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By W. E. Wrather

SERIOUS consideration was given by the Petroleum Division to a wide variety of subjects, during six busy sessions at the Annual Meeting. Beginning with a joint session on engineering research and production engineering, Tuesday afternoon, conducted by E. A. Stephenson and H. C. Fowler, problems of petroleum technology, domestic and foreign production, proved oil re- serves, economics, and stabilization were mooied almost without interruption until nearly everyone was "talked out,' and the meeting was adjourned at the end of the annual Petroleum Division dinner, late Thursday night.

Jan 1, 1933

By Earl Hanson

FIRES in heavily timbered mines are disastrous, involving danger to both life and property. Some mines have been completely ruined or so heavily damaged that reopening them would not pay. Though few mines are entirely free from danger of fire, the risk is minimized by proper care and good design of plant. The Tintic Standard mine is at Dividend, Utah, in the famous Tintic mining district, about 60 miles south of Salt Lake City. The development of the mine was begun in 1907 by the late Mr. E. J. Raddatz and his associates. From the beginning, the work was hampered by high rock temperatures and the presence of high concentrations of rock gases such as carbon dioxide and nitrogen. Development work was carried on with great perseverance for nine years, and resulted in the discovery of ore in 1916. The total production of the Tintic Standard mine to Jan. 1, 1936, amounted to 1,664,388 tons of ore, having a gross value of .$61,996,719.

Jan 1, 1936

By John H. Smith

Because of increased pressure from federal and state regulatory agencies, most acid flows will require some sort of treatment prior to being discharged to receiving streams. In many industries, the volumes of liquors are large and their acid content varied. Development of a waste treatment process minimizing equipment cost and utilizing land efficiently is mandatory. Methods of acid neutralization with lime have been known for years, however, the volume and characteristics of the resultant precipitated solids can create a disposal problem. Also, when standard lime treatment is used, the settling characteristic of the precipitated solids is normally slow. In some instances, the necessity of added dissolved solids removal, such as iron, needing aeration, add to the problem of concentrating neutralized solids.

Jan 12, 1972

By AIME AIME

A PAPER recently presented before the Anthracite Section of the A. I. M. E. by S. J. Phil- lips, Mine Inspector, Fifth Anthracite District, Department of Mines of Pennsylvania, covering the water hazards in the anthracite coal mines of the Lackawanna River Valley, was especially timely because the conditions there are duplicated to a large extent in the Wyoming Valley, which is traversed by the Susquehanna River with its many large tributary streams. Also, in the southern anthracite field, where there are a number of large creeks, similar pumping problems and mine water hazards will in time be presented if mining is continued to its conclusion.

Jan 1, 1936

By Frances H. Clark

IN a concern with the varied interests of the Western Union Telegraph Co., where practically all types of metals, both ferrous and nonferrous, are utilized, many types of failures of materials occur. These have to do not only with outside plant construction, such as corrosion and fatigue of line wire and cable, but also with inside plant equipment operating at such high speeds that rapid deterioration of metal. parts due to fatigue and wear results. Both corrosion and fatigue affect the life of copper wire so its normal life in any particular locality is largely dependent on the atmospheric conditions. Tensions vary widely owing to changes in temperature and ice and wind loadings and the wire is Subject to a great range of vibration caused by wind gusts aril vibration front trains or other heavy vehicles transmitted through the earth. High frequency low-amplitude vibrations are sometimes audible as singing in the wire. The other extreme is the vertical slashing or dancing of the wire observed during severe storms where amplitudes of 9, ft. or more at low frequencies have been observed.

Jan 1, 1942

By John Birkinbine

IN the spring of 1878 the Pine Grove Furnace, located in Cumberland County, Pa., was blown in after lying idle for several years. The furnace was constructed in 1770, and for over a century it has been in almost continual operation. The plant consisted in 1877, when the writer was first called there, of a stone stack 32 feet in height, inclosing a shaft and boshes, the latter being 8 feet in diameter. The blast was supplied by two wooden blowing-tubs discharging into a third, having a floating piston sustaining a box weighted to give the desired pressure, the power being furnished by a waterwheel. A small 18-pipe hot-blast stove heated the blast. The furnace was remodelled during the winter of '77-78, and a Weimer blowing-engine with a blowing-tub 5 feet in diameter and 2 feet stroke, and the necessary boilers, were substituted for the wooden tubs and water-wheel. The stack was raised and enlarged, and provided with a bell and hopper having a central drop. Water dam and tymp were added, and general repairs were made. The hot oven, however, was riot increased. The furnace had always been operated with charcoal as fuel, and its reconstruction was made with a view to continue the use of charcoal, but provision was made for ample blowing capacity should other fuels at any time be employed. Although liberal arrangements had been made in cutting wood, the stock of charcoal supplied in 1878 was insufficient for the increased requirements of the remodelled plant, and notwithstanding the purchase of some 80,000 bushels from an adjacent idle furnace, there was riot enough to keep the furnace in constant blast until a new supply could be obtained, particularly as the season was unusually backward. Instead of following the established precedent of many charcoal furnace managers, i. e., blow out every February, it was determined to continue in blast, using coke as fuel. Accordingly, when the charcoal stock was exhausted, on March 22d, 1879, Connellsville coke was substituted, the change of fuel being made at once; that is, the coke charges followed immediately upon the last charcoal charges. After working a few days,-the strike in the Connellsville coke region cut off the supply, and anthracite coal was obtained, a mixture of the two fuels being employed. The strike continuing,

Jan 1, 1880

By James E. York

THE honor so fairly earned and so incompletely and tardily paid to Henry Cort, the inventor of the puddling-furnace and the, rolling-mill, has been fully set forth by Mr. Charles H. Morgan,1 and needs no further emphasis here. In view of the importance of the rolling-mill in the treatment of iron and steel, the paucity of information concerning it is surprising. With the exception of a hook, written about 35 years ago, by Peter Bitter von Tunner, an Honorary Member of this Institute, and of desultory articles on simple sections, which have appeared in technical journals, I know of no pub¬lication attempting to treat this subject, although volumes have been written on the scientific theory and technical manipulations involved in other branches of the iron- and steel-industry. This strange anomaly may be due to the fact that roll-turning cannot be called a scientific business. It does not ordinarily come within the range of an educated engineer; yet it cannot be performed by an ordinary mechanic. It demands some of the qualifications of an engineer, in designing, and those of a mechanic, in execution. The men who have followed this trade have controlled the training of their successors. In many cases the technical knowledge required bas been handed down from father to son, and there has been a motive of private interest to prevent its public dissemination. Moreover, the statement of the various principles involved in the process would require, besides manual experience, a degree of scientific knowledge which roll-turners do not usually possess; and, finally, any book on the subject, in order to possess real, practical value, would have to be so fully illustrated as to make it very costly to publish. Regarding my own experience, I may say that I served a six-

May 1, 1906

By A. R. Anderson

UNTIL recently all discussions directed at justify-ing the use of mechanical-loading equipment and conveyors have referred chiefly to tons per man and cost per ton. But there is another consideration that ? will speed the adoption of mechanical loading in mines even though tons per man on present day stand-ards were not increased nor the cost per ton decreased. With restricted immigration, improved facilities for education in our mining communities, and increased opportunities for recreation, the type of man who can or will throw 20 tons of coal per day over the side of a mine car is disappearing. Whether we will it or not provision must be made to replace muscular effort by mechanical means. Fortunately, indications are that the process will be accompanied by increased output per man and lower production cost, and though the outlook may now be a bit clouded in spots, all should profit by the change. The operator should enjoy a more stable business with more assured profit, the miners should get a better livelihood with less arduous effort and under safer and pleasanter working conditions, and the consumer should gain the assurance of a supply of coal always available at reasonable prices. That sounds like the millennium in the coal business perhaps. Of course, it is not, but there is just enough of that millennium stuff in it to encourage those of us who are working with today's problems of applying loading and conveying equipment to underground opera-tions. If we discern clearly that there can be no back-sliding, and that all will share in whatever advantages accrue, we will carry on more vigorously, and may right-fully expect to have the necessary cooperation of all the elements within the industry. As nature does not seem to have followed a definite plan in the formation of coal deposits it is not likely that any one standard method or type of equipment can be evolved for mining the coal. The method of mining that maybe most advantageously employed with load-ing machines and conveyors depends on the character of the strata overlying the coal as much as anything else.

Jan 4, 1927

By N. M. Levine

WHETHER the United States and its allies can W meet the challenge of a war brought by the Communists will depend largely on who wins the battle of steel production. At the present stage of the world situation, the United States and the other members of the Western family of nations have the lead on iron curtain countries. But we have no sure way of knowing what is happening at Magnetogorsk and other Russian iron and steel producing centers. We must also face the possibility that we may have to meet the challenge alone. The fortunes of war and world politics can strip us of friends and co-fighters quickly. The destruction of Hiroshima and Nagasaki are indicative of what the world can expect if war-madness ever grasps the earth again. Our domestic supply of high grade open-pit and underground iron ore is dwindling because of the drain of three wars and higher than ever civilian consumption. The production of iron ore and its eventual use in blast furnaces are the critical problems of an armed democracy today. The world crisis has led to efforts towards beneficiation for increasing ore supplies. The huge reserves represented by the magnetic taconites at the eastern end of the Mesabi, once in production, should provide us with a substantial portion of our native ore for many years. The estimated 10 to 20 million tons of concentrates annually can be increased in an emergency. If we had a certainty of peace for the next 50 to 100 years, the situation would be a stable, hopeful one, aided by importations of high grade ore from sources such as Canada and Venezuela. The hard truth is that we have little surety of peace tomorrow morning. Let us assume 'the U. S. could build sufficient processing plants for increasing production of magnetic taconites under the pressure of national emergency. We must also recognize the power of atomic warfare to contaminate an area as large as the Eastern Mesabi. Thus, it becomes imperative to seek some means of protecting our ability to produce the steel we may one day need to survive. The nonmagnetic taconites, completely dwarfing the magnetic taconites areawise as well as tonnage-wise, might provide us with this insurance. Present indications are that they will be considerably more expensive to treat, but in a desperate situation we might be very grateful for ores yielding 40 to 50 pct Fe recoveries at grades of 53 to 58 pct Fe carrying low phosphorus. The University of Wisconsin, because of the difficult iron ore situation in the state, has been working on the nonmagnetic taconite problem for the past three years in the hope of making a contribution toward its eventual solution. In Wisconsin, the Western Gogebic Range has been the state's most effective iron producing area. Today however, only two mines are in operation, both underground and approaching depths of more than 3000 ft. The range, however, does have a large supply of nonmagnetic taconites and presents a promising field for study. While the Gogebic offers one large source of nonmagnetic taconites, Michigan and Minnesota have even greater supplies of such material. Alabama, the northeastern states and the West all have low grade iron ore sources which might be utilized under extreme conditions. The Gogebic Range located in northeastern Wisconsin and northwestern Michigan has a total length of about 70 miles, about 45 of which are in Wisconsin. The iron formation averages 500 to 600 ft in width, dips 70' to the north and strikes at approximately N 63° E. The formation is sedimentary and consists of six distinct members characterized by alternating divisions of ferruginous chert and ferruginous slate. The footwall is generally quartzitic and the hanging wall of a sideritic slatey character. The iron minerals are mainly hematites with some magnetites, goethites, limonites and small amounts of siderite. In the area studied, very small amounts of iron silicates were observed. The magnetites occurred mostly in the Anvil-Pabst and Pence members, mixed with hematites and representing roughly about 10 to 20 pct of the total iron in the formation, thereby characterizing it as nonmagnetic. The gangue is of various forms of silica such as chert, opal and flint. Complete liberation of iron and gangue minerals is rare. There is always some iron present in the chert ranging from jasper-like solutions to fairly coarse iron oxide specks. Likewise, one always finds finely dispersed silica within the iron minerals. In late 1943 the Bureau of Mines carried out a trenching and sampling program in the two mile stretch between Iron Belt and Pence in Iron County, Wis. Preliminary work was based on samples from one of the four trenches cut by the Bureau of Mines. More detailed work following the preliminary analysis was then undertaken on samples composited from all the trenches, thereby giving a wider and more representative coverage of the area. A study of the

Jan 1, 1952

By Sir Robert A. Hadfield

The Hadfield method of producing sound steel ingots has been the subject of a paper read before the Iron and Steel Institute, so that it will be unnecessary to describe it fully here. The object of the method is to make poseible the production of steel ingots in which the pipe is almost entirely obliterated, and it is applicable particularly to the production of sound ingots, from which good rails could be rolled. The method in brief consists in casting the ingots on cars, usually with the small end down. Each ingot mold is provided with a sand top, rammed up in the well-known manner. After the mold is filled to the desired height with steel, a layer of slag about 0.5 in. thick is placed upon it and the balance of the mold is then filled with charcoal. Then, through suitable piping, an air blast is directed in numerous jets upon the charcoal, which is burned thereby, the combustion supplying addi, tional heat to the top of the ingot, which helps to keep the top fluid and to retard its solidification, while the lower parts are rapidly losing heat by its transfer to the mold. By one plan the ingots are cast in molds placed upon bogies, movable trucks, or platforms, in the position A, Fig. 1. The ingots are cast vertically on bogies, say four or more ingots on each bogie, as may be found most convenient, and the upper surface of the steel is maintained in a molten condition during the transit of the ingots from the casting pit to the stripper. This is effected by a series of air pipes, for example, three in number, with jets or holes on the under surface of such pipes, placed preferably horizontally, arranged in such a manner as to cause jets of air to impinge on the upper surface of the ingots. These holes or jets are made throughout the entire length of the overhead pipes, the length of such pipes being

Jan 1, 1914

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943

By Nicholas Kowall, K. L. Clark

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By K. L. Clark, Nicholas Kowall

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By A. E. Brugger

SOME 2,000 years ago Pliny is supposed to have said, "Out of Africa always something new." It may perhaps even now be news to a great many that the Belgian Congo has in recent years been producing approximately a quarter of a ton of diamonds annually. For that is what the 1 1/4 million carats, the recovery from 40-odd operating mines, and about 20 or 25 per cent of the world's normal consumption, amounts to. In 1915, first exploitation operations produced less than 50,000 carats from two mines. The rapid expansion of operations following the Euro¬pean war meant a most rapid development of a virgin land. The interior is now reached by air in one day from the mouth of the Congo River, where steamers unload mail and passengers from Antwerp. This trip formerly consumed 4 to 6 weeks by a narrow-gage, wood-burning, railroad around the rapids of the lower Congo and Livingston Falls; by river boat to the heads of navigation, Djoko Punda on the Kasai or Luebo on the Lulua; and thence by caravan of native porters over narrow-trails to head¬quarters on the Tshikapa. Hundreds of miles of automobile roads have been constructed over veldt and through forest, bridging streams and ferrying rivers. The railway from Capetown to the Katanga copper district to the East, once two months away by trail is now reached in 2 or 3 days over fair automobile highway. Native "boys" who a few short years ago wore little more than a smile and a string of beads and to whom a wheelbarrow was a complicated piece of machinery, are today driving Fords, tending boilers and engines and operating electrical equipment, or are capable mine workmen, machinists and artisans, and dressed in all manner of cast-off white man's clothing. Even as late as 1920, due to difficulties of securing and transporting machinery during and just after the war, the crudest hand operations were the rule for the excavation, sizing, and concentration of the diamondiferous gravel. All washing and concentration is now mechanized, using steam or electric power, and where operations are sufficiently large to permit competition with native labor costs, excavation and transportation are also accomplished by machinery.

Jan 1, 1932

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By N. Standish

Heat transfer coefficients have been measured in beds of various packings irrigated with mercury and molten fusible alloy countercurrent to hot gases. The measured coefficients for both systems were found to increase with gas velocities and liquid rates. Correlations were determined which show this dependence and also indicate that heat transfer in these systems is influenced by the liquid flow characteristics and the thermal conductivity of the gas and the solid packings. A heat transfer model has beer2 proposed which explains the various features of the experimental results. On the basis of this study, which gives an insight into the heat exchange in the melting zone of the blast furnace, it was concluded that by comparison with the furnace stack heat transfer coefficients are about 1.5 times higher in the melting zone. EACH year large tonnages of metal are produced in operations which, in part, involve liquid metal irrigation of "packings" countercurrent to hot gases. The melting zone in blast furnaces and in cupolas is a good example of packings irrigated with a liquid melt countercurrent to gases. In all instances of this kind large amounts of heat are exchanged and it is desirable to have some knowledge of heat transfer phenomena involved in these systems. So far the most common method of analyzing furnace efficiencies, fuel requirements, and the general thermal state of the furnace has been through the use of heat balances. As heat balances are essentially statements of the first law of thermodynamics they give no real indication of the factors which govern heat transfer between phases in the various zones of blast furnaces. Hence, rational improvement in production efficiency and the development of theoretical models is only possible if the heat transfer characteristics are known at every stage of the process and related to the important variables involved. This has been generally recognized for some time but it was only recently that Kitaev et al.' have produced a comprehensive treatment of heat transfer in solid-gas countercurrent systems such as the blast furnace stack and the packed bed regenerator. Using their treatment it is now possible to predict the effect of particle size, thermal conductivity, bed porosity, and the flow rates of both the gas and the solid material on the heat transfer in the blast furnace stack. However, the stack of a blast furnace is only one part of an integral unit for which the heat transfer analysis cannot be complete without also considering the heat exchange in the melting zone. The complexity of heat transfer processes in this region of the furnace has so far escaped quantitative description. Yet, the melting zone accounts for a greater amount of heat exchange than all the other zones of the furnace put together. Moreover, if the reduction of oxides in the melting zone proceeds in part in the liquid state the importance of heat transfer on furnace productivity and on the metal and slag temperatures is obvious. THEORY Heat transfer for two-phase flow in packed beds is a complex problem involving a number of heat exchange paths for which interphase areas are not known with any degree of certainty. Analytical solution is, therefore, difficult. This difficulty is emphasized by noting that Rabinovich~ and Luck have only recently solved the steady-state heat transfer for simplified two-phase heat exchangers of known area. However, useful progress can be made for the system considered by making a not unreasonable assumption that the usual heat transfer considerations apply and restricting treatment to the steady state. For these conditions the rate of heat transfer dq in a height dz of a packed bed of unit area is: dq = UaATdz [I.] Integration of Eq. [I] then gives the total heat transferred: assuming both U, the overall heat transfer coefficient, and a, the interphase area, to be independent of bed height. Since a, in these systems, is unknown it is convenient to combine this term with U. The group U, then represents the overall heat transfer coefficient on a volumetric basis. If AT is linear with q, then for a bed of unit volume Eq. [Z] can be integrated to give: is the log mean of terminal temperature differences. From Eq. [3] U, can be readily calculated as q and {AT)im are experimentally obtained quantities, but a difficulty arises in interpreting its meaning. Two approaches are possible depending on whether the effect of packing in the transfer of heat is neglected or not. If the packing is thermally decoupled then the resistance concept gives the relationship: which states that the overall resistance is the sum of the gas phase and the liquid phase resistances (assuming areas are equal throughout). Because the resistance to heat transfer in liquid metals is negligible by comparison with that of the gas,4 Eq. [4] can be simplified, i.e.:

Jan 1, 1969

By G. E. Johnson

E. D. HYMAN*—How much sorting of scrap is done ? G. E. JOHNSON (author's reply)—We do practically no sorting. We charge "run of mine" scrap to the furnace. The unmeltables, mostly iron, are in such demand today that there is no difficulty in disposing of them. It may soon be desirable to sort out from the unmeltables as much of the brass as possible. J. J. BRUGMAN†—We have somewhat similar problems in the secondary aluminum business. What is your method of removing the unmelted material from the furnaces? Why have you such an apparently small space in which to charge your materials? Do you find that you have to seal that opening, or can you have it open and continuously charge at one end and pull out the other ? G. E. JOHNSON—Our means of melting scrap is efficient only to the extent that we use the waste heat from the vaporizing chamber to do the job. It is a batch process. We open the charge door and place the scrap on the hearth by hand shoveling. The door is then closed during the melting down period. After the melting is complete, the opposite door is opened and the unmeltables are raked out. The doors are approximately 3½ X 4½ ft and are not sealed during the process only closed. They are nominally tight. Some metal is oxidized in the process. We have visualized a means of conveying the materials through this melting unit with the metals that are melted trickling out during its travel. T. H. WELDON‡—Mr. Johnson, in line with the last question, is it necessary to seal the furnace between the melting down and the vaporizing unit, or have you got an inverted syphon in the bottom of the chamber? G. E. JOHNSON—That was one of the first things we encountered. We had to have a sealed opening, and it is a molten metal seal. You have indirectly asked me another question, which was: "Do you have to seal up the melting unit?" I would say we should exclude as much air as possible, although we are not too efficient in doing that. We allow the melting unit doors to be open when we charge and when we remove unmeltables. You can readily see that that would lead to the idea of having a controlled atmosphere in the melting unit, and I think this would do a more efficient job of melting the scrap. T. H. WELDON—How often do you charge the furnace? G. E. JOHNSON—We charge the melting unit, and rake out the unmeltables, about every hour. H. R. HANLEY*—Are any provisions made for controlling the rate of oxidation for the production of various size particles for certain characteristics of the zinc oxide product? G. E. JOHNSON—Yes, there are many. You are getting pretty much into the fine points of zinc oxide manufacture. Some of us still think we have something to learn about that. In general, this muffle furnace as I have described it to you produces a rounded particle of zinc oxide which is generally formed by a rapid oxidation of the zinc vapor, followed by rapid cooling. We have gone to the other extreme in some of our experiments. We have changed the furnace to produce a type of zinc oxide, such as we thought was peculiar to American process zinc oxide, by controlling the temperature at the point of oxidation and maintaining that temperature for a much longer period of time than we do when we make the rounded shape. There are other relationships that this furnace readily provides. One of the important factors is the ratio of air to zinc vapors. We can vary that by varying the air supply to the baghouse, or vary the rate at which we are vaporizing the zinc by the simple expedient of regulating the temperature over the carborundum arch. We have a number of variables that permit us to produce all of the grades of French process zinc oxide from lead-free up through the highest grades of seal oxides. There are many controls that we can apply to the operation. What I have said is but a brief condensation. K. MORGAN*—Can Mr. Johnson give us some idea of the fuel consumption of the furnace ? How much oil does he use per ton of zinc distilled? I am also interested to know what sort of heat transmission he gets through the arch? What is the thickness of the tiles used to construct the arch? Some time ago we built a small furnace for a different purpose, using a carborundum arch, and we found that the reflectivity of the molten zinc surface was so great we had to use a very high arch temperature. We found we made an improvement by having a layer of carbon on the surface of the zinc. Has Mr. Johnson had any experience on these points ? Does he make any sort of insolu-bles which he leaves in the furnace which he cannot tap out ? G. E. JOHNSON—I believe your first question was the fuel consumption. If I recall, somewhere in this paper there is a test that I quote. I believe we used 800 gal in a given period of time. Offhand I cannot translate that into tons of metal. I might also state that we have this understanding; that the carborundum arch, as the temperature becomes higher, becomes more efficient in heat transmission. As a matter of fact, I believe it is at about 2600°F or higher that the highest efficiency of heat transmission becomes available. We have calculations that I cannot quote from memory which indicate that the carborundum arch does a really very fine job for this type of furnace. Another point that we had considered was the fact that this furnace could be readily constructed so as to furnish an ideal source of heat for waste heat boilers. If a carborundum arch was used over the melting unit, we would have no zinc vapors in the gases at all— just clean combustion gases from which we would have removed some of the heat. L. P. DAVIDSON†— The insolubles

Jan 1, 1950

By T. R. Ingraham

The thermal decomposition of Nickel (II) sulfate was examined by determining the total pressure of SO3, SO2, and O2 developed over a sample when it was heated in an evacuated system fitted with a Pyrex-bellows mercury manometer. The equilibrium pressures were combined with previously published data on the oxide and sulfide systems to establish a predominance volume diagranz for the Ni-S-O system over the normal range of roasting temperature and gas composition used in the treatment of nickel minerals. The protective coating of NiSO4 which forms on the oxide during roasting, and which causes the sulfation reaction to almost cease, may be disengaged readily by temperature cycling. When nickel sulfide is roasted in air, either nickel sulfate or nickel oxide may be formed by altering the experimental conditions. Because of the differing stabilities of various metal sulfates and oxides, possibilities exist for separating some of the constituents of mineral mixtures by the technique of selective sulfation and oxidation roasting. The experimental information required to make reasonable predictions of the possibilities of this technique is incomplete and, in some cases, in conflict. As part of a general program of providing some of the required information, a study EXPERIMENTAL Materials, Apparatus, and Procedure. Fisher certified reagent-grade nickel sulfate hexahydrate was used in the source material for both nickel sulfate and nickel oxide. The manufacturer's analysis indicated: 0.001 pct Fe, 0.005 pct Cu, 0.003 pct Co, 0.001 pct C1, other 0.15 pct. The material was dehydrated, before use, by heating at 420°C for 5 hr. The oxide was prepared by roasting the sulfate in an open tray in a muffle furnace for 10 hr at950°C. Preliminary experiments which were made by thermogravimetric analysis and X-ray diffraction analysis established that only one crystal form of nickel oxide and one of nickel sulfate were involved in the equilibrium shown in Eq. [I]. The apparatus used in the experiments was described previously.1,3 The main feature is a corrosion-resistant, flexible Pyrex bellows which is used to protect the mercury in a u-tube manometer. Before a run was begun, the apparatus was washed thoroughly with hot hydrochloric acid and water and dried by heating under vacuum. The mixed sulfate -oxide sample was contained in a platinum bat rest-

Jan 1, 1967