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By Greenleaf W. Pickard

The Parral mining district is located in the southern part of the state of Chihuahua in north-central Mexico, in the border area of the physiographic provinces of the Mesa Central and the Sierra Madre Occidental, at an average elevation of 1700 meters. This is one of the most highly productive lead-zinc districts of Mexico. The principal operating units are the Prieta, Santa Barbara and San Francisco mines. The Santa Barbara-San Francisco del Oro area is located 25 kilometers to the southwest of the Prieta mine. It has a system of generally narrow veins in fault zones, entirely in the shale series. The Santa Barbara veins follow long, persistent fractures, while the San Francisco del Oro veins are in relatively short fractures. The Veta Colorada structure, located 5 kilometers to the northwest of the Prieta mine, was a major producer of high grade silver ore with low lead-zinc content during the eary 1900's. It follows a major north-south fault zone in andesite and is noteworthy for a number of wide oreshoots of limited vertical extension along its 10 kilometer length. The Palmilla and Esmeralda mines are on the south end of the Veta Colorada structure. Numerous smaller mines are operating in the Parral area. During the last 45 years the Prieta mine has produced approximately 15,000,000 tons of complex sulfide ore, principally from one single vein. Extensive stoping has

Jan 1, 1970

By J. L. Thompson

Lime made in a coal-fired rotary kiln has two distinct parts: the interior of the pebble which constitutes about 90% to 95% of the mass, and the surface dust layer which is the remaining 5% to 10%. Uncalcined carbonate and impurities in the product may be present and will not contribute to the hydration reaction. Sulfur, in the form of calcium sulfate, inhibits the hydration reaction out of all proportion to its actual weigh- percent concentration (perhaps more than 100 times). If the stone contains dolomite, this will also inhibit the reaction as its rate of hydration may be nearly three orders of magnitude slower than that of calcium oxide. Early in the hydration reaction dolomite appears practically intert, but given sufficient time, it will hydrate. The heat of reaction is nearly the same as for calcium oxide, but the time necessary for complete hydration may be hours; whereas for calcium oxide it is only fractions of a second. The dust layer on the surface also inhibits hydration as it contains a collection of compounds which have low heats of hydration. This layer can tie up additional calcium and delay or prevent its reaction. In addition to these chemical processes, an important physical characteristic of the lime is its specific surface area. This is effected by the thermodynamics of calcination and the original stone grain chemistry. All of these factors are agglomerated in the gross slaking rate of lime.

Jan 1, 1980

By Otto W. Nuttli

The magnetic method of prospecting is well suited to determination of faulting in the basement rock. In addition to establishing the horizontal position of the fault, it often furnishes valuable information concerning the depth and amount of faulting. Consider a simple case of a vertical fault, represented in cross-section in Fig. 1. Let AA' represent the plane of observation (ordinarily the surface of the earth), and BB'B"B"' the upper surface of the basement. Assume that the sedimentary rocks are nonmagnetic, so that the magnetic susceptibility of the material above the basement is zero. Let k indicate the susceptibility of the basement rock, a- the density contrast between it and the neighboring sedimentary rocks, and t the amount of vertical displacement.

Jun 1, 1955

By B. J. Dotson, P. N. McCreery, R. L. Slobod, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By P. N. McCreery, R. L. Slobod, B. J. Dotson, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By Paul Billingsley

Introduction. THE Georgetown mining district is located in Deerlodge county, Mont., about 20 miles west of Anaconda. It lies along the divide between the headwaters of Warm Springs creek, draining eastward, and Flint creek, flowing west and north through the Philipsburg valley. The actual divide is formed by Cable mountain, a narrow ridge running north and south, terminating to the south in low hills overlooking Georgetown lake, and to the north in a high, rugged plateau that falls off to the west to the wide valley of Flint creek. Oil the eastern, or Warm Springs, slope of Cable mountain is the Cable mine, with the Hidden Lake mine a few miles north. On the western slope is the Southern Cross group, with smaller mines, the Twilight, Cincinnati, Red Lion, and Big Bill, at intervals to the northward. The Georgetown mines lie in the hills south of Cable mountain; the Philipsburg mines, of which the Granite Mountain, Bimetallic, Hope, and Trout are the chief, form a separate group to the north, overlooking Flint Creek valley and Philipsburg. (See Fig. 1.1) The region ranges in elevation from 5,000 to 9,000 ft. It is, with the exception of the lower valleys, well timbered with small fir and pine, although Cable mountain and the higher summits to the northward rise slightly above timber line. The main valleys have the smooth contours of glaciation, and their mouths are frequently choked with morainal deposits.

Jan 9, 1913

By Robert D. Lonqyear

SOMEWHAT biased by pride in twentieth century achievements, most of us mining engineers and diamond-drill operators look upon core drilling as a relatively modern practice. The invention of the diamond drill is generally ascribed to Rudolf Leschot, who made use of diamonds in 1846 in drilling blast holes in the Mont Cenis tunnel in Switzerland. In vain we search Agricola and other early writers on mining for signs of diamond drilling. We have, therefore, concluded that it was unknown until the middle of the last century. The trouble with this conclusion, as most prospectors will tell us, is that we "don't dig deep enough"; for it now appears that the archeologists have been putting one over on us for the last fifty years.

Jan 1, 1936

US 4,189,461-Hydrometallurgical extraction of values from a sulfide ore of copper, silver, nickel, cobalt, molybdenum or zinc Ore is leached in a first stage with an aqueous nitric acid leach liquor and In a second stage the preleached mineral is oxidized with nitrogen dioxide to enable the metal values to be solubilized. The second-stage leach liquor is routed to the first stage, while first-stage liquor is subjected to electrolysis or other treatment for values This patent is a continuation- in-part of US Patent No. 4,132,758, dated Jan 2, 1979. R E Lueders and T C Franiewicz, assigned to Kennecott Copper Corp Feb. 19, 1980. 8 pp. (423-27). Filed. 2-23-78 (880,552). (Drawing below)

Jan 1, 1982

By Edel Moldenke

BURMA has long been known for its ruby, tungsten, and tin deposits, and, lately, for having the largest lead-zinc mine in the world, the Bawdwin Mine of the Burma Corpn. All the coal used, however, is imported from Calcutta; this is a bituminous coal of about 11,000 B.t.u., 24 per FIG. 1.-MAP SHOWING LOCATION OF COAL FIELDS AND TRANSPORTATION ROUTES. cent. ash, and costs about $8 per ton. Bituminous coal has not, thus far, been found, but many lignite deposits are known. The most promising lignite deposits are in the Namma field, Fig. 1, situated in the Northern Shan States of Upper Burma, about 30 mi. south of Lashio, the terminus of the Burma Railway, 750 mi. north of Rangoon. The

Jan 7, 1921

1944 WALTER HULL ALDRIDGE New York, N Y 1946 PETER M ANDERSON Johannesburg, South Africa 1946 CHARLES CAMSELL Ottawa, Ont, Canada 1946 CHARLES AUGUSTUS CARLOW Fife, Scotland 1946 CECIL H DESCH London, England 1946 WILLIAM FRASER London, England 1917 HERBERT HOOVER New York, N Y 1941 DANIEL COWAN JACKLING San Francisco, Calif 1939 HENRY KRUMB New York, N Y 1942 ESSINGTON LEWIS - Melbourne, Vic , Australia 1921 C MCDERMID London, England 1944 WALTER C MENDENHALL Washington, D C 1942 PAUL DYER MERICA New York, N Y 1913 EZEQUIEL ORDONEZ Mexico City, Mexico 1938 A M PORTEVIN Paris, France 1937 GEORGE S RICE Washington, D C 1934 T A RICKARD Victoria, B C, Canada 1946 JOHN R SUMAN Houston, Texas 1946 WONG WEN-HAO Chungking, China

Jan 1, 1952

By John V. Beall

There were no easily identifiable tourists. Everybody carried attaché cases and sported the buttoned-down look in dress. They were all there at the Hotel Indonesia to make a deal. But deals don't come quickly over there and those that staved and persevered became bored. They clung to the air conditioning of the Hotel and sought hobbies to while away the weeks-and even months. It is not an easy life but it can pay off fog sonic company. The government officials are neither stupid nor lazy. They are new at their jobs. Many are ex-army men and they know they must learn before they can enter into a contract with confidence. So they take time, and time is on their side.

Jan 1, 1970

By W. J. Slatosky

As a means of effecting better control of endpoint temperatirres at the Jones & Laughlin basic oxygen furnace plant, a set of mathematical equations has been developed. The eqlutions are the product of a themlochemical anaysis of the process and aye designed to calculate the required scrap, lime, and hot metal additions in terms of a number of independent variables. Results of test heats have warranted adoption of this technique by the Prodrrction Department. BECAUSE of the autogeneous nature of the basic oxygen steel-making process, bath temperature can be controlled without an external fuel supply by charging the furnace with additions that are thermally balanced. The thermal requirements of the charge materials are such that, during the refining process, they throttle the heat generated by the metallurgical reactions in a manner designed to result in a speci-fied temperature at the completion of the heat. In the past, operating personnel at the basic oxygen furnace plant of Jones & Laughlin's Aliquippa Works relied on their experience and technical knowledge of the process to determine the quantities of charge additions needed to result in a finishing temperature in the range 2880"to 2920" F. (The charge consists primarily of 93 tons of scrap and hot metal plus an amount of lime sufficient to maintain a basicity ratio of 2.8 to 3.2). Estimates of these materials are based on a consideration of the effects on finishing temperature of 1) iron silicon content, having a variation of 0.8 to 1.8 pct; 2) iron temperature, ranging from 2250°to 2600°F; and 3)any excessive cooling of the furnace due to a production delay. The end temperature of the preceding heat also serves as a guide in that, if a heat was within the specified temperature range, the succeeding heat could be charged with materials of nearly the same proportions, provided the hot metal used in each of the two charges was of approximately the same temperature and composition. On the other hand, if a heat was outside the specified tapping range, or if the hot metal used in that heat was of different analysis and temperature from that of the iron to be charged, an adjustment in the proportion of additions is in order for the following heat. Due to the complex thermochemical behavior of the process and to the inexact and subjective nature of the described method of determining charge additions, consistently accurate temperature control was not to be expected. Therefore, those heats out- side the specified tapping range necessitated subsequent adjustments by either reblowing the cold heats for a suitable length of time so as to elevate the bath temperature to the desired level, or cooling hot heats with a proper amount of scrap. Because extra time is required to make these adjustments, production is delayed. In an attempt to devise a method for improving temperature control, an analysis of the thermochemistry of the process was undertaken. This, in turn, led to the development of a set of mathematical equations which enable the calculation of the quantities of scrap, lime, and hot metal needed to result in any specified tapping temperature range. The analysis was not intended to be a repetition of work done by others such as McMulkinl or ~hilbrook.' It was meant to be an extension of their work so that charge additions could be calculated not in terms of silicon alone but, rather, as a function of all independent variables. This paper presents the derivation of these relationships, their effectiveness in controlling bath temperatures, and a method of utilizing them on an operational basis. The Heat Balance—The first step undertaken in the analysis of the problem was the enumeration of the pertinent variables. A list is presented in Table I where it is noticed that these quantities have been separated into the following three categories: important variables, variables considered as constants, and variables to be neglected. The breakdown was an arbitrary one designed to facilitate the analysis; otherwise, the mathematical treatment would have been exceedingly cumbersome and complex. Fortunately, experience has shown that these simplifying assumptions do not seriously impair the accuracy of the calculations. These variables along with the limiting assumptions listed in Table n were then used to write a heat balance of the process by applying the equation of continuity, Rate of Rate of Rate of Increase = Income - Outgo PI ] of Heat of Heat of Heat.

Jan 1, 1962

By AIME AIME

FRANK T. SISCO is a native of Lawrence, Kansas. He received his earlier education in Clinton, Iowa and his university training at the University of Illinois. His experience in the steel industry has included service in the chemical, testing, and metallurgical departments of the Illinois Steel Co., of South Chicago; the Hess Steel Corp., of Baltimore; the IJ. S. Naval Ordnance Plant at Charleston, W. Va.; and the American Steel and Wire Co., Waukegan, Ill. He severed for seven years as chief of the metallurgical laboratories of the U. S. Army Air Corps at Wright Field, Dayton, before coming to New York in 1930 to become metallurgist and editor of the Alloys of Iron Research, the position he now holds.

Jan 1, 1940

By R. G. Agarwal, Ramey Jr. H. J., Al-Hussainy R.

Although it has long been realized that gas recovery from a water-drive gas reservoir may be poor because of high residual saturations under water drive, it appears that only limited infomlation on the subject has been available until recently. This study was performed to show the qiiantitative potential importance of water influx. Results indicate that gas recovery may be very low in some cases: perhaps as low as 45 per cent of the initial gas in place. Gas recovery under water drive appear to depend in an important was on: (I) the prodirction rate and manner of production; (2) the residual gas saturation; (3) aquifer propertie.); and (4) the volumetric displacement effciency of water invading the gas reservoir. The manner of estimating water-drive gas reservoir recovery can vary considerably. Examples are: the steady-state tnethorl. the Hurst modified steady-state method, and various unsteady-state methods such ac. those of van Ever-dingen-Hurst, Hurst, and Carter-Tracy. The Carter-Tracy water influx expression was used in this study. In certain cases, it appears that gas recovery can be increased significantly by controlling the production rate and manner of production. For this reason, the potential importance of water influx in particular gas reservoirs should he investigated early to permit adequtrtr planning lo optirtize the pay reserves. INTRODUCTION In recent years, the economic importance of natural gas production has become increasingly apparent. This has been evidenced by more intensive exploration efforts aimed at gas production, and exploitation of both deep, as well as low-permeability gas reservoirs. Technical developments such as deep-penetration fracturing have made development of such formations economically feasible. Unfortunately, water influx has forced abandonment of a number of gas reservoirs at extraordinarily high pressures. Although reservoir engineering methods for estimating water influx have long been available, it appears that application of these methods to the water-drive gas reservoir has been sporadic.'a Available methods for estimating water influx which can be applied to the water-drive gas reservoir problem include the steady-state method,1 the Hurst modified steady-state method and various unsteady-state methods such as those of van Everdingen-Hurst. Hurst, and Carter-Tracy. Interesting applications of these solu- tions to gas reservoir and the aquifer gas-storage problems have appeared recently.3,12,14 The experimental study of residual gas saturations under water drive by Geffen et al. in 1952 indicated that residual gas saturations could be extremely high. A value of 35 per cent of pore volume is often used in field practice when specific information is not available. The study of Geffen et al. showed that residual gas saturation might be much higher in some cases. Naar and Henderson concluded that the residual non-wetting phase saturation under imbibition should be about half of the initial non-wetting phase saturation. The Naar and Henderson result that residual gas saturation under water influx should be about half the original gas saturation is recommended as an estimate if laboratory measurements are not available. Thus, it is clear that a considerable portion of the initial gas in place might be trapped in a water-drive gas reservoir as residual gas at high pressure. A full water-drive would result in loss of residual gas trapped at initial reser.voir pressure. Consideration of transient aquifer behavior leads to the conclusion that high-rate production of water-drive gas reservoirs could result in improved gas recovery by reduction of the abandonment pressure. However, there appears to be little quantitative information on this possibility. One of the few advantages of water-drive gas production appears to be improved deliverability through water-drive support of the reservoir pressure. There may also be an advantage in higher condensate recovery caused by pressure maintenance for gas-condensate water-drive reservoirs. In view of the preceding, this study was made to assess the potential importance of water-drive in gas reservoir engineering. The Carter-Tracy approximate water-influx expression was used because this equation offers some advantages in hand-calculation which do not appear to have been generally recognized.' However, calculations were performed in the main with a high-speed digital computer to permit evaluation of the effect of water-drive under a large variety of conditions. CALCULATION METHOD Water-drive gas reservoir performance can be estimated in a manner completely analogous to oil reservoir calculations: a materials balance is written for the reservoir, and a water influx equation is written for the aquifer. Siniltaneous solution provides the cun~ulative water influx and the reservoir pressure. When reservoir performance data (gas produced and reservoir pressures) are available, it is usually possible to match performance data to determine the initial gas in place and the water influx parameters —

Jan 1, 1966

By AIME AIME

T HOUGH Ira B. Joraletnon has not had an eastern address since 1907, he is a New Yorker by birth, having been born at Antwerp, in the northern part of the state, on July 27, 1884. He got his scholastic training at Harvard, which gave him his A.B. degree in 1905 and an A.M. two years later. For the next fifteen years except for the war period, he was with the Calumet & Arizona Mining Co., with headquarters at Warren, Ariz., being assistant man- ager when he left that company in 1922. During the first World War he spent a year and a half in France, where he achieved the rank of major in the signal corps, air division.

Jan 1, 1941

By John L. Walte

Consolidation Coal Co.'s Renton mine, a 680 000-t/y (750,000-stpy) underground operation located in western Pennsylvania, has reduced the time required for overcast construction in its advancing operations by adopting a prebolting technique followed by multiple blasting. In the past, the mine's overcasts had been excavated by the continuous mining machines used to advance the section. More recently, the overcasts were blasted down and then rebolted with a stoper drill. The new system, using a two-part combination bolt, has proven very successful in speeding up overall construction time and providing more positive horizontal control in blasting. The prebolting approach allows the roof to be blasted down and loaded out without the need for rebolting the shot-out area.

Jan 6, 1978

This excellent paper by Dr. Colombo parallels quite closely the bench and pilot work done by the Hanna Research Laboratory on the Mesabi oxidized taconites. Because of the vast reserves and future ore requirements the need to perfect the selective flocculation-flotation process becomes very necessary. The selective flocculation process is a very efficient method of desliming, leaving a fairly clean, upgraded product for flotation. However, one of the problems that we have encountered in this process was some very fine, -2 micron liberated goethite in the slimes that did not flocculate. The complete slime removal is not necessary. We remove slimes to the extent of about 5% of the iron units. However, on difficult treating ores we would remove more slimes. The reclaimed water from our pilot plant has a turbidity of about 1000-3000 ppm. We can obtain lower turbidity water but to do this would involve additional lime as a tailing flocculant and we would run the risk of flocculating the entire ground pulp in the selective flocculation process because of the increased Ca level in the water. We have about seven different geological ore types out of 17 recognizable ore types that are treatable. All of these ore types require different degrees of dispersion and grinding which is a problem. The use of acrylic acid polymers as a selective flocculant has been patented by the American Cyanamid Co. This will-have to be

Jan 1, 1979

By J. R. Elenbaas, J. A. Vary, D. L. Katz

The development of gas fields, oil fields and aquifers for storing natural gas is treated from two main vieu.-points: (I) the volumetric storage capacity for gas in a given situation and (2) the prediction of the number of wells required for the delivery of gas. Other experiences in the design and operation of storagc fields are incluclerl INTRODUC TION Storage of natural gas in underground reservoirs near the terminus of long distance pipelines has been the prime factor in opening the space heating market to the natural gas industry. Storagc has permitted a major. increase in both the load and the load factor of pipe-lines; some are now operating at steady load throughout the year. Thus, underground storage has been responsible for the rapid increase in demand for natural gas in recent years. Three types of reservoirs have been used for gas storage: natural gas reservoirs, oil reservoirs, and waterbearing sands or aquifers. This paper presents the factors to be considered when developing gas storage reservoirs of these three categories. There are two prime considerations tor any storage reservoir: (1) the volume of gas which a given reservoir will store advantageously and (2) the number 01 wells needed to provide the required peak deliverability. These two problems will be considered for the three types of reservoirs just noted STORAGE IN PARTIALLY DEPLETED GAS FIELDS Early storage operations consisted of replenishing the natural gas in a depleted gas field situated adjacent to the market. Today, newly discovered fields near the market may be considered for storage, and this discussion applies equally to both types of reservoirs. For reservoirs originally containing gas or oil, the question of the impermeability of the cap rock nor-mally does not arise. However, such fields are likely to have many wells drilled either to or through the reservoir under consideration. Positive assurance must be obtained that such wells are or can be made mechanically tight. Corroded casings may need to be lined or permanently plugged. Abandoned wells should bc reopened and properly cemented. The volumetric capacity for gas storage depends upon space available in the porous rock as well as pressure and temperature of the gas in the reservoir. The production-pressure decline data on partially depleted gas reservoirs without water drive permit calculation of the reservoir space for gas. Isopachous maps of sand volume and porosity data for the reservoir rock provide an alternate method of calculating the pore volume for water-drive reservoirs. The pressure range selected for the storage cycle depends upon ()) the safe upper limit of pressure. 2) the flow capacity of wells and (3) compression requirements when injecting gas into the reservoir or delivering to market. Normally, gas and oil fields have pressures at discovery in the range of 0.43 to 0.52 psi/ft of depth. Pressures of around 1.0 to 1.2 psi/ft of depth appear to lift the overburden1-3 and invite uncontrolled movement of fluids in the porous rock. Some top pressure is normally selected for a storage reservoir ranging from below discovery pressure for deeper reservoirs to 0.65 psi/ft of depth for shallower reservoirs. Pressures to 0.66 psi/ft have been experienced without difficulty. The lower pressure limit is set by water intrusion accompanying low pressures, reduced flow capacity for wells at lower pressures and compression requirements. Depletion-type gas reservoirs often encounter water problems in the later stages of gas production. Such water intrusion may be due to movement from the surrounding aquifer. Accordingly, displacement of this water back into the aquifer by gas pressure and subsequent surges of water corresponding to the gas storage pressure cycle must be considered. Storage fields often produce in four months a volume of gas equal to its initial content. Rapid decreases in reservoir pressure occur, such as 20 psi/day. Accordingly, closed-in pressure observation wells which reflect the pressure in the bulk of the reservoir are required for following the operation of the reservoir. It has been found that a plot of observation wellhead pressures against gas content, Fig. 1, is very useful in observing operation of the field, checking the inventory and predicting future behavior. The plot is based on a given quantity of base or cushion gas in place. The injection and withdrawal curves may spread depending upon the homogeneity of the reservoir rock. permeability of the rock, well spacing and flow rates.

By A. J. Lena, M. F. Hawkes

Changes in hardness, tensile properties, microstructure, electrical resistance, and X-ray diffraction effects indicate that lattice strains are necessary for the embrittlement of ferritic stainless steels when heated for relatively short times at 475°C (885°F). It is suggested that 475°C (885°F) embrittlement is due to the accelerated formation of an intermediate stage in the formation of s under the influence of these strains. FERRITIC stainless steels (low carbon alloys of iron with more than 15 pct Cr) are subject to two forms of embrittlement when heated in the temperature range of 375° to 750°C. The embrittlement which occurs after long time heating between 565" and 750°C is well understood; it is caused by the precipitation of the hard, brittle s phase. Sigma is an intermetallic compound of approximate equi-atomic composition with an extended range of formation in Fe-Cr alloys. The maximum temperature at which this form of embrittlement can occur is dependent upon chromium content; and is approximately 620°C for a 17 pct Cr steel and 730°C for a 27 pct Cr steel. The other form of embrittlement occurs after relatively short heating periods in the range of 375" to 565°C; in the higher chromium steels, hours may be sufficient as compared to months for s embrittlement. This phenomenon is not at all well understood and several controversial theories have been proposed. The rate and intensity of embrittlement increase with increasing chromium content but the maximum rate occurs at 475°C re-gardless of chromium content. As a result of this, the phenomenon has been termed 475°C (885°F) embrittlement. The effect of 475°C embrittlement on the properties of ferritic stainless steels has been thoroughly reviewed by Heger.1 The embrittlement causes a pronounced decrease in room temperature impact strength and ductility, a large increase in hardness and tensile strength, and a decrease in electrical resistivity and corrosion resistance. Microstructural changes accompanying embrittlement are minor and difficult to interpret with a general grain darkening, appearance of a lamellar precipitate, grain boundary widening, and precipitation along ferrite veins having been reported at various times. With the exception of reported line broadening, X-ray diffraction studies by conventional Debye analysis of solid samples have been of little value. BY making use of electron diffraction methods, Fisher, Dulis, and Car-roll' have recently shown the existence of a chromi-um-rich, body-centered cubic phase in 27 pct Cr steels which had been aged at 482°C (900°F) for as long as four years. Two types of theories have been advanced to account for the embrittlement. The first of these requires the precipitation of a phase not inherent in the Fe-Cr system with various investigators suggesting a carbide,3 nitride,3 phosphide,4 or oxide." Theories of this type have difficulty accounting for the influence of alloying elements on the embrittlement and for the facts that a minimum chromium content is necessary for embrittlement and the intensity of embrittlement increases with increasing chromium content. The second type of theory that has been proposed relates 475°C embrittlement to s phase formation which is inherent in the Fe-Cr system. An assumption of this kind can adequately explain the influence of alloying elements, for they exert an effect on 475°C embrittlement similar to that on s phase for-mation as can be seen in Table I. The minimum chromium content is essentially the same for both phenomena and it has been shown12,13 that s is a stable phase in the embrittling temperature range. In addition, it has been reported14,15 that pure alloys embrittle to the same extent as commercial type alloys. There are, however, several factors which have prevented complete acceptance of a s phase theory. Foremost of these is that the embrittlement can be removed by reheating for short time periods above 600°C, which in the higher chromium steels is within the stable s region. No s has ever been observed after one of these curing treatments, nor has any s been found as a result of embrittlement at 475°C. In addition, the simple precipitation of s cannot explain the time-temperature relationships for reactions between 350°and 750°C. This behavior is shown schematically in Fig. 1. Newell 16 and Ried-rich and Loib4 have shown that 475°C embrittlement follows a C-type curve as illustrated, while Short-

Jan 1, 1955

By J. Chipman, N. J. Grant, B. M. Shields

The vacuum tin-fusion method of analysis for hydrogen, developed by Carney, Chipman, and Grant, has been modified to permit the analysis of the evolved gases for hydrogen by means of a thermal conductivity cell. A properly prepared sample can be analyzed in 10 min with a probable error of ±0.12 ppm. A study of various methods for storage of hydrogen samples shows that samples can be safely held in a dry ice-acetone bath as long as six days. Storage in liquid nitrogen is necessary for samples to be held one week or more. HE vacuum tin-fusion method, as developed by I- Carney, Chipman and Grant,' is the only analytical procedure which has shown promise of being fast enough for use in the control of hydrogen during steelmaking. It was felt that further simplification and faster speed of operation could be effected by the use of thermal conductivity measurements for analysis of the gases evolved in the tin-fusion method. The application of conductivity measurements to the tin-fusion method is possible because: 1—the evolved gas is essentially a mixture of hydrogen, nitrogen and carbon monoxide with a hydrogen content usually over 50 pct, 2—the evolved gas is collected at a relatively low pressure, and 3— the thermal conductivities of CO and N2 are practically identical while that of hydrogen is very much greater. The major part of this research program was devoted to the construction and calibration of a vacuum tin-fusion apparatus which analyzes the evolved gases for hydrogen by means of a thermal conductivity cell. The second phase of the problem was associated with the development of a procedure for storage of samples prior to analysis. With the rapid quenching method for hydrogen sampling,' which seems to be the most practical for steel mill use, it is necessary that the samples be stored safely during the interval between sampling and analysis if the hydrogen content of the molten metal is to be maintained in the supersaturated solid samples. The thermal conductivity bridge has been used for a number of years in the analysis of certain gas mixtures. An elementary discussion of the theory and practice of gas analysis by thermal conductivity measurements is given by Minter.3 A more comprehensive discussion of the theory and of the various measuring circuits is presented by Daynes.' A complete knowledge of the theory and properties of the thermal conductivity of gases and gaseous mixtures can be gained by a study of the standard textbooks on the kinetic theory of gases."' The existing data on the thermal conductivity of single gases are reviewed by Hawkins: that for a number of binary gas mixtures by Daynes' and Lindsay." The thermal conductivity method may be applied to the determination of the composition of a binary mixture if: 1—the thermal conductivity of the mixture varies monotonically with composition, and 2— the two gases have measurably different thermal conductivities. The greater the difference between the two gases, the greater the sensitivity of the method.10 he method is applicable to the analysis of multicomponent mixtures when all of the gases in the mixture except one have nearly the same thermal conductivity. Fortunately, the mixture of hydrogen, nitrogen, and carbon monoxide evolved by the tin-fusion analysis' falls in this latter classification. The thermal conductivities of nitrogen and carbon monoxide are practically equal; and the thermal conductivity of hydrogen is approximately seven times that of the other two. Therefore, the thermal conductivity of a gaseous mixture of hydrogen, nitrogen, and carbon monoxide at known temperature and pressure can be related directly to the percentage of hydrogen in the mixture by suitable calibration. Usually the thermal conductivity of a mixture of gases is measured at atmospheric pressure where the thermal conductivity is independent of pressure over a wide pressure range. At very low pressures (below 1 mm Hg), the thermal conductivity of gases varies with the pressure. This phenomenon has been utilized in the Pirani vacuum gage for the measurement of pressures in the range of 10" to 10-0 mm of mercury.= Very little has been published concerning the variation of thermal conductivity with pressure at intermediate pressures between 1 mm Hg and 1 atm. However, preliminary measurements indicated that the thermal conductivities did vary with pressure over the range of pressures (up to 10 mm Hg) at which gases are delivered from the vacuum pump. Therefore, the calibration of the thermal conductivity cell had to be planned to include the effects of both gas composition and pressure. Such a calibration chart is shown in Fig. 4. Most industrial applications of the thermal conductivity method of gas analysis have used a compensated Wheatstone bridge circuit containing two

Jan 1, 1954