most extensive use of it. In 1863 Ernst Solvay devised the ammonia-soda or Solvay process, and by 1874 the first of many Solvay plants was built. These were to supplant the LeBlanc method and dominate soda-ash production until the present time. Although of lesser importance, natural sodium carbonate deposits continued to support operations in various parts of the world. Shortages during World War II stimulated production of "natural" soda ash, particularly at Searles Lake, Calif., and at Lake Magadi, Kenya. Within the last ten years in the United States, a notable surge in production has occurred based on the vast trona deposits in Wyoming. Table 1 lists some principal producers of natural soda ash and the character of the source deposits. Uses and Specifications Sodium carbonate (Na2CO3) is a white, crystalline hygroscopic powder, an aqueous solution of which is strongly alkaline. Most commercial soda ash is a product that must meet high standards of purity and uniformity. Two forms are commonly sold: a fine, powdery material called light ash, and a more coarsely crystalline dense ash; these weigh 32 to 39 and 60 to 66 lb per cu ft, respectively. Dense ash may be produced by adding a little calcium chloride to the sodium carbonate solution to control crystal size and prevent agglomeration. Specifications and typical analyses of light and dense ash in the United States are shown in [Table 2]. Sizing generally achieves about 75% of light ash and 90% of dense ash between +30 and -100 U.S. screen mesh. World use of sodium carbonate now exceeds 24 million tpy, of which the United States produces more than 7 million tons. The market for soda ash is dominated by the glass industry, which uses almost half the supply. Inorganic chemicals, including phosphates and silicates, consume about 30%. Other principal uses include the manufacture of soaps and detergents, petroleum, caustic soda, organic chemicals, and paper; and nonferrous and ferrous metallurgy. [Fig. 1] shows the percent consumption by use of soda ash in Europe, Japan, and the United States. The price of soda ash in the United States remained relatively stable during the 1960s at about $33 per ton; in 1972 it reached $35 per ton. The price in 1975 was $42 per ton. Geology Mineralogy [Table 3] is a list of the more common sodium carbonate-bearing minerals. Anhydrous sodium carbonate is almost never found in nature; only natron, thermonatrite, and trona have been used directly as sources of sodium carbonate. At Searles Lake, burkeite and hanksite are important in the reconstitution of

Jan 1, 1975

By Edwin A. Rides

HISTORICAL ORIGIN OF THE EXPORT CREDIT AGENCIES Almost since the inception of international commerce sellers, having manufactured and/or sold and shipped goods to an overseas buyer, have been obliged to accept the risk that they will not be paid for one reason or another. There are many reasons why payment may not be forthcoming, for example, the goods may be lost at sea, or rejected by the buyer or the buyer nay simply not be creditworthy. These risks were brought into sharp relief as international trading became more sophisticated and the practice of giving credit to buyers gathered momentum. Inevitably enterprises sprang up which offered same mitigation of this exposure, accepting houses and later confirming houses and banks were prepared to assure acceptable credit risks an behalf of the seller, usually by discounting trade paper, and for many years the market ticked over reasonably satisfactorily. However, after the 1914-18 War international trade was at an extremely low ebb and its inherent risks were accentuated to a point where they were often commercially unacceptable. Yet a healthy and vigorous international market was indispensable to recovery of the world economy and a number of governments, led by the United Kingdom, perceived a need to offer their exporters a comprehensive form of insurance, particularly to facilitate the extension of credit to foreign buyers. In the United Kingdom the Export Credits Guarantee Department (ECGD) was set up to encourage trade through the provision of export credit insurance. Over the ensuing years others followed suit and now most of the developed trading nations and many developing nations have similar agencies. PRESENT DAY IDLE OF THE EXPORT CREDIT AGENCIES (ECAS ) Traditionally then the BA's role was to encourage trade through the provision to exporters of insurance against the risks of non-payment by overseas buyers of their goods and services. However, during the 1970's the manufacturing industries of most of the developed nations found themselves facing severe competition for business, particularly in the developing world. As a result the more aggressive ECA's began to introduce ancillary forms of cover designed to reduce exporters' risks outside of the credit field. For instance, most of the European agencies now have a form of cover against foreign exchange risks here contracts are denominated in currencies other than that of the exporter's country. Most of the agencies also provide cover to exporters against the risk of unfair calling of bid, advance payment, performance bonds etc and in certain countries, where high inflation rates were endemic, a form of cover against cost escalation. In certain circumstances it is also possible for an exporter to obtain cover against losses arising as a result of the involvency of a partner in a consortium or joint venture. These are all forms of insurance but, also during the 1970's, many of the national export credit programmes took a major step away from their original raison d'etre by facilitating the provision of preferential financing terns for the acquisition of capital equipment by an overseas buyer. This new line of business quickly became an important ingredient of major export financing packages and, as we shall see later, turned out to be extremely costly for the countries providing it.

Jan 1, 1985

By A. J. May

THE Star shaft is near the north boundary of the group of mining claims belonging to the Ground Hog Unit of the American Smelting and Refining Co., near Vanadium, N. Mex. The shaft bins and surface plant are served by a siding from the Atchison, Topeka and Santa Fe railroad, and this factor of railroad transportation influenced the choice of site. This paper describes the shaft sinking only, and does not cover the surface plant or other parts of the mine or its equipment. Experience with this shaft seems of interest because of the mechanical mucking, good rate of progress, and the costs obtained at the present level of labor and material costs. The shaft has four compartments, as shown in fig. 1. Equipment: Riddell Mucker: The mucking was done by a clamshell bucket and a Riddell mucker, which, as in other shafts sunk with this machine, consisted of a carriage mounted on axles with double flanged wheels that traveled back and forth on a swinging track, parallel to the long axis of the shaft (fig. 2 to 6). Three air motors were mounted on the carriage; one hoisted the clam, one operated the bucket opening and closing device, and the third moved the carriage along the track. The carriage was designed with guide shoes and could be hoisted to the surface in either skip compartment without trouble (fig. 4). During blasting operations the clam was tied on the rails and the carriage was hoisted up a few sets to protect it from flying rock. No attempt was made to hoist the carriage and clam together lest the clam catch in the timbers. The track on which the carriage operated was built of extra heavy 6 in. pipe with 1x2 in. strap welded on top for rails. A 1/2x4 in. angle was welded on the bottom of the 6 in. pipe with a 1 in. round rod welded in the angle for a filler and additional strength. The end or cross pieces of the track which kept the track to gauge, were also made of reinforced, heavy 6 in. pipe and were bolted to the long members on which the carriage traveled (fig. 2 and 3). This section of track was used, instead of heavy railroad rails, for two reasons: (1) this section would bend before it snapped and was much safer for the men in the bottom; and (2) it was a better blasting shield, and protected the timbers better, in fact, only five wall plates were broken by blasting in 1926 ft of shaft, although 150 to 225 lb of 40 pct powder was loaded per round, depending on the ground conditions. The swinging track was supported by four 5/s in. hoisting cables anchored to the end plates. There were also four safety cables fastened two to three sets above the carriage, which would catch the carriage if one of the supporting cables should fail for any reason (fig. 7). Clamshell Buckets: Two clams were used, each of 3/s yard capacity, both manufactured by Blaw Knox, Nos. 662 and 663. The No. 663 clam was 4 in. wider and 5 in. shorter than the No. 662, but seemed to dig and load more satisfactorily. It was easier to hoist and lower when it came up for repair. It did not turn over as easily, had less spill

Jan 1, 1950

THE strike and dip of bedded formations is readily determined by trigonometry if some marker horizon is intercepted by three holes. If no marker can be identified and if orientation of the cores is unknown, as is the usual case in diamond drilling, the determination still can be made readily by the use of a stereonet if the bearing, inclination, and angle the bedding makes with the core axis is known for each of the three holes. Such determination, valid only if the bedding orientation is fairly uniform within the area drilled, is considered simpler, faster, and more effective than any solution previously published. Method: The steps of this procedure are as follows: 1) Mark north and south poles on tracing paper placed over stereonet.* 2) Plot the three diamond drillholes by drawing a line from the center of the net in the direction of the bearings of the holes. Then rotate the paper until each line, in turn, lies along the equatorial diameter of the net; the end of each line is determined by the inclination of the hole measured in degrees from the periphery toward the center of the net along the equatorial diameter. Fig. 1 illustrates a vertical hole and a hole inclined at —23" due east. 3) With the projection of one diamond drillhole along the equatorial diameter, measure from the end of the hole, to the east and then to the west, a dis- tance in degrees equal to the core axis-bedding plane angle. Find two more points by measuring the same number of degrees north then south along the great circle from the end of the drillhole. Draw a circle, the center somewhere along the direction of the projection of the drillhole, to connect these four points. Draw circles for the other two diamond drillholes in the same manner. See Fig. 1 for two circles representing core axis-bedding plane angles of 35" and 23" and Fig. 2 for these plus a third circle representing a core axis-bedding angle of 42" in a hole bearing S 50 W inclined at —52". 4) Rotate the tracing paper until one great circle on the stereonet is found which is tangent to all three of the circles or parts of circles derived in the previous step. Trace this great circle on the paper and join its ends with a straight line passing through the center of the net. The bearing of this line is the strike of the bedding. In Fig. 2 the bedding strikes N 77 E. 5) Rotate the paper until the strike is along the polar diameter of the net. The dip of the bedding is determined by measuring along the equatorial diameter the distance in degrees from the periphery of the net to the great circle derived in step 4. The dip of plane illustrated in Fig. 2 is 55" to the N 13 W. Fig. 3 indicates the solution for three holes whose bearings and inclinations are N 20 W and —43o, due E and —30°, S 30 W and 23" with core axis-bedding angles of 30°, 50°, and 43" respectively. The bedding (stippled area) strikes N 44 W and dips 70" to the southwest.

Jan 1, 1956

By D. W. Frommer, M. M. Fine

Mineral dressing research showed that iron concentrates of commercial quality could be produced from the Pea Ridge deposit near Sullivan, Mo. Magnetic separation and flotation, on a laboratory scale, yielded concentrates ranging from 60.0 to 71.4 pet Fe at recoveries of 89.9 to 97.6 pct. Early in 1957 St. Joseph Lead Co. announced discovery of three new centers of iron ore deposition in east central Missouri.' The discovery resulted from exploratory drilling in the vicinity of a magnetic anomaly or high. A deep hole, drilled into the Pre-Cambrian porphyry to determine the cause of anomaly, penetrated a magnetite-rich deposit.' The magnetic surveys that revealed the anomalies were begun by the Missouri Geological Survey in 1929 and were continued into the 1930's.3 At that time an area in Crawford County known as the Bourbon magnetic high was located. A second anomaly, similar in size and intensity, was discovered about six miles to the northeast in Franklin County in the vicinity of Sullivan. This area was not studied in detail until the early 1940's. To determine the cause of the anomalies, the USBM drilled four holes at the Bourbon site in 1943-1944.4 The most productive hole penetrated four mineralized zones having a total thickness of 127.5 ft. These zones contained magnetite in rhyo-lite porphyry at depths between 1600 and 2000 ft. Additional iron ore below 2000 ft was considered a possibility at the time. Some years later, the USGS, Missouri Geological Survey, St. Joseph Lead Co., and others cooperated in sponsoring an aeromagnetic survey of the Bourbon-Sullivan area which resulted in discovery of a third high, about eight miles distant at Pea Ridge. This deposit, with an estimated reserve of 50 to 100 million tons of iron ore, is considered the main find, although other orebodies in the same general area are of definite interest.' When this discovery was announced, St. Joseph Lead also revealed plans to exploit the deposit jointly with Bethlehem Steel Co. A new corporation, Meramec Mining Co., was established, and 1962 was set as the target date for completing physical plant.2 Annual production goals of 2 million tons of beneficiated and pelletized iron ore were proposed. Preparation of the site for shaft sinking was begun in June 1957. Orebody and Character of Samples: Drilling to date has established the Pea Ridge orebody as a crescent-shaped pipe about 300 ft wide. Some drillholes were bottomed at 2800 ft in very good iron ore.6 he orebody is predominantly magnetite, although hematite and a mixture of hematite and magnetite occur in the upper areas and peripheral walls. Drillhole cores representing ore from different areas and depths of mineralization were grouped into composites for testing. These composites consisted of: 1) medium grade mixed hematite and magnetite, 2) high grade mixed hematite and magnetite, and 3) high grade magnetite. The medium grade ore came from three holes with depths of i350 to 1900 ft. The high grade mixed hematite and magnetite cores came from the 1790 to 2812-ft interval of one hole. Partial chemical analyses of the three samples, given in Table 1, reveal that all are excessively high in phosphorus and sulfur, and sample 1 is

Jan 1, 1960

By H. W. Meyer, H. N. Lander, F. D. Delve

A method of calculating the changes in blast-furnace performance brought about by burden and/or blast modifications is presented. Essentially the method consists of three simultaneous equutions derived from materials and heat balances. These equations can be used not only to evaluate quantitatively the effect of changes in process operating variables on furnace performance, but also to provide a useful means of evaluating changes in process variables which cannot be measured directly. It has been customary for a number of years to use simple heat and materials balances as a basis for assessing blast-furnace practice. A good example of the method used to set up these balances is that proposed by Joseph and Neustatter.1 This approach to process assessment has limited utility, however, in that it cannot be used to predict the furnace coke rate or production under new operating conditions. Using an approach based on multiple correlation of blast-furnace variables, R V. Flint2 has developed an equation which may be used to predict the change in coke rate that will result from some changes in operating conditions with a reasonable degree of accuracy. Although this equation has useful applications in production planning, it cannot be used to study the relationships between the operating variables and the fundamental thermochemi-cal characteristics of the process. In attempting to analyze the blast-furnace process quantitatively, the idea of dividing the furnace into zones3 may at first appear attractive. In our present state of knowledge, however, it is not possible to define with any accuracy the physical limits of such zones in relationship to their temperatures or to the reactions which may occur in them. Although its application is restricted, the zonal approach to blast-furnace analysis is useful in some instances. For example, the change in the calculated flame temperature in the "combustion zone" caused by injecting steam constitutes information which is helpful in understanding why the addition of steam to the blast is best accompanied by an increase in blast temperature. The zonal approach cannot, at the present time, be used to establish the relationships between process variables and process performance if the whole process rather than part of it is to be considered. One of the earliest approaches to the problem of relating blast-furnace operating variables to pro- duction and coke rate was that developed by Marshall.4 Essentially Marshall's work showed that it was possible to estimate the performance of a furnace by solving three simultaneous equations which consisted of rudimentary carbon and heat balances plus a further equation relating the production, wind rate, and the carbon burned at the tuyeres. Although these equations did not include all of the chemical and thermal variables of the process, their derivation and application seems to be the earliest attempt which achieved any success in relating prior furnace operating data to the calculation of furnace performance under different blast conditions. Work carried out in Germany has been directed mainly towards prediction of coke rates using material and thermal balances rather than statistical methods. wesemann5 used prior furnace operating data as part of the basis for predicting the change in coke rate accompanying a change in burden composition. This author employed a method of successive approximations to estimate the secondary changes in slag volume and stone rate brought about by the change in coke rate. The most recent analysis, which seems to have been developed concurrently with the thermochemical model presented in this paper, has been described by Georgen.6 This author has succeeded in improving on Wesemann's approach by expressing the total changes in the slag volume and stone rate in terms of the change in coke rate itself. This is accomplished in a manner similar to that used in the thermochemical model described in this paper. Although Georgen makes use of a calculated furnace heat loss, he does not relate the heat loss per unit of hot metal to the production rate as is done in the present work. Georgen's approach may be used to calculate the changes in materials requirements accompanying changes in furnace operation; it cannot be used to assess the resulting changes in production. The fact that blast-furnace behavior can be interpreted by consideration of the heat requirements of the process was demonstrated by Dancy, Sadler, and Lander.7 In the analysis of blast-furnace operation with oxygen and steam injection these authors showed that it was possible to account for the changes in production and coke rate

Jan 1, 1962

By W. M. Wojcik, R. F. Kowal

Oxygen and sulfur distributions in commercial, 5-ton ingots of killed, medium carbon steel are described. Oxygen distribution is found to vary with deoxidation practice. Irregular distribution of oxygen within ingots makes necessary special precautions in sampling of rolled products for analysis of oxygen. Oxygen distribution is discussed in terms of recently published solidification concepts which had been successfully applied to simpler cases of segregation. These concepts have been found inadequate to explain observed oxygen distributions. Convective movements of the liquid metal, as determined by tracer elements, are shown to be capable of accounting for the observed distributions of oxygen. IN an effort to explore the origin of surface and subsurface imperfections in pierced steel products, a study of oxygen and sulfur segregation was made on ingots cast in open-top and hot-top molds. The results of our previous investigations1"3 have indicated the importance of the location and amount of oxide inclusions in an ingot. Inclusions close to the surface of the ingot have been found to contribute greatly to the formation of imperfections in the surface of finished products. This study of the effects of deoxidation and casting practice on segregation and the resulting oxygen distribution in ingots was initiated to determine the parameters controlling the location of inclusions in an ingot. Segregation of solute elements during solidification of low-melting binary alloys has been studied in the past.1, 5 Formation and growth of inclusions in iron melts have been studied under specific conditions."- In spite of these and other recent studies,10-12 segregation during solidification of commercial, killed steel ingots is not well understood. Consideration of solidification rates, of segregation during solidification of the chill, dendritic, and central zones, and of material balances for the segregated elements has indicated that a simplified theoretical solidification model is not adequate. However, the observed high oxygen contents in localized volumes of the dendritic zone can be rationalized if additional effects of convection currents in the ingots, precipitation, and rapid growth of new phases are considered. EXPERIMENTAL PROCEDURE Steelmaking and Processing. A group of nine killed. medium carbon steel heats having compositions listed in Table I have been studied. The deoxidation and mold practices used were varied to give a wide range of steel oxygen contents. The amounts of aluminum added to the ladle and the ingot casting practices (hot top and open top) were the main variables. The steel was made by a duplex practice in 160-ton tilting basic open-hearth furnaces. All nine heats were top-cast into 24 by 24 in. big end down, fluted molds, to a height between 60 and 76 in., using both open tops and exothermic hot tops. The deoxidation practice and the tapping and teeming details for each heat and ingot studied are given in Tables II and III, respectively. Hot-top practice is indicated by the letter H following the heat designation. Furnace and ladle temperatures were measured by standard disposable-tip, Pt/10 pet PtRh thermocouples. Teeming-stream temperatures were obtained as described by Samways et al.,13 by immersing a Pt/10 pet PtRh thermocouple, covered by a silica sheath, into the teeming stream under the nozzle. The output of this thermocouple was recorded with Leeds & Northrup Speedomax potentiometer. Calibration of the latter thermocouples was based on the freezing point of a pure iron/oxygen alloy (2795°F). The accumulated errors of measurements were within ±10°F. The thermocouple measurements were supplemented in this investigation by continuous recording of a ratioing, two-color pyrometer (Shawmeter), protected from smoke by a blast of clean air within the sighting tube, and calibrated to read with better than ±10°F accuracy. Following teeming of three heats, P, R, and T, tracer elements were added to the steel in the molds to obtain a record of the progress of solidification. As soon as the teeming stream was shut off, a 0.010-in.-thick steel can containing a mixture of crushed standard ferro-titanium and ferro-vanadium (0.05 pet of each alloy element) was plunged into the middle of the steel pool to a depth of 6 in. In about 30 sec no indication of the can or its contents remained. The surface of the open-top ingots solidified in 20 to 30 sec. A study of liquid metal movement and the precipitation of oxides was facilitated materially by use of the tracer technique as titanium has a low distribution coefficient between solid and liquid steel while vanadium has a high distribution coefficient.

Jan 1, 1965

By Thomas W. Wälde

BACKGROUND Foreign investment has been a major factor in bringing about the substantial mining industries of Chile, Peru, Bolivia, Venezuela, Brasil and Guyana. But economic nationalism and sentiment against foreiqn domination of vital national industries grew in the 1960s and most major mining projects were transferred into state owner ship. Among the state mining enterprises formed were CODELCO - Chile, MINERO-PERU/ CENTRCMIN - Peru, CCMIBOL - Bolivia (in 1952), Hierro-PERU, GUY-BAU/BIDCO - Guyana, etc. New investment during that time was discouraged because it was subject to the restrictive conditions of the investment regulations of the Andean-Pact, a grouping of Chile, Bolivia, Peru, Ecuador, Venezuela and Colombia. The philisophy was that mineral resources were to be developed exclusively by national enterprises. Essential foreign inputs had to be acquired "depackaged" as separate purchases of equipment and technical assistance services. As a result of the worldwide economic recession which hit the mining industries in 1980-1982, many projects that were viable in 1970 were not developed by the new state enterprises due to lack of capital, managerial and technical abilities and due to problems with marketing. As a consequence of the long-term decline of metal prices, governments experienced difficulty in getting investment organized through national or foreign enterprises and have had to face up to the trade-offs between national control and active mineral development. A change has since taken place in governmental policies. The 1981 Peruvian mining law, the 1982 mining law of Uruguay, the 1979/1980 mineral promotion laws of Argentina, all witness the gradual shifting of emphasis from restriction to promotion. The investment rules of the Andean Pact have been progressively softened through national regulation and today are more or less irrelevant. Nationalizations and forced renegotiations have not occurred in the last few years. Countries have gone to great lengths (without much success) to re-attract foreign investment on terms that accommodate the political sensitivities of the South American countries and the practical requirements of investors and financiers. For this analysis, three contracts have been selected which reflect this accommodation in three South American countries, where miner a1 production plays a major role in the national economy. These con tracts reflect both the attitudes and traditions of the individual countries, but also mark the shift in mineral investment policies that has taken place. EL INDIO AGREEMENT The 1977 investment agreement between Chile and St. Joe Minerals marked a dramatic relationship between Chile and foreign mining investor s. In Chile, mining of copper has played a major role in the country's history. Large scale copper mining was initiated and developed by Kennecott and Anaconda. The nationalization of these two companies under the Allende government in July 1971 started a wave of nationalizations of foreign-held mining and petroleum operations since then in many parts of the world. The military government supported the new Chilean state mining companies ((30DELCO and ENMI) , but it also attempted to accelerate mineral development by prom ting foreign private investment, thus reversing the nationalistic policies followed by the Allende and the preceding Frei government. The new policy by the military government is expressed in Decreto-Ley 600 (1974) which governs foreign investment in Chile. Decreto-Ley 600 is

Jan 1, 1985

By Joe O. Ledbetter

INTRODUCTION Health physics as a profession really got a significant start during the Manhattan Project of World War 11. The Health Physics Society has recently published its 25th anniversary issue of the journal (June 1980). There was concern over radiation exposures during and after uranium production, especially about radium and its daughter products [Jackson 19401 and, as evidenced by the frequency of articles in the literature, there still is. The reason for this concern was expressed by Harley as "Workers engaged in the mining and pro- cessing of radium-bearing materials are exposed to dusts of the parent, to radon, and to the radon daughter products. In- haled radioactive particulates may be retained in the lung or redistributed to other organs of the body. Relatively minute de- posits of radioactive substances, particularly alpha emitters, have been clearly shown to be the etiological factor in a variety of injuries to industrial and re- search workers. " [Harley 1953] Emphasis in measurements has been placed on radium in water and radon in air, since these are the principal mobilized phases; however, it should be kept in mind that radium-containing particles do become suspended in air as aerosols and radon absorbs in liquids. Much of the uranium mining and production is being carried out aboveground. The principal difference between underground and surface (pit or leach) mining of uranium is the reversal in the relative importance of roles for the types of radiation dose. For aboveground the major radiation exposure is external gamma ray, whereas for underground it is internal alpha; for aboveground, the whole body penetrating is of greater importance than the lung alpha dose. AS a result of the politics involved and the law- suits for any and all diseases as being occupationally- caused, today , more than ever before, the successful performance of the activities connected with uranium production--before-, during-, and after-the-fact-- must include the provision of first class radiation protection. Such protection can be achieved by good measurements, thorough risk evaluations, and adequate controls. Meeting the ALARA (As Low As Reasonably Achievable) philosophy necessarily entails the determination of what is reasonable exposure. The necessary and sufficient elements of radiation safety under the ALARA dictum require a hard look at the dose versus effects data. There are times when the health physicist needs to make decisions of judgement rather than compliance with a well-defined regulation value. In order to facilitate such decisions, the real world must be separated from opinions that are merely artifacts of statistical variation and from the unprovable "what ifs" that are slanted to question the morality of any non-Luddite. UNITS VOCABULARY FOR DOSIMETRY There have been many radiation quantifying and dosimetric units introduced in the past. Fortunately, most of them did not catch on enough to become required knowledge for reading the health physics literature. The unit definitions necessary for our purposes here are the following: -curie (Ci)--unit of radioactivity equal to 3.7 x 10 10 disintegrations per second Webster&apos;s 19711 or the quantity of radionuclide that undergoes 3.7 x 10 nuclear transformations per second. Environmental levels of radioactivity are usually measured in picocuries (10-l2 Ci) per cubic meter for air and in picocuries per liter (pCi/~) for water and sometimes for air. .roentgen (R)--exposure dose of x or gamma rays that gives 1 esu of charge (either sign) to 1 cc of dry air @ STP. The roentgen is equivalent to an energy absorption of 86.7 ergs/g of air [Gloyna and Ledbetter 19691. .rad--radiation absorbed dose of 100 ergs per gram of absorber. The SI unit for absorbed radiation dose is the Gray; 1 Gy = 100 rads. orem--radiation absorbed dose of 1 rad times the quality factor (QF) for that radiation. The QF is 1 for x rays, gamma rays, beta rays, and posi- trons. For heavy ionizing particulate radiation, QF is a function of the amount of energy trans- ferred per unit length of travel, i.e. , the linear energy transfer (LET); the values of QF:LET in keV/um are as follows: 1:<3.5; 1-2:3.5-7; 2-5:7-23; 5-10:23-53; and 10-20:53-175 [Morgan and Turner 19 671 . For radiobiology, relative biological effectiveness (RBE) is recommended for use instead of the quality factor above that is for radiation protection: the RBE is the ratio of the dose of 200 kVp x rays to the dose of radia- tion in question (both in rads) to cause the same

Jan 1, 1980

By Carlos G. Valenzuela

The value generally accepted for stacking-fault energy, of copper has been approximately 40 ergs per sq cm based on Fullman&apos;s2 value for the coherent twin-boundary energy and the assumption that is twice the twin boundary energy However, Thornton and coworkers8 determined that the lower limit of for copper is approximately 60 ergs per sq cm, based on measurements of dislocation-node radii. They suggested that the assumption of = 2t is invalid. It is the purpose of this note to present results which indicate that the values of obtained by measurement of twin-grain boundary intersections and the values obtained by measurement of dislocation-node radii are actually compatible. The most reliable values for of the a brasses, based on electron-microscope observation of dislocation nodes, are probably those values reported by Smallman and Green6 who applied the Siems correction (1961) to data obtained by Howie and Swann.3 These values shown in Fig. 1 give an extrapolated value of approximately 70 ergs per sq cm for pure copper. In the present work, Fullman&apos;s method for determining the stacking-fault energy of copper was extended to the a brasses. High-purity copper (99.999 pet) and high-purity zinc (99.999 pet) were mixed in proportioned amounts and melted in sealed and evacuated quartz tubes. The alloys were homogenized for a week at 750°C and chemically analyzed by means of X-ray fluorescence. These alloys, along with a specimen of pure copper, were rolled to 98 pet reduction and a thickness of 0.009 in., resealed, and annealed for 40 hr at 715°C. Values for the ratio of twin-boundary energy to the grain-boundary energy, it gb, were obtained from measurements of dihedral angles formed at the intersections of twin boundaries and grain boundaries by using Fullman&apos;s2 mechanical analogy of surface tensions acting at the intersection of an annealing twin and a grain boundary. The angles between the twin traces and the grain boundaries were measured for a large number of twin-grain boundary intersections at a magnification of X500 using a rotating mechanical stage on a Reichert metallograph. The rotary stage has a calibrated angle scale with vernier so that measurements can be made to 0.1 deg. The mean twin-grain boundary energy and standard deviation were calculated for copper and each of the brasses by the use of an IBM 7072 computer. It was found that the mean value of gb stabilized after approximately 100 twin-angle measurements. This was determined by plotting the mean against the number of angles measured. Since the measured angles deviate from true dihedral angles, a correction factor for grain orientation, discussed below, was applied. The stacking-fault energy was then calculated from these values and the values of grain-boundary energy derived by Taylor.7 The data obtained are tabulated in Table I. Values for stacking-fault energy are plotted in Fig. 1. The value of gb for the specimen of 1.03 pet Zn is close to the value obtained by Fullman2 for OFHC (99.98 pet) copper, 0.045. It is believed that the purity of the copper affects gb significantly. The 99.999 pet purity Cu used in this investigation yielded a value of yt/ygb, 0.76, which is much higher than that obtained by Fullman. Additional evidence suggesting that the purity of

Jan 1, 1965

By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.&apos; Also, tantalum in combination with rhodium,&apos; iridium,&apos; or platinum&apos; stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963

By A. U. Seybolt

In part 111&apos; of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report&apos; it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By L. A. Wilson, P. J. Root

The relative costs of heating a reservoir by steam injection and by combustion have been examined. The comparison was based on a model similar to that proposed by Chu.&apos; The cost of boiler feed water, the price of fuel, pressure and plant capacity were parameters in determin-ing the costs of air compression and steam generation. The analyses compare the cost of heating to the same radius by the two methods. Results suggest that the two primary factors for comparison are the price of fuel and the amount of crude burned during underground combustion. The cost of fuel has a greater effect on the cost of heat from steam than it does on its cost by combustion. As a result, analyses indicate that when the price of fuel is low, steam may be unequivocally cheaper than air. The influence of heat loss is such, however, that as the heated radius increases combustion becomes relatively more competitive depending upon the amount of crude burned. This implies that steam may be cheaper for small stimulation jobs (huff and puff) but combustion may be more economically attractive for heating large areas (flooding). INTRODUCTION Use of thermal methods of recovery is an accepted fact today. After an induction period of several years, processes are being widely used that involve reservoir heating to augment recovery. Of the several techniques, steam injection and forward combustion appear to be destined to dominate the field. Although the objectives of both are the same, the basic differences between generating heat in situ and injecting heat after surface generation influence the cost in different ways. This study compares the cost of heating a reservoir either by steam injection or by forward combustion. There has been no consideration of recovery. Presumably, recovery from the swept region would be high in either case. The sole consideration was the cost of heating to the same radial distance by either process. PROCEDURE THE MODEL The basis for comparison was a mathematical model similar to that used by Chu&apos; for combustion. The model simulates a radial heat wave in two-dimensional cylindricaI coordinates. It includes heat generation, conduction and convection within the reservoir and conduction in the bounding formations. Thus, heat losses from the formation are considered. Three significant modifications were made. 1. Equal logarithmic increments rather than equal increments were used for the mesh spacing in the r direction. By this technique large distances were simulated with relatively few mesh spaces. 2. A backward difference approximation to the convection term was used to avoid troublesome oscillations which result from a central difference approximation when the convection term is large. 3. The radial increments of the combustion zone motion were not necessarily uniquely related to the mesh configuration. The cumbersome step function introduced by the heat of vaporization of steam was circumvented by assuming the enthalpy of the steam to be a linear function of temperature between reservoir temperature and steam temperature. This is equivalent to assuming an average heat capacity numerically equal to the difference between the enthalpy of saturated steam and the enthalpy of water at reservoir temperature divided by the difference between the two temperatures. Heat losses obtained by this model are in essential agreement with those obtained by the analytical solution of Rubenshtein.&apos; A detailed description of the model is presented in the Appendix. Using the model, the times required to heat to particular radial distances were obtained as a function of injection rate and other physical parameters. For the steam case, injected fluid was assumed to be saturated steam at pressures of either 500, 1,000 or 1,500 psia. The corresponding temperatures are 467, 544 and 596F, respectively. Thickness ranged from 10 to 50 ft and injection rate ranged from 100,000 to 1 million Ib/D. Reservoir and overburden temperatures at the injection well were assumed to be that of saturated steam at the injection pressure. The effect of maintaining the overburden temperature at the well at a different temperature (initial reservoir temperature) was examined with no significant change in behavior. The influence of wellbore heat losses for the steam case was determined in the following manner. The rates of heat loss as a function of time were estimated using an approach similar to that suggested by Ramey." he data were based on injection through 2%-in. tubing in 7-in. casing. Integration of these data over the entire iniection period yielded the total heat loss. Total heat losses were then corrected to their equivalents in steam (this number resulted from dividing the total heat loss by the latent heat). This was considered additional steam required to accomplish the reservoir heating and the total cost was increased accordingly.

Jan 1, 1967

By Peter J. Szabo

INTRODUCTION The time period from the detailed feasibility study to the post investment audity usually ranges from three to eight years depending upon the nature of the mining project considered. It is the only after the post investment audit that we know the adequacy of the assumptions made concerning operational risk assessment in the detailed feasibility or acquisition economics. The post investment audit results from numerous mining projects can best be described by a verse by John Greenleaf Whittier&apos;s Maaud Muller. It reads "For all sad words of tongue or pen the saddest are these &apos;It might have been!"&apos; Dissecting the negative results of numerous mining projects we find faulty assumptions concerning markets, geology, capital investment and operational risk assessment. Although in hindsight many of these assumptions could have been considered impossible or impracticle to have forecast with any degree of certainty, we find that refined assumptions concerning operational risk assessment could have been made with only a modicum of additional "Due Diligence". Anyone who invests in a mining property should employ a much higher discount rate of future cash flow, (usually in the minimum range of 25%-30%), than he would expect from such safe investments as Treasury Bills or high grade Utility Bonds. The nature of this steep discount translates to a large uncertainty concerning the timing and actualization of assumptions contained in the detailed feasibility study. We must remember that when a project gets beyond 20 years, any contribution to the value of the project of cash flow is minimal due to the nature of the discounting process. Thus for each full or partial day lost in the development or early operation stage of a project, the financial impact will be greater than similar lost days later on in the project. Adequate operational risk assissment is particularly critical when bidding on competitive tenders for coal deposists in remote locations such as the Bowen Basin in Queensland, Australia. Because of the market attractiveness of these coal deposits for supplying end users in the Far East, Middle East and Europe, state governments require competitive tender biddings via the Authority to Prospect process. Front end bonuses and super royalty payments must be commited before the actual mining conditions are known. Time to submit firm offers from the actual request for proposal vary from 90 to 120 days. Thus any operational risk assessment must be detailed, realistic and reflective of the actual project. When one searches the literature, one finds limited qualitative data on operational risk assessment in valuation papers. Usually this facet of valuation takes a secondary role to such areas as reserves, markets, and environmental considerations. When one comes to the question of operational risk assessment more often than not one finds the use of "rules-of-thumb", such as tons per man shift, average production, average seam height, etc., are used to forecast results on which banks and other financial institutions are required to make investment decisions. Because of the extremely competitive environment of the 1970&apos;s and 1980&apos;s numerous financial institutions approved loans without adequate "Due Diligence", and are currently paying a steep price in terms of non performing loans and charge offs. One must always remember that each operation is unique with its own characteristic

Jan 1, 1985

By D. J. Schmatz

DISCUSSION OF RESULTS The qualitative correlation between low-temperature ductility and prior high-temperature creep strain in nickel obtained in this investigation confirms the result obtained on high-purity brass by Chen and Machlin. However, the quantitative effect is much smaller in nickel. Comparison can be made on the basis of a prior high-temperature strain that is a certain percentage of the total high-temperature elongation to rupture. In the research of Chen and machlin, the prior high-temperature strain of 1/2 pct equaled 8.5 pct of the total high-temperature elongation at rupture. For nickel, in our experiments, 8.5 pct of 21.2 pct equals 1.8 pct. For eh = 1.8 pct, the loss in ductility in percent equals x 100 = b.5 pct. That is, for equivalent bo Formation of Beta Manganese-Type Structure in Iron-Aluminum-Manganese Alloys D. J. Schmatz IRON-aluminum alloys have gained much interest in the past few years for use as a base material for elevated-temperature alloys because of their excel- high-temperature strain the loss in low-temperature ductility is 8.5 pct for nickel as compared to 60 pct for pure a, brass. It is also interesting to note the observation that in nickel the low-temperature fractures, even at the most extreme high-temperature pre-strain, were partly trans crystalline and partly intercrystalline. In the case of a brass, these fractures were completely intercrystalline. According to the data on the percent of the grain boundary area that is cracked, at 22 pct high-temperature elongation, about 12.5 pct of the grain boundary area does not carry load. Thus, the inter-crack areas are carrying a stress that is about 11 pct higher than the nominal stress. A simple model predicts that the overall elongation, which is primarily the elongation in the bulk of the specimen, will correspond to the nominal stress when the stress in the intercrack area equals the tensile strength. Quantitatively this model predicts the equation The form of this equation will agree with that found if the strain-hardening exponent, n, equals unity. Actually this model is too gross an approximation to yield good quantitative results. The question naturally arises as to whether in ordinary hot-working, such as hot-rolling, intercrys-talline cracks are introduced that affect the low-temperature properties. It appears that the answer is that such a possibility cannot be overlooked, if the hot-working induces tensile stresses at temperatures above the equicohesive temperature and if the material tends to be notch sensitive at low temperature. ACKNOWLEDGMENT This research was supported by the Aeronautical Research Laboratory, Directorate of Research, Wright Air Development Center, United States Air Force. REFERENCES lC. Zener: Fracturing of Metals, 1948, Cleveland, ASM. &apos;H. C. Chang and N. J. Grant: Mechanism of Intercrystalline Fracture. AIME Trans., 1956, voL 8, p. 544; lownal of Metals, May, 1956. &apos;E. S. Machlin. CreepRupt ure by Vacancy Condensation, AIME Trans., 1956, vol. 8, p. 106; lownd of Metals, February, 1956 &apos;C. Chen and E. S. Machlin: On a Mechanism of High-Temper at ure Inter-crystalline Cracking, lownd of Metals, July. 1957. p. 829. Alloys lent oxidation resistance. Binary alloys of aluminum in iron are ferritic and consequently have poor hot strength. Alloys of iron-aluminum-manganese were made in an attempt to produce an austenitic alloy containing sufficient aluminum to retain the oxidation resistance of binary alloys of iron-alumi-

Jan 1, 1960

By F. V. Lene, E. J. Westerman

The recrystallization behaviors of two extruded and cold-drawn experimental sintered aluminum powder alloys, containing 1.75 and 3.0 pct Al2O3 by weight, were compared with that of extruded and cold-drawn commercially pure alumirzum. The kinetics of recrystallization of the alloys are described semiquantitatively. For the alloy containing 1.75 pct A l203 the rates of nucleation and of growth were also semiquantitatively determined. THE most striking property of aluminum alloys strengthened by a dispersion of Al2O3, the so-called SAP alloys, is their stability at elevated temperatures. One of the manifestations of this stability is their resistance to recrystallization after they have been cold worked. Most of the commercial grades of either the Swiss SAP or of Alcoa&apos;s Aluminum Powder Metallurgy Products have not been recrys-tallized after cold working, even when they are heated for a long time at a temperature near the aluminum melting point. Lenel, however, observed that the dispersion strengthened aluminum alloys with a larger spacing between the oxide particles than that of most commercial grades would recrys-tallize.1 It appeared to be of interest to further investigate the mode and kinetics of recrystallization of these alloys, and to compare their recrystallization behavior with that of commercially pure aluminum. Because homogeneous deformation of these SAP alloys in tension did not provide sufficient cold work to induce recrystallization, they were cold worked by wire drawing; the nonuniformity of this deformation unavoidably complicated the interpretation of the recrystallization studies. EXPERIMENTAL DETAILS Extrusions—Two types of sintered aluminum powder extrusions were used in this study. One type, designated AT-400, was produced from Reynolds atomized aluminum powder consisting of spherical particles averaging 3µ in diam and containing 1.75 wt pct of Al2O3. This powder was very similar to the R3M powder from which extrusions were previously prepared with an average spacing of 0.9µ between oxide particles.2 The second type, designated MD 2100, was produced from Metals Disintegrating Co. flake powder containing 3.0 wt pct of Al2O3, with an average flake thickness of 0.8µ. The average spacing between oxide platelets in MD 2100 extru- sions was 0.45µ.2 Powder compacts of 3/4-in. diam were extruded at 1000°F into 0.097-in. diam (AT-400) and 0.093-in. diam (MD 2100) wires by methods previously described.3 In order to compare the recrystallization behavior of sintered aluminum powder extrusions with that of wrought commercially pure aluminum 3/4 in. rod stock of 1100 F aluminum was extruded at 1000°F into 0.102-in. diam wire. Wire Drawing—Tungsten carbide dies were used for the AT-400 and 1100 F alloys. They had an included angle of about 15 deg and reduced the wire area approximately 7 pct per pass. Steel dies with an included angle of 11 to 13 deg and an average reduction per pass of 10 pct were used for drawing the MD 2100 alloy, because drawing this alloy through the carbide dies produced overdrawing defects. Heat Treatment—The cold-drawn wires were cut into small samples, and the deformed ends were etched off. The samples were each wrapped tightly in a single layer of aluminum foil, and individually isothermally annealed in a lead bath. Metallography—The modes and kinetics of recrystallization were determined by metallography. Mounted and polished specimens were anodized in a solution of 1.8 pct HBF4;4 examination under polarized light clearly revealed their grain structures. The recrystallized grains were generally much larger than those of the unrecrystallized matrix, and could clearly be distinguished because they alternated between maximum and minimum light reflection when the microscope stage was rotated, while the unrecrystallized matrix had a comparatively homogeneous "salt and pepper" structure. The fractional recrystallized volumes of the dispersion hardened alloy wires were determined by cutting and weighing of recrystallized and total transverse areas on photomicrographs. The recrystallized grains in the 1100 F alloy were too small to be cut out individually; therefore a combination of cutting and lineal analysis was used in this case. RESULTS AND DISCUSSION Modes of Recrystallization—The modes of recrystallization of the three alloys varied widely. In the 1100 F alloy nucleation and growth started in the region midway between the center and the surface;

Jan 1, 1961

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper&apos; on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.&apos; In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.&apos; The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1&apos;9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

By F. H. Ellinger

TI HE crystal structure of neodymium has been re-A ported by Quill1 and by Klemm and Bommer"s to be hexagonal-close-packed, Strukturbericht-type A3, with a, = 3.650.4, c, = 5.890.4, c/a = 1.614. Klemm and Bommer,% owever, pointed out that the observed intensities of the lines of the neodymium powder pattern agreed only in part with the intensities calculated for the type A3 structure, and that the neodymium powder pattern showed extra lines which could not be traced to impurities. They found that these extra lines could be accounted for by doubling the c-axis, but apparently they did not consider their evidence to be sufficiently conclusive to justify reporting the doubled c-axis. In the present work, the structure of neodymium was found to be double hexagonal-close-packed. The neodymium metal used in the present investigation was obtained through the courtesy of F. H. Spedding of the Ames Laboratory. Its major impurity was stated to be 0.03 pct Ca. The author&apos;s spectrographic analysis indicated high purity and carbon was determined to be less than 30 ppm. X-ray powder specimens were prepared from filings stress relieved in vacuum at 200°C for 50 hr. Powder photographs were taken in an 114.6 mm diam camera (Straumanis film mounting) at room temperature and in a 19 cm diam Unicam high temperature camera at elevated temperatures. Copper x-radia-tion was used for all the photographs. The powder pattern of neodymium was found to index to a hexagonal unit cell with dimensions, as determined from the high angle Ka doublets, of: a.= 3.655+0.001.4; c, = 11.796+0.004.4; and c/a = 3.227 at room temperature. The measured density of neodymium shows that this cell contains 4 atoms, the calculated density is accordingly D, = 7.02 g per cu cm. The diffraction data for the first 15 lines of the powder pattern are listed in Table I. In a double hexagonal-close-packed unit cell, the 4 atoms would be in the positions (0,0,0), (0,0,%), (1/3, 2/3, 1/4), and (2/3,1/3,%) of space group P 6,/mmc. On the basis of these positions, the relative intensities of the reflections were calculated using the expression: 1+cos2 20 I oc \Frp 1 &apos; sin2 0 cos 0 where F is the structure factor and p is the multi- plicity factor. Since absorption was not taken into consideration, comparison of observed and calculated intensities should be made only for neighboring reflections. Each atom has 12 neighbors, 6 in the basal plane at a distance of 3.655.4 and 3 above and 3 below at the closer distance of 3.626.4. These distances correspond to an average radius of the neodymium atom of 1.820.4. The description of this structure in terms of A, B, and C close-packed layers of atoms is ABAC ABAC. ...... The structure repeats every fourth layer and the stacking sequence of the second, third, and fourth layers corresponds to cubic-close-packing of atoms. A series of powder photographs taken at successively increasing temperatures up to 680a10"C revealed that the double hexagonal-close-packed structure is stable up to this temperature. Acknowledgments The authw wishes to thank W. H. Zachariasen and A. S. Coffinberry for their helpful comments on this work and also Marion Gibbs for measuring the diffraction films. This work was sponsored by the United States Atomic Energy Commission.

Jan 1, 1956

By P. N. Richards, M. K. Ormay

The present Paper extends the previous work on cold reduced, low carbon steels to preferred orientations developed after various heat treatments. In recrystal-lized rimmed steel, cube-on-comer orientations increased with cold reductions up to 80 pct. Above that {111}<112> and a partial fiber texture with (1,6,11) in the rolling direction dominated. During grain growth, cube-on-corner orientations have been observed to grow at the expense of {210}<00l>. In re-crystallized Si-Fe (111) (112) and cube-on-edge type orientations are dominant near the surface and the (1,6,11) texture near the midplane for reductions up to 60 pct. With larger reductions {111)}<112> and the (1,6,11) texture are dominant. In cross rolled capped steel a relationship of 30 deg rotation was observed between the (100)[011] of the rolling texture and the main orientations after re crystallization. Most orientations present in recrystallized specimens can be related to components of the rolling texture by one of the following rotations: a) 25 to 35 deg about a (110) b) 55 deg about a (110) C) 30 deg about a (Ill) THE orientation texture of recrystallized steel is of interest where the product is to be deep drawn, because preferred orientation is related to anisotropy of mechanical properties such as the plastic strain ratio (r value);1,2 and in electrical steel applications where a high concentration of [loo] directions in the plane of the sheet improves the magnetic properties of the material. It is interesting to note that both these aims are to a large extent achieved commercially, even though the orientation texture of cold rolled steel does not show large variation3 and the recrystallized orientations are generally given as being related to the as rolled orientations mostly by 25 to 35 deg rotations about common (110) directions.4-6 There is, as yet, no single completely accepted theory on recrystallization. The three mechanisms that have been investigated and discussed are: a) Oriented growth b) Oriented nucleation c) Oriented nucleation, selective growth Largely from the observations of the recrystalliza-tion process by means of the electron microscope,7-11 there is now considerable evidence that the "nucleus" of the recrystallized grain is produced by the coalescence of a few subgrains to form a larger composite subgrain, which finally grows by high angle boundary migration into the deformed matrix. From the intensive work on the recrystallization of rolled single crystals of iron, Fe-A1 and Fe-Si al-loys4-" he following observations have been made: 1) The change in orientation during primary recrys-tallization can usually be described as a rotation of 25 to 36 deg about one of the (110) directions. 2) The (110) axes of rotation often coincide with poles of active (110) slip planes. 3) If several orientations are present in the cold rolled structure, the (110) axis of rotation will preferably be a (110) direction that is common to two or more of the orientations. 4) With larger amounts of cold reduction (70 pct or more) departure from these observations became more frequent. 5) After larger cold reductions, rotations on re-crystallization about (111) and (100) directions have been observed. K. Detert12 infers that a rotation relationship of 55 deg about (110) directions is also possible, by stating that the recrystallized orientation {111}<112> can form from the orientation {100}<011> of cold reduced partial fiber texture A.3 The observation by Michalak and schoone13 that (lll)[l10] formed during recrys-tallization in fully killed steel containing (111)[112],— as well as (001)[ 110] which is related to the {111}<011> by a 55 deg rotation about <110>-implies a possible 30 deg rotation relationship about the common [Ill]. Heyer, McCabe, and Elias14 have recrystallized rimmed steel after various amounts of cold reduction, by a rapid and by a slow heating cycle and found that the preferred orientations strengthened with increased cold reduction. The most pronounced orientation up to about 70 pct cold reduction was found to be {1 11}< 110>, after 80 pct cold reduction both {111}<110> and {111}<112>, after 85 and 90 pct cold reduction, {111}<112>, and after 97.5 pct cold reduction it was {111}<112> and (100)(012). In the present work, the orientation textures of the recrystallized specimens are examined under various conditions of steel composition, amount and method of cold reduction, and method of recrystallization. The relationships between the preferred orientations of the as rolled and recrystallized specimens, and the conditions for the formation of the various orientations during recrystallization are investigated.

Jan 1, 1970

By J. E. Powell, F. H. Spedding

WHILE rare earths are reported to be widely distributed in nature and are not really rare," in practice, there are only a few minerals which are sufficiently rich in rare earths to serve as practical sources. Perhaps the best known of these is monazite which is a phosphate mineral containing rare earths and thorium. This mineral occurs as a dense brown sand in gravel beds and is particularly rich in the light rare earths of the cerium subgroup. This mineral is processed commercially for its thorium, cerium, and lanthanum content, and, consequently, furnishes rich concentrates from which neodymium, praseodymium, samarium, europium, and gadolinium may be obtained. Unfortunately, monazite is rather lean in rare earths heavier than gadolinium. A second mineral which is rich in the light rare earths is bastnasite, a fluoro-carbonate. Extensive deposits of this ore have been discovered in the western United States and have received considerable newspaper publicity in recent years. While bastnasite is very rich with respect to cerium, lanthanum, and neodymium, it contains even less heavy rare earths than does monazite. One of the better sources of heavy rare earths of the yttrium subgroup is gadolinite, a black silicate rock from which the rare-earth content can be extracted readily by acid leaching. It is obtained chiefly from Norway at the present time, although there are known deposits in the United States. Other sources of heavy rare earths include fergu-sonite, euxenite, and samarskite which are refractory tantalo-columbate ores. These minerals require caustic fusion or reduction to carbides with carbon before the rare-earth content can be extracted. All of the minerals which are rich in the heavy rare earths contain yttrium as a major constituent. After the rare earths have been extracted as a group from an ore by chemical means, it is generally convenient to precipitate them from acid media with oxalic acid in order to eliminate certain non-rare-earth impurities such as iron, beryllium, etc., which are usually present. The oxalate can then be readily ignited to R2O3. The oxide can be dissolved in acid and is the starting point for subsequent separation into the pure components. Perhaps the principal reason why the rare earths have not been studied as extensively as other elements of the periodic table, whose natural abundances are comparable, is that they are extremely difficult to separate from each other by the usual chemical means. Prior to 1945, the separation of one trivalent rare earth from another was a laborious process. All separations were based on repeated fractionation processes, i.e., fractional precipitation, fractional decomposition, fractional crystallization, etc. These processes were repeated from a few hundred to many thousands of times in order to obtain individual rare-earth salts of reasonable purity. Of course, mention should be made that, in the few cases where a rare earth could be oxidized or reduced to a valence state other than three, more conventional chemical means could be utilized to separate the oxidized or reduced ion from the other normally trivalent rare earths. The ionic states which deserve special mention are CeIV, SmII, Eu11, and Yb11. When it is possible to remove an element of the series efficiently, due to an optional valence state, its immediate neighbors also become easier to isolate. For example, binary mixtures of lanthanum and cerium, and praseodymium and cerium can be obtained by a relatively small number of fractional operations. The tetravalent state of cerium then allows the complete resolution of the binary mixtures by ordinary chemical means. Although the tetravalent state of cerium has been known for a long time, the divalent states of samarium, europium, and ytterbium were not used extensively in separations prior to 1930 because they are relatively unstable in aqueous media.&apos;-" No attempt will be made to give a comprehensive review of the extensive literature dealing with the separation of rare earths. Rather, this paper will be confined to a review of those methods which have been developed at Iowa State College during recent years, and which have proved extraordinarily successful for the isolation of highly pure rare earths in quantity. It was obvious that, if pure rare earths were to become generally available, methods would have to be developed wherein the thousands of fractional operations made necessary by the similarity of rare-earth properties could be performed automatically. The development of chromatographic techniques and ion-exchange resins appeared to offer a mechanism by which this objective could be accomplished. A number of early attempts were made to separate rare earths by these means; for example, Russell and Pearce12 passed a mixture of rare earths through a cation-exchange column and reported

Jan 1, 1955