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By John Chipman, Helen Towers

DEVELOPMENT of a simple radioactive tracer technique for measurement of the diffusion coefficient of calcium ion in liquid slag has already been reported. The investigation was of a preliminary nature designed to explore the possibilities of using radioactive isotopes and to establish a method, and no great accuracy was claimed for the results. It was shown, however, that Ca15 could be used successfully, and the values obtained for the diffusion coefficient appeared to be of the right order of magnitude. However, it was considered that a better technique could be devised for carrying out the diffusion. The experiments were, therefore, continued to find a more accurate method, to check the calcium results, and to extend the investigation to include measurements of the diffusion coefficient of silicon in the same slag. There were two flaws in the original technique. Convection was the cause of too many failures, and the interface between the two slags in the diffusion cell was curved rather than plane, probably due to a surface tension effect caused by the addition of the tracer Ca45 in the form of chloride. Two methods of overcoming these defects were tried. Since it was planned to study diffusion of the short-lived isotope Si"' also, the development of methods was restricted to those which gave promise of being reasonably rapid. Method 1—The principle was identical to that previously used with respect to the diffusion conditions, but there were three differences in technique. Temperature control was more rigid, the tracer was added to the slag as Ca45O rather than the chloride and, finally, an effort was made to translate to high temperatures the elegant method developed by Cohen and BruinV or bringing together the two liquid layers and beginning the diffusion. A master slag was melted in graphite, ground to a fine powder, and analyzed (38.5 pct Ca0-20.9 pct Al2O3-40.5 pct SiO2). The tracer was received as Ca45C12 in an aqueous solution of CaC12 + HC1. From this, calcium oxalate was precipitated, ignited to calcium oxide, and added as such to the slag to give an activity of approximately 5 µc per g. The mixture was then melted into the form of a cylinder 3/16 in. diam and about 1 in. long. A solution identical to the tracer solution without Ca45 was given exactly the same treatment. The resulting Ca40O was mixed with that slag which was to form the tracer-free half of the diffusion cell, and this was likewise melted into a cylinder of the same size. Slag cylinders, two with and two without Ca15, were set in graphite blocks as shown in Fig. 1, and the crucible was lowered into position in the fur-

Jan 1, 1958

By P. Wynblatt, J. E. Dorn

The effect of strain rate, temperature, and interstitial impurity concentration on the flow stress was investigated in a poly crystalline Fe-2 pct Mn alloy. The temperature dependence of the flow stress was found to be independent of the interstitial impurity concentration, removal of interstitials merely decreasing the atherma1 stress level. Below 160%, the large temperature dependence of the flow stress was interpreted in terms of the Dorn-Rajnak theory of the Peierls mechanism of plastic deformation. Above 160"K, some other thermally activated intrinsic meckanisln seems to be operating. The strong temperature dependence of the flow stress of bcc iron at low temperatures has been studied by numerous investigators and interpreted in terms of several different thermally activated dislocation mechanisms. The following mechanisms have been proposed: a) interaction of dislocations with interstitial impurity atoms1 or with solute atoms in general; b) interaction of dislocations with clusters of impurity atoms;3 c) resistance to the motion of dislocations due to jogs on screw dislocations;* d) resistance to the motion of dislocations due to the Snoeck effect;' and e) interaction of dislocations with the intrinsic resistance of the bcc lattice or Peierls "hills". In previous work: it was found that the plastic behavior of polycrystalline iron containing 2 wt pct Mn (and 100 ppm C + N) is in good agreement with predictions based on the Peierls mechanismlo from 77" to 160°K whereas from 160" to about 370°K another as yet unidentified thermally activated mechanism is operative. The purpose of the present investigation was to determine the effect of interstitial impurities on the temperature dependence of the flow stress, by purifying the previously investigated alloy with respect to interstitial impurities. The investigation revealed that removal of the interstitial impurities to a level that eliminated Cottrell locking and the Portevin-LeChatelier effect (i.e., serrations in the stress-strain curve due to dynamic strain aging) affects neither the strong temperature dependence of the flow stress at low temperatures nor the general characteristics of the higher-temperature behavior. Such purification, however, lowered the athermal yield stress. I) EXPERIMENTAL PROCEDURE AND RESULTS The material used in this investigation consisted of an Fe-2 wt pct Mn alloy having the following additional elements present: 0.004 pct C, 0.006 pct N, 0.05 pct 0, 0.004 pct S, 0.003 pct P, and 0.001 pct Si. This was the same material as that studied in the previous investigation and will henceforth be referred to as the "impure material". The as received -jr by 2 in. hot-rolled bars were cold-rolled to 0.08-in. thickness, recrys-tallized under argon for 30 min at 80O0C, and further cold-rolled to 0.053-in. thickness. Flat tensile specimens 3 in. wide having a 1.625-in.-long gage section were machined from the sheet and then purified. The first stage of purification consisted of holding the specimens at 850°C for 24 hr in a stream of hydrogen saturated with water vapor at room temperature. Material prepared in this fashion will subsequently be referred to as "wet hydrogen purified material". It has been estimated that this type of treatment reduces the carbon content of iron to less than 5 ppm.' The second stage of purification consisted of holding the specimens in a closed system through which hydrogen was circulated past the heated specimens as well as a zirconium hydride getter. The specimens were held at 850°C and the getter at 800°C. The process was continued for 212 hr. The starting material for this process was wet hydrogen purified material. Material prepared in this manner will be referred to as "ZrHz purified material". The technique used was substantially the same as that described by Stein et al.' who have shown that the carbon level at the end of the process is reduced to about 5 parts per billion. The mean grain size of the three materials was found to be -60 C( for the impure material and -160p for the wet hydrogen and ZrHz purified materials. All tensile testing was carried out on an Instron Testing Machine either in controlled-temperature baths or at fixed-point baths such as boiling liquid nitrogen, and so forth. When fixed points were used the temperature was kept constant to better than *1°C whereas in all other tests the temperature variation was less than *2°C. Test of Purity. It was not possible to determine the purity achieved at each stage of the purification because the resulting level of interstitial impurities was near or below the limit of sensitivity of standard analytical techniques. It was possible, however, to obtain a qualitative measure of the extent of purification from the appearance of the stress-strain curves for the three materials. Fig. 1 shows the stress-strain curves for the three different materials tested at 300°K. It can be seen that the effect of wet hydrogen

Jan 1, 1967

By A. Eilers

A number of the copper refineries in this country have lately separated some of the rarer metals from the slimes in the refinery tanks. One of these has furnished me the following table of recoveries from given amounts of blister. I publish this to show the proportions, to gold and silver and to each other, in which these rarer metals may be expected to occur in copper from certain localities. GarFIeld, Utah :—The blister copper comes principally from the Bingham porphyry copper mines. Steptoe, Nev. :—All the blister copper is produced from the Nevada Consolidated mines. (Also porphyry deposits.) Omaha, Neb. :—Blister copper comes principally from concentrated copper-lead mattes shipped from the different lead-silver plants of the Rocky Mountain region to the converters at the Omaha lead refinery. Mountain, Cal. :—Ores occur in connection with diorite (?).

Jan 1, 1914

By Kenzo Murao, Sei Nakao

HISTORY OF ASHIO SMELTER The Ashio copper mine, which formed the main part of Furukawa mining industry, is located inland of Kanto area, and is known as the oldest copper mine of Japan. The mining started even since 1610, and Mr. Furukawa began management in 1877. Afterwards, within a short period, the mine became to have the highest productivity in the Far East. The total quantity of mined copper reached approximately more than 800 thousand tons. The mother rock of the ore deposit in Ashio was rhyolite, and was formed of sissurefulling and irregular clod that was called Kajika deposit. The lode was nzrrow of 6 to 7cm. The mineral was formed mainly of chalcopyrite, including also pyrite, pyrrhotite, and arsenopyrite that were not favorable. After the founding of the copper mine, the Ashio smelter started the operation of Mabuki process as the beginning in 1611, and subsequently adopted the processes of the blast furnace, reverberatory furnace, and flash smelting furnace of the present use. As indicated above, the copper ore of Ashio mine included arsenic. For the purpose to remove it, the operation of the arsenic trioxide production using MacDougall's multiple hearth roaster was started in 1918, and it maintained the status of having the most qualified technique within the country. However, as the completeness in the disposition of anti-pollution and safety had been requested in those years, we studied and developed a unique equipment in 1970. It excludes the heavy metals especially arsenic and copper from the waste water of sulfuric acid process of Flash Smelter's exhaust gas.

Jan 1, 1976

By David R. Mitchell

Many of the difficult operating problems of the preparation of coal for market, of sampling coal shipments and in the utilization of coal are caused by segregation in the coal mass. Segregation may be of two kinds: i.e., "size segregation," in which particles of the same size in a mass of coal containing a range of sizes collect together and "density segregation," in which particles of the same density or specific gravity in a mass of particles of varying density gather together. Mechanics of Segregation Size segregation cannot take place with closely sized coal. As the size range increases, the tendency for size segregation increases. Similarly, cleaned coal with particles of approximately the same specific gravity have very little tendency for density segregation. The wider the density range of particles and the more particles of different density, the greater the chances are for density segregation. The following discussion deals primarily with coal of a wide size range as screenings and of wide density differences as uncleaned or run-of-mine screenings. If a mass of coal containing particles of a wide size range is subject to the stream action of a moving current of water, the small particles are transported farther than the coarser. Particles of different density in a stream of moving water are subject to the laws of classification, the heavier settling out first. The familiar sluice box of the gold miner and the action of rivers and other streams in classifying material according to

Jan 1, 1938

By David R. Mitchell

Many of the difficult operating problems of the preparation of coal for market, of sampling coal shipments and in the utilization of coal are caused by segregation in the coal mass. Segregation may be of two kinds: i.e., "size segregation," in which particles of the same size in a mass of coal containing a range of sizes collect together and "density segregation," in which particles of the same density or specific gravity in a mass of particles of varying density gather together. Mechanics of Segregation Size segregation cannot take place with closely sized coal. As the size range increases, the tendency for size segregation increases. Similarly, cleaned coal with particles of approximately the same specific gravity have very little tendency for density segregation. The wider the density range of particles and the more particles of different density, the greater the chances are for density segregation. The following discussion deals primarily with coal of a wide size range as screenings and of wide density differences as uncleaned or run-of-mine screenings. If a mass of coal containing particles of a wide size range is subject to the stream action of a moving current of water, the small particles are transported farther than the coarser. Particles of different density in a stream of moving water are subject to the laws of classification, the heavier settling out first. The familiar sluice box of the gold miner and the action of rivers and other streams in classifying material according to

Jan 1, 1938

By D. J. Carney, J. Chipman, N. J. Grant

SINCE the beginning of this century it has been known that hydrogen contributes to the porosity of steel and that it is harmful to its mechanical properties. The evidence for this has been largely qualitative. Steel to which hydrogen was purposely added. in sufficient .amounts was shown to be either porous or brittle or both, whereas similar steel of low hydrogen content was shown to be free of porosity and to possess normal physical properties. There have been a considerable number of qualitative experiments of this type. Also, early in this century, a few attempts were made to measure the amount of hydrogen normally dissolved in commercial steels. This was usually done by placing the sample under an inverted liquid column such as mercury and collecting the evolved gas. These attempts, while not successful in measuring actual amounts of dissolved hydrogen gas, were able to prove that this gas will diffuse out of steel at room temperature, and that the amount of hydrogen dissolved is normally very small. On the basis of such qualitative evidence, hydrogen has been and still is blamed for a great number of the troubles encountered in the steel industry. In recent years, partial solutions for many steel-working problems have been obtained. These have led to increased interest in accurate quantitative work on hydrogen in steel, with the expectation that the results might possibly answer a few of the remaining unsolved problems. Commercially, two of the obvious questions which are in need of an answer are: (1) what are the most important sources of hydrogen, and (2) what quantity of hydrogen can be tolerated in various steels? There are many other unanswered questions. To begin to find the answers it seemed logical to start at the beginning of steel production with the liquid metal. Further, it seemed almost imperative to solve first the problems of analysis and sampling of the metal for hydrogen. Once these problems have been solved, it would be possible to answer more of the important commercial problems mentioned above. As a consequence, it was decided to design an analytical apparatus and, upon satisfactory completion of this, to develop an accurate method of sampling liquid metal for hydrogen.

Jan 1, 1951

By Shiro Ban-ya, John F. Elliott, John Chipman

The activity of carbon in Fe-C austenite at 1150°C has been determined for concentrations up to about 2.1 pct C using the equilibrium: C + COz = 2CO; equations have been derived expessing the activity as a function of carbon content on the basis of twelve mathematical models. Several of these represent the data satisfactorily. ACCURATE information on the thermodynamic properties of austenite in the binary system Fe-C is needed as a basis for studies of transformation and precipitation in steels of all sorts, alloy as well as plain carbon. The many attempts to approach this problem through statistical thermodynamics require sound and dependable experimental data in order to evaluate the several models which have been suggested. In this paper we are concerned with the experimental determination of the activity-composition relation in austenite at the temperature of its widest range of stability, approximately the eutectic temperature (1153°C). Accurate investigation of the activity of carbon in austenite may be said to have begun with the work of Dunwald and wagner.' A more detailed study was carried out by R. P. smith2 on the two equilibria: More recent work on these two equilibria has been reviewed by Chipman,3 who pointed out the experimental hazards associated with studies of Eq. [I]. Studies of this reaction involve rather small values of the ratio these are susceptible to errors due to traces of moisture in the apparatus according to the reaction: Ellis, Davidson, and Bodsworth4 evaluated K, for their experimental temperatures and used desiccants to control water vapor pressure. While they were able in this way to obtain consistent values for K1 it cannot be said that all of the uncertainties of the method have been overcome. Results by both methods reported by Schurmann, Schmidt, and wagener5 appear to be consistent except at very low carbon content. Reaction [2] was employed in the experimental work reported here. It is to be recognized, however, that it is not applicable to projected studies of certain alloy steel compositions involving stable oxide-formers.

Jan 1, 1970

By H. Biloni, R. Morando

The surface structure and substructure of Al-Cu alloys solidified as conventional ingots and under particular conditions such as those used by Bower and Flemings are studied. The influence of lampblack coating on the mold walls is especially considered and the results compared with those obtained in copper and graphite molds where no coatings exist. When high heat extraction conditions exist the observations show that mechanism of copious nucleation is responsible for most of the chill zone. When the heat extraction through the mold walls is low, a coarse grain structure with dendritic morphology arises, with a size that depends on the degree of convection present, analogous to that analyzed by Bower and Flemings. In both cases the effect of the convection on the macroscopic and microscopic appearance is discussed. The ingot macrostructure consists of one or more of three zones: "chill zone", "columnar zone", and central "equiaxed zone". The mechanism of the columnar-equiaxed transition has been subject of considerable interest and at present at least three theories exist about the formation of the equiaxed region: 1) the constitutional supercooling theory1 maintains that the equiaxed crystals nucleate after the columnar zone has formed, as a result of the constitutional supercooling of the remaining liquid; 2) chalmers2 pointed out, however, that there were several objections to this proposal, and that consideration should be given to the possibility that all the crystals, equiaxed as well as columnar, originated during the initial chilling of the liquid layer in contact with the mold; 3) Jackson et aL3 and O'Hara and ~iller~ suggested that a remelting mechanism of the dendrite arms is responsible for the formation of the equiaxed region. After the work of Cole and Bolling and other authors6 it became evident that convection (natural, reduced, or forced) plays a very important role in the transition from columnar to equiaxed and on the size of the resultant equiaxed structure. Until recently the accepted explanation of the chill zone was that it occurs as a result of copious nucleation in the liquid layer in contact with the mold walls.798 The columnar region is a subsequent result of the growth of favorably oriented grains and, as a result of a selection mechanism studied by Walton and Chalmers,9 elongated grains with marked texture are formed. Recently, however, Bower and Flemings" using an ingenious laboratory experiment introduced the idea that the "copious nucleation" mechanism is not responsible for the formation of the chill zone and that the presence of convection, introducing some form of "crystal multiplication", plays a decisive role in the formation of the chill zone. Unfortunately, it is important to consider that for their conclusions Bower and Flemings extrapolated the results obtained in their special experiments to the case of conventional ingots, and that these authors only analyzed the macrostructures of the specimens. Let us consider the work by Biloni and chalmers" concerning predendritic solidification. These authors were able to show that a study of the segregation substructure of A1-Cu gives information about the nucleation and growth of crystals formed in contact with a cold surface. A spherical predendritic region characterizes the first part of every grain nucleated in contact with the surface as a result of the chill effect. The aim of this paper is to elucidate through the observation of the segregation substructure the conditions under which (in the Bower and Flemings type of experiments and in conventional ingots) either the nucleation or the multiplication mechanism gives rise to the structure in contact with the mold walls. I) EXPERIMENTAL TECHNIQUES The experiments were performed on two alloys: Al-1 wt pct Cu and A1-5 wt pct Cu. The purity of the aluminum was 99.99 pct and the copper 99.999 pct. The results obtained with both alloys were similar. In the Bower and Flemings type of experiments the apparatus employed to obtain rapid solidification against a surface was similar to that used by those authors. The liquid was drawn by partial vacuum into the thin section mold cavity. Plate casts were 5 cm wide and usually 7.5 cm high. The thicknesses of the cast were 0.1 and 0.3 cm. Two different materials were used for the mold, copper and nuclear-grade graphite. The internal mold surfaces were polished and left uncoated for some experiments. In other experiments, the copper or graphite surface was coated with a thin film of lampblack material. In some of these particular experiments one of the mold walls was left with an uncoated region (usually in the form of a cross). The conventional ingots were cast in graphite or copper molds. In different experiments the mold walls were sometimes uncoated or coated with lampblack material. The results obtained in conventional and Bower and Flemings copper molds were compared with those obtained with copper molds coated with a very thin film of graphite; the results obtained were essentially similar. The size of the conventional ingots was 5 cm diam and 7 cm high in all cases. The cast surfaces produced by the Bower and Flemings type of experiments and conventional methods were observed macroscopically and microscopically without any metallographic preparation. As Biloni and Chalmers showed," the observation of the chill surface can give considerable information about the structure and segregation substructure.

Jan 1, 1969

By Elliot P. Rexford

IN the early days of concrete construction, the question of quality of sand or gravel to be used as aggregate in concrete was given little or no consideration. If the construction engineer had sufficient quantity for his structure within a reasonable distance, he was contented and gave no thought to the possibility that the material might have adverse physical, chemical, or thermal properties which could cause future deterioration of his concrete and possible failure of his structure. Today a very different situation exists. With the building of larger and larger concrete structures, with a longer and longer life expectancy, the quality of the aggregate material has become of major importance. Even in small concrete structures aggregate quality cannot be passed off lightly and the quality of the aggregate must be such as to give the anticipated life without costly maintenance. The first question to arise in the selection of an aggregate is what makes a sand or gravel suitable or unsuitable for use in concrete, and how can its quality be judged. No one rock type can be depended upon to furnish sound durable material in all instances. Granitic rocks, for example, make very satisfactory aggregates in some cases, but they are among the most unsuitable of materials when they are fractured, weathered, or highly micaceous. Limestones make excellent concrete aggregates on the one hand, and on the other they may be unsound and lack durability if they contain appreciable clay, they may have a harmful chemical reaction with the cement if they contain amorphous silica, or they may have thermal characteristics which make them highly unsuitable for use in concrete. Each rock, gravel, or sand must be proved on its own merits for the particular job under consideration. The selection of suitable aggregate materials may be divided into two major phases, the geological phase which is carried on largely in the field, and the testing phase which of course is a laboratory problem; both are important. Very often the geological phase alone is sufficient for the selection of satisfactory aggregates for minor structures but for major structures both phases must be thoroughly investigated. Geological Phase In the southwest part of the country nearly every major rock type, igneous, metamorphic, and sedimentary, may be found with all imaginable intermediate phases and in all imaginable stages of alteration. Frequently very different rock types, different as to geological age, composition, and condition occur very close together. Alluvium and stream-bed sands and gravels will consist of many different rock types and even ledge rocks may vary radically as to texture and composition within the area of a quarry site. Some of the rocks make suitable aggregate materials whereas others are highly deleterious in concrete. Too often the good and the bad occur together and more than ordinary caution is required in aggregate selection. Aggregate Sources: Concrete aggregates are usually obtained from stream-bed sands and gravels or from ledge rocks. Each has certain favorable and unfavorable characteristics and it is sometimes necessary to investigate both types to determine the most suitable source for a specific structure. Stream Beds: The predominant sources of aggregate materials in southern California and Arizona are stream beds. Vast quantities of sands and gravels are brought from the mountain ranges by the rivers during times of flood but most of these streams are dry a large part of the time and hence these deposits make easily accessible sources of aggregate materials. From many standpoints stream-bed materials make very acceptable aggregates. The gravel pebbles and the sand grains are

Jan 1, 1951

By Elliot P. Rexford

IN the early days of concrete construction, the question of quality of sand or gravel to be used as aggregate in concrete was given little or no consideration. If the construction engineer had sufficient quantity for his structure within a reasonable distance, he was contented and gave no thought to the possibility that the material might have adverse physical, chemical, or thermal properties which could cause future deterioration of his concrete and possible failure of his structure. Today a very different situation exists. With the building of larger and larger concrete structures, with a longer and longer life expectancy, the quality of the aggregate material has become of major importance. Even in small concrete structures aggregate quality cannot be passed off lightly and the quality of the aggregate must be such as to give the anticipated life without costly maintenance. The first question to arise in the selection of an aggregate is what makes a sand or gravel suitable or unsuitable for use in concrete, and how can its quality be judged. No one rock type can be depended upon to furnish sound durable material in all instances. Granitic rocks, for example, make very satisfactory aggregates in some cases, but they are among the most unsuitable of materials when they are fractured, weathered, or highly micaceous. Limestones make excellent concrete aggregates on the one hand, and on the other they may be unsound and lack durability if they contain appreciable clay, they may have a harmful chemical reaction with the cement if they contain amorphous silica, or they may have thermal characteristics which make them highly unsuitable for use in concrete. Each rock, gravel, or sand must be proved on its own merits for the particular job under consideration. The selection of suitable aggregate materials may be divided into two major phases, the geological phase which is carried on largely in the field, and the testing phase which of course is a laboratory problem; both are important. Very often the geological phase alone is sufficient for the selection of satisfactory aggregates for minor structures but for major structures both phases must be thoroughly investigated. Geological Phase In the southwest part of the country nearly every major rock type, igneous, metamorphic, and sedimentary, may be found with all imaginable intermediate phases and in all imaginable stages of alteration. Frequently very different rock types, different as to geological age, composition, and condition occur very close together. Alluvium and stream-bed sands and gravels will consist of many different rock types and even ledge rocks may vary radically as to texture and composition within the area of a quarry site. Some of the rocks make suitable aggregate materials whereas others are highly deleterious in concrete. Too often the good and the bad occur together and more than ordinary caution is required in aggregate selection. Aggregate Sources: Concrete aggregates are usually obtained from stream-bed sands and gravels or from ledge rocks. Each has certain favorable and unfavorable characteristics and it is sometimes necessary to investigate both types to determine the most suitable source for a specific structure. Stream Beds: The predominant sources of aggregate materials in southern California and Arizona are stream beds. Vast quantities of sands and gravels are brought from the mountain ranges by the rivers during times of flood but most of these streams are dry a large part of the time and hence these deposits make easily accessible sources of aggregate materials. From many standpoints stream-bed materials make very acceptable aggregates. The gravel pebbles and the sand grains are

Jan 1, 1951

By AIME AIME

T. E. PURCELL, general chairman . of the local committee, opened the seventh meeting of the Fuels Division A.S.M.E. and the Coal Division A.I.M.E., at the William Penn Hotel, Pittsburgh, Oct. 28-29, by introducing Harry M. Moses, president, H. C. Frick Coke Co., who welcomed the 500 registrants to "our town." Mr. Moses, in his brief talk, declared that in the postwar period each of the new centers must have a reason for existence. Pittsburgh, he said, has no iron ore, or bauxite, and limestone is scattered and not near by; but Pittsburgh does have low-cost fuel within reasonable distance. Its problem is the economical utilization of the low-cost fuels that remain, as the high-quality fuels are gone. Mr. Moses expressed confidence in this group in the solution of the problem and looked forward to what they would do. Harold V. Coes, the first A.S.M.E. president to attend one of these conferences, responded. He thoroughly believed in these joint meetings - in the cross-fertilization of ideas. Each Division learns from the other. Mr. Purcell then turned the meeting over to J. E. Tobey who presided over the coal research session that followed.

Jan 1, 1943

By C. L. T. Edwards

In the preparation of this paper, the author has drawn upon experience with the operation of a blast furnace on Ioo per cent scrap burden, which he believes was the first operation of its kind in the country. It is the writer's further belief that much of the controversy attending discussions of this subject may be obviated by the presentation of a group of facts that should be known by blast-furnace men and open-hearth men alike. The following question has been raised: "Is iron made with scrap in the blastfurnace charge as good iron as that made without scrap—made with straight ore?" This question may he answered in part by the fact that the open-hearth men of the Bethlehem Steel Co. who used pig iron from a blast furnace that operated on Ioo per cent steel scrap found no difficulty in the processing of such iron other than that to be expected from the known analysis. Operation with ioo PeR Cent Steel Scrap During World War I, there was accumulated at the Bethlehem plant of the Bethlehem Steel Co. some 22,000 tons of alloy-steel turnings and borings. This scrap material was highly corroded and, like alloy-steel turnings of that period, were as a drug on the market. There was also a small tonnage of scale, rich in valuable metal. If this scrap could be worked up into pig iron, it would become readily available for use in the open hearth. In order that the pig iron should contain the maximum percentage of nickel, permission was obtained from the Management to try a Ioo per cent scrap operation. Accordingly, a blast furnace was swung over on July 25, 1919; the percentage of steel scrap increased more or less irregularly until July 29, when Ioo per cent steel turnings were charged. Except for occasional charges of nickel scale as an "cxtra," the operation continued uninterruptedly until Aug. 27, when the furnace was swung back to the regular ore—ore and scrap—operation. During this period, the furnace production ranged from a low of 568.60 tons to a maximum of 766.07 tons. At the swing-over from Ioo per cent scrap to the regular burden, the charge I hung up rather severely. While the latter condition has nothing to do with the object of the paper, a brief discussion of the experience will appear later because of the interest it may have for blast-furnace operators. In Table I, results of the first and last days of the ore charge are shown, July 25 and July 29. The last column shows a summary for the period of maximum scrap ' charge. The furnace employed had a hearth 16 ft. o in., bosh 22 ft. o in., stock line 15 ft. 6 in., bell 11 ft. 6 in., batter in., bosh angle 73' 27' and a Balrer-Neuman top, with gas-engine blowers. Analyses Range of material charged Gravel: SiO2, 64.40 to 70.54 per cent; A1203, 3.52 to 4.58; CaO, 7.27 to 9.49; MgO, 5.09 to 6.14; FeO, 1.67 to 3.34, ignition loss, 9.50 to 13.83. I

Jan 1, 1942

By C. L. T. Edwards

In the preparation of this paper, the author has drawn upon experience with the operation of a blast furnace on Ioo per cent scrap burden, which he believes was the first operation of its kind in the country. It is the writer's further belief that much of the controversy attending discussions of this subject may be obviated by the presentation of a group of facts that should be known by blast-furnace men and open-hearth men alike. The following question has been raised: "Is iron made with scrap in the blastfurnace charge as good iron as that made without scrap—made with straight ore?" This question may he answered in part by the fact that the open-hearth men of the Bethlehem Steel Co. who used pig iron from a blast furnace that operated on Ioo per cent steel scrap found no difficulty in the processing of such iron other than that to be expected from the known analysis. Operation with ioo PeR Cent Steel Scrap During World War I, there was accumulated at the Bethlehem plant of the Bethlehem Steel Co. some 22,000 tons of alloy-steel turnings and borings. This scrap material was highly corroded and, like alloy-steel turnings of that period, were as a drug on the market. There was also a small tonnage of scale, rich in valuable metal. If this scrap could be worked up into pig iron, it would become readily available for use in the open hearth. In order that the pig iron should contain the maximum percentage of nickel, permission was obtained from the Management to try a Ioo per cent scrap operation. Accordingly, a blast furnace was swung over on July 25, 1919; the percentage of steel scrap increased more or less irregularly until July 29, when Ioo per cent steel turnings were charged. Except for occasional charges of nickel scale as an "cxtra," the operation continued uninterruptedly until Aug. 27, when the furnace was swung back to the regular ore—ore and scrap—operation. During this period, the furnace production ranged from a low of 568.60 tons to a maximum of 766.07 tons. At the swing-over from Ioo per cent scrap to the regular burden, the charge I hung up rather severely. While the latter condition has nothing to do with the object of the paper, a brief discussion of the experience will appear later because of the interest it may have for blast-furnace operators. In Table I, results of the first and last days of the ore charge are shown, July 25 and July 29. The last column shows a summary for the period of maximum scrap ' charge. The furnace employed had a hearth 16 ft. o in., bosh 22 ft. o in., stock line 15 ft. 6 in., bell 11 ft. 6 in., batter in., bosh angle 73' 27' and a Balrer-Neuman top, with gas-engine blowers. Analyses Range of material charged Gravel: SiO2, 64.40 to 70.54 per cent; A1203, 3.52 to 4.58; CaO, 7.27 to 9.49; MgO, 5.09 to 6.14; FeO, 1.67 to 3.34, ignition loss, 9.50 to 13.83. I

Jan 1, 1942

By S. Shapiro, R. G. Ames

Background Research on the respiratory health of coal miners has focused predominately on the relationship between coal mine dust exposure and ventilatory function impairment (Lapp et al., 1972; Jacobsen, 1976), on the prevalence of coal workers' pneumoconiosis (Lainhart et al., 1969; Morgan et al., 1973), and on coal miner mortality (Ortmeyer et al., 1974; Rockette, 1977). Lesser attention has been paid to the effects of other mining exposures. For example, underground exposure to diesel exhaust emissions (Reger et al., 1980; Ames et al., 1982,1984). An omission in US coal mining research, however, has been identified by the US Office of Technology Assessment (OTA) as the failure to study the effects of inhaled polyvinyl chloride (PVC) thermal decomposition and combustion products (Seltzer, 1979). These products may be released in the mine environment by cable fires, cable explosions, smoldering cables, and conveyor belt fires. In addition to the OTA concern, recent findings of chronic respiratory conditions and other health complications resulting from exposure to PVC decomposition and combustion products in firefighters (Peters et al., 1974; NBS, 1980; NIOSH, 1982; Wallace, 1982), and in survivors of several large scale PVC-fueled fires (Dyer and Esch, 1976; Wallace, 1981, 1982), add immediacy to the concerns. PVC decomposition and combustion PVC decomposition is initiated at temperatures far below ignition (Hartstein and Forshey, 1974; Wallace, 1981). Hence, exposures to decomposition products from smoldering cables may be important health hazards in addition to cable insulation combustion products. Hydrochloric acid (HCL) appears to be the principle toxic substance from the thermal decomposition of PVC since up to 60% by weight is released as HCL (Barrow et al., 1979). HCL is released both as a gas and as an adsorbant on soot particles (Stone et al., 1973), thus allowing penetration of respiratory defenses. In addition, laboratory results indicate that phosgene (carbonyl chloride), a potentially lethal gas, may be produced in significant quantities from electrical arcing of wires covered with PVC insulation (Woolley, 1971; Brown and Birky, 1980). Health concerns related to PVC Toxic effects resulting from high level exposures to PVC pyrolysis and combustion products in animals (Cornish and Abar, 1969) and in humans (Wallace, 1981) is beyond question. Analyses have reported acute, or short-term, health effects resulting from exposure to PVC decomposition and combustion products (Peters et al., 1974; Polakoff et al., 1975). Recently, however, several studies have found that acute effects are often followed first by apparent healing, and then by delayed chronic effects. This pattern of consequential respiratory involvement among persons involved in major PVC-fueled fires has been noted in firefighters, specifically the 1975 New York Telephone Exchange fire (Dyer and Esch, 1976; Wallace, 1982), and the survivors of the 1977 Beverly Hills Supper Club fire (Wallace, 1981). An obstructive syndrome (low FVC and FEV1) was seen in 15% of workers three months following fighting a PVC-fueled fire (Colardyn et al., 1976). Long-term respiratory symptoms seen in studies of survivors of PVC-fueled fires include the bronchitis symptoms of cough and phlegm, and lung dysfunction (Wallace, 1981). Additional support for the thesis of longer-term respiratory effects resulting from PVC-fueled fires is derived from the finding that four persons who initially survived the Beverly Hills Supper Club fire died within nine months of the fire of severe respiratory impairment (Wallace, 1981).

Jan 1, 1986

By A. L. Barnes, A. M. Rowe

A heat transfer study was made of hot gas injection into oil shale through wells interconnected by vertical fractures. This analysis involved the simultaneous numerical solution of a nonlinear, second-order partial differential equation that describes two-dimensional conduction heat transfer in oil shale and a nonlinear first-order partial differential equation that describes convection heat transfer in the fractures. Three nonlinear, temperature-dependent coefficients were used in this work; they are thermal conductivity, thermal capacity and retorting endothermic heat losses of oil shale. Vertical fractures were considered to be of finite height. Although vertical conduction heat transfer was not considered, an estimate of the error resulting from this limitation was made. The effects of injected gas temperature, injection rate, system geometry, cyclic injection and time upon retorting efficiency were investigated. Results from this study show that the rate of retorting oil shale is a direct function of both injection temperature and rate, and the theoretical producing air-oil ratio:(AOR) is an inverse function of temperature. Retorting rates are constant until "breakthrough" of the 700 F isotherm at the producing well, assuming constant injection parameters. Retorting rates for bounded systems are higher than the analogous unbounded systems and likewise AOR's are less. The use of an alternating injection-soak routine with high injection rates is less efficient than continuous injection at lower rates. These results indicate that injection temperatures on the order of 2000F or greater may give theoretical AOR's in the economic range. INTRODUCTION Over half of the known oil shale reserves are located in the U.S., and most of them lie in the Piceance Creek basin of Western Colorado. The Colorado oil shale outcrops on the edges of the Piceance Creek Basin. At the outcrops the shale beds are relatively thin, from 25 to 50 ft thick. In the center of the basin the oil shale is as great as 2,000 ft thick and is covered with 1,000 ft of overburden. It has been estimated that there are over 1,000 billion bbl of oil in shales having an oil content over 15 gal/ton in this basin. Oil shale does not contain free oil but an organic matter called kerogen. Kerogen yields petroleum hydrocarbons by destructive distillation. It must be heated to approximately 700F, at which temperature it decomposes into shale oil, gases and coke. The U.S. Bureau of Mines and, more recently, oil companies have conducted considerable research on surface retorting methods to economically recover oil from this shale. Another approach to exploit the oil shale deposits, in particular that portion having 1,000 ft of overburden, is to retort the oil shale in place and produce the liquid and gaseous hydrocarbons through wells drilled into the shale. Some research has been done on this approach.l,2 There are several variations to the in situ retorting approach. These variations fall into one of two groups, depending upon the geometry of the system: (1) retorting in a highly fractured or broken up matrix; (2) retorting from single fractures between production and injection wells. The latter is the group studied. Several investigators,3-6 using various assumptions, have studied flow of heat through horizontal systems. The objective of this work was to make a heat transfer study of in situ retorting oil shale by hot gas injection through wells interconnected by single vertical fractures of finite height. The oil shale thermal conductivity, thermal capacity and retorting endothermic heat losses were considered to be functions of temperature. A knowledge of the

Jan 1, 1969

By Kenneth F. Whinery, John M. Campbell

Basically, the Buckley-Leverett theory involves two systems which are similar in nature but are differentiated by time. These systems may be described by the fractional flow and frontal advance equations which essentially characterize the mechanics of oil movement while being expelled from the reservoir. The fractional flow equation originally developed by Leverettl may be expressed in the more usable form The development of this equation is based on Darcy's law describing fluid flow through porous media and applies to the flow at only one point (it is a point function). For simplification, the fractional flow equation is written in the above form because the capillary forces always increase the fractional flow of the displacing phase regardless of the direction of flow or the displacing phase. If, for simplicity, the effects due to gravity and capillary pressure differences are neglected, the fraction of the displacing fluid, f, at any point in the flowing stream is related to the properties of the system by 1 Thus, it is seen that in the absence of capillary and gravitational effects, fd for a given sand and fluids varies only with saturation and pressure. The magnitude of the viscosity ratio, —a has an effective range (range of about 30) in the system where gas is displacing oil and a much smaller range for water displacing oil. In order to make the fractional flow equation more versatile, it is necessary to connect the fractional flow at a given point and saturation with time. This problem was approached by Buckley and Leverett" who developed the frontal advance equation, Eq. 3 states that the rate of advance of a plane that has a fixed saturation, Sd, is proportional to the change in composition of the flow stream caused by a small change in the saturation of the displacing fluid. It is, essentially, a transformation of a material balance equation representing the net rate of accumulation of the displacing phase within a homogeneous sand block. This accumulation is proportional to the difference between the rate at which the displacing fluid enters the sand and that at which it leaves. Eq. 3 describes the velocity with which a plane of constant displacing phase saturation advances through a porous system. Buckley and Leverett," Babson,' Kern," Welge, and others have adequately discussed the basic mechanism and application of the fractional flow and frontal advance equations. APPLICATIONS OF THE FRONTAL ADVANCE THEORY TO PETROLEUM RECOVERY Two general applications of the Buckley-Leverett frontal advance theory involve the system in which the oil is being displaced by an expanding gas cap overlying the oil zone and that in which the oil is being displaced by water. Displacement by Gas in the Presence of an Immobile Water Saturation A system in which gas is the displacing phase may be thought of as having two forces effecting the displacement process. These forces are the gravitational force and that force exerted by the displacing gas. The gravitational effects control the displacing efficiency of the gas. The gravitational effect will be less at higher rates of flow, thereby reducing the effectiveness of the displacement of the oil by the gas. The more efficient displacements occur at flow rates which are less than the gravity free fall rate. Capillary forces can be neglected without materially changing the magnitude of the gas saturation. The Mile Six pool is used herein to illustrate the calculating procedures in evaluating gas drive-gravity drainage field perfomlance. These calculations represent the determination of the gas-oil contact when the distribution of the hydrocarbon pore volume is considered. Two methods

By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,' the revised activity coefficient of silicon

Jan 1, 1965

By W. G. Moffatt, J. Wulff

BRAZED joints and their strength have for some time been of great practical as well as theoretical interest. A good summary of the previous work in this field may be found in the reports of the Armour Research Foundation. In spite of excessive scatter in test data, the fact that the strength of a brazed joint may exceed the ultimate strength of the brazing material itself by many times continues to be of interest and of value in engineering. That this is qualitatively due to plastic constraint of the brazing material by the faying surfaces of the base metal is not in dispute, yet no complete interpretation of the data exists. The purpose of the present work is not to provide such a new interpretation, but to report new experimental data which we hope may lead to a better understanding of the important variables concerned. The work of Bredz' definitely shows that the thinner a brazed joint is, the greater is its strength. Dianeter of a joint has seldom been taken into

Jan 1, 1958

By Henry M. Howe

The natural effect of large ingot-size should be to increase segregation. I have previously pointed1 to the excessive segregation in many large ingots as tending to confirm this, but I have shown that in case of ingots less than 16 in. square this expected effect of ingot-size is liable to masked by that of Note.—The "maximum enrichment" of each ingot, i.e., the excess of the richest spot over the average of the whole ingot, is first calculated in percentage of that average. The average of the maximum enrichment of the several ingots of a given group is the abscissa in Fig. 1. The number beside each spot tells the number of cases which that spot represents. FIG. 1.—Influence of Ingot-Size on Maximum EnrichNent in Steel Ingots. other variables. Under these conditions we should expect that, if large ingot-size really does tend to increase segregation, this effect would be shown by taking the average of large numbers of cases, so that the effects of these other variables might off-set and cancel each other.

Jan 1, 1910