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By Milton E. Wadsworth, Daniel B. Brimhall

Column leach studies of a low-grade porphyry copper ore were made. The technique used involved alternating oxygen absorption and copper leach cycles. The leach solution was displayed from the column with oxygen. The volume of oxygen reacting with the ore was measured with a gas burette. The copper released as a result of exposure to oxygen was correlated with the oxygen uptake. The oxidation rate was found to be dependent on the pH of the solution wetting the particles and was markedly increased by increasing the temperature of the system. Decreasing the particle size of the sample increased the oxidation rate. A material balance on the system indicated 1 mole of oxygen yielded in excess of 1 mole of copper in solution. A discussion of the important parameters is presented and the results are related to dump leaching in general.

Jan 1, 1974

By E. Asselin

Electrochemical polarization experiments were conducted on alloy 625 in ammonia solution between 25 and 225°C and the results were compared with those of an oxygen solubility model. Results confirm that corrosion is under oxygen control, Normalized corrosion rates are determined based on the rate of oxygen diffusion to the corroding surface, and the corrosion rate at 200°C (-9.7 µA.cm-2) is roughly 24 times higher than the corrosion rate at 25°C (0.4 nA,cm-2), An oxygen-solubility model for Supercritical Water Oxidation (SCWO) conditions was generated using the Redlich¬Kwong-Soave (RKS) equation of state, Results of the model confirm many of the experimental observations from SCWO reactors which suggest that corrosion is at a maximum at temperatures just short of the critical point, The RKS/oxygen diffusion model predicts that the corrosion rate at 365° C is ?85 times higher than the corrosion rate at 25' C. Given that a normalized corrosion rate is obtained, this type of model could be useful for selection of SCWO reactor materials.

Jan 1, 2005

By Yoji Imai, Akio Watanabe, Masakazu Mukaida

"To clarify the feasibility of alkoxides and acetylacetonates as precursors for laser CVD of metal oxides, vapors of tantalum or titanium alkoxides and zirconium acetylacetonate were irradiated by KrF excimer laser and deposits were characterized by XRD and XPS measurements. As for tantalum and titanium, non-stoichiometric crystalline oxides grew nearly phototropically, however, zirconium oxides deposited showed only halo-pattern by XRD measurements. Electric conductivity measurements of tantalum oxides implied the improvement of the insulating properties by the addition of activated oxygen to the ambient.IntroductionThere has been renewed increasing attention to the metallic oxide thin films because ofits promising usefulness in many applications, such as high-Tc superconductors and ferroelectric devices. A variety of thin film preparation techniques have been studied such as sputtering, chemical liquid deposition (sol-gel and metalorganic decomposition), pulsed laser deposition and chemical vapor deposition (CVD). Among them, we think CVD is the most promising method because it offers a high controllability of morphology and good step coverage at relatively high growth rate. Preparation of oxide films by CVD can be achieved using a precursor containing metallic element and oxygen containing gas such as N20 at the same time. However, metalorganic (MO) compounds which contain both metallic element and oxygen, directly bonded to metallic element, seems to be more favorable because some of MO has a good properties for CVD such as a rather high vapor pressure, stability in ambient and low toxicity."

Jan 1, 1998

By Massimiliano Zanin, William Skinner, Owusu Clement, Jonas Addai-Mensah, Daniel Fornasiero

This paper highlights the importance of pulp aeration in the selective separation of chalcopyrite from chalcopyrite/pyrite mixtures of varying pyrite content (20-80 wt.%). Laboratory batch flotation studies and oxygen demand tests were performed to predict the optimum amount of air required for the selective separation of chalcopyrite from pyrite. The pulp oxygen demand was shown to increase with increasing pyrite content but decrease with time as more air is introduced into the system. Complementary batch flotation tests showed significant improvement in chalcopyrite flotation under moderate pre-aeration of the pulp. However, a continuous decrease of chalcopyrite flotation was observed under highly aerated conditions. The amount of air required to achieve maximum chalcopyrite flotation recovery correlated positively with the mass fraction of pyrite in the pulps. The greater the wt.% of pyrite in the chalcopyrite/pyrite pulp, the longer the aeration time required. The optimum aeration time was established as the time before which the oxygen consumption rate constant reaches a bottom plateau. Surface analysis (XPS) indicated that the continuous decrease in pyrite recovery observed with increasing aeration time was due to the formation of more iron oxy/hydroxide on its surfaces, the same species accounting for the decrease in Cp recovery after prolonged aeration.

Jan 1, 2014

By S Brown

With oxygen conditioning routinely used in both the lead and zinc circuits at Pasminco Elura Mine a more sophisticated method of determining oxygen demand was required. It is known that different ore types have different oxygen consumption rates, however oxygen is added at a fixed rate regardless of ore type in the plant. Therefore, a simple laboratory test was devised to measure the oxygen demand of ores. The paper describes the technique employed, and provides an interpretation of the results. These data, together with pulp chemical measurements (Eh, pH and EDTA extraction data) were correlated against laboratory flotation performance to establish the relationship between oxygen demand and the position of the grade/recovery curve.

Jan 1, 2000

By Stephen R. Grano, Jon Glatthaar, Philippe Steinier, Christopher J. Greet

"The importance of the oxygen content of sulphide mineral pulps in determining which reactions occur, and their subsequent influence on flotation behaviour is grossly underestimated in most operating concentrators. While pH is routinely monitored, Eh and dissolved oxygen measurements are obtained infrequently. However, dissolved oxygen measurements in conjunction with other pulp chemical parameters (i.e. pH, Eh, and EDTA extractable metal ion analysis), can provide valuable insight into where and what type of reactions are occurring within a circuit. Unfortunately, these readings yield “instantaneous” measurements of the pulp chemical parameters.What is needed is a means of establishing how reactive a pulp is, and how this reactivity changes as components of the system are manipulated. Oxygen demand provides an opportunity to do this. Several attempts at measuring the oxygen demand of a pulp have been made in the past with varying degrees of success. Most notable among these are Noranda and BOC Gases.Learning from these experiences, Magotteaux have developed the MagO2 ® demand vessel to measure the oxygen demand of mineral pulps. This paper described the apparatus, and through a case study on Broken Hill lead/zinc ore demonstrates how the MagO2 ® demand vessel is used.INTRODUCTIONThe role of oxygen in flotation is complex. While a considerable body of work exists demonstrating the strong involvement of oxygen in the interactions between sulphide minerals and collector (Gaudin and Finkelstein, 1965; Gaudin, 1974; Woods, 1984; Laajalehto, Nowak and Suoninen, 1993), the presence of oxygen can also affect the oxidation state of sulphide and non-sulphide minerals, which can impact on their flotation behaviour. Further, sulphide mineral oxidation is related to their oxygen demand (Spira and Rosenblum, 1994)."

Jan 1, 2004

By Robert W. Bartlett, Keith A. Prisbrey

"Natural biooxidation of shallow, refractory ore heaps, relying on gaseous oxygen diffusion from the heap surface is attractive because of its simplicity and potential low cost, especially without using a lined pad, which is possible if percolation of leachate through the heap is avoided. In this case, the excess oxidation enthalpy must be removed by water evaporation from within the wet ore heap, and the rising water vapor flux within it will impede the downward oxygen flux. An analysis of this process shows that for typical values of pyrite grades and limited temperature increases in the ore heap, the oxidation rate and penetration into the heap is reduced to values between about 30 percent and 50 percent of those obtained when leachate percolation occurs and water evaporation is not a significant mechanism of heat removal.IntroductionHeap biooxidation of refractory gold ores, needed as a pretreatment step to liberate the gold for subsequent extraction by leaching, requires large amounts of oxygen for the normal amounts of sulfide minerals that are typically present, one to two percent pyrite and/or arsenopyrite.The importance and potential limitations of oxygen transport into commercial ore heaps, which are much larger than encountered with column tests of ore and with pilot heaps, has been recognized111 • Commercial ore heaps using radial stacking conveyors are typically about nine meters high and may be 100 meters or more in lateral dimension. Three oxygen transport mechanisms have been identified and analyzed: ( 1) natural convection, which arises from an increase in buoyancy caused by the temperature rise and gas composition changes associated with the exothermic oxidation of the sulfide minerals within the ore heap, (2) forced air ventilation, using low pressure fans and air distribution pipes within the heap, and (3) diffusion of oxygen in the gas-filled void spaces within the ore heap driven by the oxygen concentration gradient from the surface of the heap to the mineral oxidation loci within it."

Jan 1, 1997

By N. S. Dalal, B. Jafarl, M. M. Suryan, V. Vallyathan

"The biologic events leading to coal workers' pneumoconiosis (C'WP) are not yet fully understood. There is no good correlation between toxicity studies or animal models with human epidemiologic and pathologic data. Several studies have shown that the severity and prevalence of the CWP in miners correlate strongly with the rank and type of the coal mined. However this has not been found to be the case with laboratory animal models or in vitro studies. In 1980 Russian scientists Artemov and Resnik suggested that the discrepancy may be related to the excessive amount of short-lived free radicals present in freshly generated coal mine dust. Because of their short life, such free radicals would be absent in the ""stale"" coal dust used in most animal experiments. To test this hypothesis we have undertaken a systematic study of the generation, reactivity with oxygen and biological significance of free radicals in coal dust.Electron spin resonance (ESR) was used as a technique for the direct detection of radical production and kinetics of decay. ESR signals from the newly generated radicals decreased with time on exposure to oxygen or when stored in biological buffers at a rapid rate. In vitro biological tests were carried out which suggest that the reaction between the newly generated radicals and oxygen plays a significant role in the sample's cytotoxicity.Materials and MethodsESR measurements were made at X-band (~9.7 GHz) using a computer-controlled Bruker ER200D ESR spectrometer. 11te two coals studied in detail were obtained from the Pennsylvania State University Coal Depository. These were, a bituminous sample, PSOC-1172 (72% carbon) and an anthracite sample, PSOC 867 (95% carbon). Coal particles of several millimeter (mm) dimensions were evacuated to a pressure of ~10-3 mm Hg typically overnight. Without exposure to air, these particles were ground in an agate mortar with an agate pestle for about 30 minutes and then sieved through a 20 \1111 mesh filter before ESR measurements or cytotoxicity studies. As an index of cytotoxicity, hemolysis was measured according to the method of Harrington, with minor modifications. Sheep erythrocytes (2%) were incubated with test samples at 37°C for one hour, and the hemoglobin released was quantitatively estimated photometrically. Additionally, release of alveolar macrophage enzyme lactate dehydrogenase (LOH) was estimated after incubation of the macrophages with the coal particles at different time intervals after the grinding. Enzyme activity was assayed according to the method of Wrobleski and LaDue and expressed as percent of enzyme released in 2 hours per million cells with 1 mg of coal."

Jan 1, 1989

By W. Hoecker, S. Watson

The use of oxygen (Goldox™) in gold leaching has emerged as a significant modification in the past nine years. The Goldox™ process was ori gi na 11 y developed by Afrox Ltd ( part of the BOC Group) and is currently used in South Africa, Australia, Canada and the United States. Although a variety of benefits have been observed with oxygen, this paper out 1 i nes the main ones with reference to Australian plant data. The case studies were categorised into the ore type: Oxide, blends and primary ore.

Jan 1, 1992

By David J. Krichten

A method of retrofitting air-fuel burners with oxy-fuel capability overcomes the potential problems associated with oxygen combustion in aluminum melting furnaces. The retrofit burner uses the existing combustion air connection, burner housing, and burner tile and replaces the gas tube with an oxy-gas burner. Maintaining a portion of the air flow to the burner reduces the potential for localized overheating. Proper design of the burner reduces NOx emissions by moderating the flame temperature with furnace gas recirculation. Economic analysis of using oxygen shows the benefits are increased productivity and reduced overall unit cost of melting. In practice, the melt rate in rotary furnaces increases by up to 50% and by up to 35% in reverberatory furnaces. Oxygen utilization reduces total melting cost by 112-314 cents per pound of aluminum melted.

Jan 1, 1997

By J. E. Forbes

Oxygen enrichment of the converter air at Rustenburg Platinum Mines by J. E. FORBES (Associate Member)* An account is given of the adoption of oxygen enrichment to accelerate converting operations and so permit the handling of larger quantities of feed materials. In addition to achieving its object, the use of oxygen-enriched air (6 per cent oxygen by volume) results in an increase in the concentration of sulphur dioxide in the converter off-gas. The slags have the same composition as those produced without oxygen enrichment, and the operation of the converters is easily controlled.

Jan 1, 1977

By G. S. Victorovich

Technical progress in primary smelting has changed the face of the copper industry in the years since the Second World War. Much of this change has resulted from a wide acceptance of flash smelting technology. In addition, research has been directed toward devising converting processes to replace conventional Peirce-Smith converting technology. One major thrust has involved a revival of the old " ", idea of oxygen flash converting of comminuted mattes. This paper reviews the 60-year history of flash converting. Particular attention is paid to Inco's investigations into the processing of white metal containing significant amounts of nickel and, in some cases, iron. Thermodynamic analysis and laboratory experimental results are presented which throw light on the behaviour of nickel and other salient features of flash converting. The possible role of oxygen flash converting in the copper pyrometallurgy of the future is briefly discussed vis-a-vis direct production of copper.

Jan 1, 1993

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the Ger- man techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low- cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first German assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission- to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high- cost coke and anthracite for the production of water gas. Although varying degrees of success have been achieved and the water gas produced generally has been higher in calorific value, in only a few isolated in- stances has there been any sustained use of bituminous coal for water-gas production for public utility uses after the shortages of anthracite and coke have been lessened.

Jan 1, 1946

By S. F. Urban, G. Derge

AT the time this investigation was initiated variations were observed in the quality of different heats of basic electric-furnace steels, although they had been made under purportedly similar conditions. This indicated that these variations were related to normally unobserved variations in the character of the bath, especially during the "refining" period. Although the slags used for this operation are commonly referred to as "reducing" slags, and are regarded as having a "deoxidizing" action on the bath, no reliable measurements of this action were available. It was decided, therefore, to study the behavior of oxygen in the metal for a large enough number of heats to learn its normal variations and to relate these variations to regularly observed conditions [f] operation. The most important general conclusion reached was that the time a heat is held under a reducing slag should be reduced to a minimum, which was about an hour and a half under the conditions studied. Beyond this time no observable beneficial effects are obtained from the reducing slags, insofar as oxygen and sulphur content of the bath are concerned. It is likely that added time may increase hydrogen content as well as heat costs. The oxygen content of the bath is never reduced below the amount in equilibrium with the carbon. Concurrently with this work, J. S. Marsh1 presented data that supplement and support many of the results of this paper. PROCEDURE The work was done in two different electric-furnace shops of the same plant. The selection of heats was made primarily with regard to the convenience of heat schedules. Companion slag and metal samples were taken just prior to slag-off and throughout the refining period for an initial set of 17 heats, and before slag-off and near tap for an additional 13 heats. Slag sampling presented no particular problem; a spoonful of slag was poured onto a metal plate and when sufficiently cool was sealed in an airtight container. Sampling the metal for oxygen presented a more complex problem. Because of the lack of previous experience in sampling electric-furnace baths, a number of methods were compared. Chilled Wedge Samples2 An unkilled metal sample is removed from tie furnace in a well-slagged carbometer spoon and poured immediately into a heavy copper mold designed to provide rapid freezing. Three different types of molds were used to determine the optimum for electric-furnace heats. The Big Wedge Mold (a) was a 4 by 4 by 4-in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 1 ½ in. long, and ¼ in. maximum thickness, and was finally adopted as the most satisfactory design. The Long Wedge Mold (b) was a 2 by 2 by 5 ¼ -in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 2 ¾ in. long, and ¼ in. maximum thickness. The Small Wedge Mold (c) was 2 by 2 by 4-in. split copper mold, yielding a wedge-shaped casting 1 in. wide, 1 ½ in. long, and ¼ in. maximum thickness.

Jan 1, 1947

By Wilford Stork

CERTAIN influences of oxygen on iron have been known for many years and it has always been considered one of the worst enemies of the iron and steel founders. Nobody had a good word for it, hence little was done to make use of this oxygen. In all the fields of foundry practice, the desideratum was "melt without oxidation of the metal." In the consideration of the influence of oxygen on cast iron, we must not confuse this condition with oxidized iron caused by poor melting conditions, due to a high bed, heavy charges, low coke ratio, excessive melting rate, high blast, or poor charging. It is admitted that oxygen absorbed by iron melted under these conditions has a deleterious effect on the properties of the iron. The writer has had experience both in the melting under such poor conditions and in remedying these bad conditions and considers the product far inferior to iron melted under normal conditions. As stated by Dr. Richard Moldenke,1 such iron has a higher melting point and high combined carbon, is sluggish, and contains slags and oxides in solution in the liquid, causing slag inclusions and gas occlusions, thus producing defective castings. This oxidized condition cannot be counteracted or removed by any of the known deoxidizers; it can be remedied only by proper melting conditions. Such iron is really burned, whereas the iron considered in this paper was melted under normal conditions with moderate blast, correct bed height, light charges of iron, and low coke consumption and is not in this category at all. In 1914, the late J. E. Johnson, Jr., startled the metallurgists of the world when he published his results on the advantages of oxygen on cast iron.2 His work is so convincing and so logical, in spite of the common and well-established notions on the subject, that nobody has been able to refute a single argument. Such an eminent authority on iron and steel metallurgy as Prof. H. M. Howe has accepted the work in all its details in his latest book3 The work of J. E. Johnson, Jr., has revolutionized

Jan 6, 1919

R. S. MACPHERRAN,* Milwaukee, Wis. (written discussion?);-Mr. Stork's paper is very interesting, but I am unable to agree with some of his conclusions. He argues very strongly for the beneficial effect of oxygen, but gives no actual determinations of this element to support -his views. He states that the oxygen resulting from a high bed, heavy charges, low coke ratio, etc. must not be confused with the oxygen under normal conditions. I will be glad to know in what respect these oxygens differ or in what state they occur. Is it his opinion that the beneficial type is present as a dissolved gas and the other as metallic oxide? I will not discuss the first five of his six points, as I have not seen enough trustworthy determinations of oxygen in cast iron to form any conclusions as to its effect. I have never known the addition of manga-nese, however, to reduce the strength of cast iron. Under the sixth point, I would say that the addition of steel lowers the total carbon content, and by this action will increase the strength independently of oxygen. This reduction of carbon operates also to raise the melting point. It is interesting to note here that the author, in order to get proper fluidity for his cylinders, was obliged to reduce his oxygen by raising the manganese in the charge.

Jan 12, 1919

GEO. F. COMSTOCK,* Niagara Falls, N. Y. (written discussion?).¬A study of this paper raises a question on which it is hoped Mr. Stork will throw more light; that is, why does an oxygen content generated on poor melting conditions have a deleterious effect on the properties of the iron, while an oxygen content generated by the oxidation of steel scrap in the cupola is beneficial to the strength and chilling ability? In each case the oxygen is absorbed at the same time and place in the process of melting and it is by no means clear why the superiority of semisteel should be assigned solely to its oxygen absorption, when oxygen absorbed without the steel addition is admitted to be injurious. It is not apparent why oxygen caused to be absorbed by the steel addition should not pro-duce the effects of burning, sluggishness, slag inclusions, gas occlusions, etc., the same as oxygen absorbed by the iron in the cupola for any other reason, and it would seen that other factors to which he has not given sufficient emphasis must enter into the author's results. To an impartial reader of this paper, who was most favorably inclined toward J. E. Johnson, Jr.'s theory of the improvement of cast iron by oxygen, the discrepancy in the author's reasoning or statements is difficult to accept, and it is hoped that an explanation will appear in the final discussion.

Jan 11, 1919

R. MOLDENKE, Watchung, N. J. (written discussion*).-It is some-what difficult to discuss the paper of Mr. Stork, when the description of the cupola melting occurrences indicates that his practice is open to question. The evident burning of much of the steel charged,. coupled with the remarkably low silicon content of the mixture as shown by the resulting product, throws the entire melting practice into that of making cupola malleable. If anything is wanted here, it is a. high bed to melt upon, and yet Mr. Stork in the very beginning of his paper speaks of the evils of oxidation due to a "high" bed, etc. The experienced foundry-mall would judge at the outset that Mr. Stork has kept his bed in the cupola too low, and naturally got a lot of oxidation from the blast. The oxidation of steel when used in large quantities in cupola mixtures is a well-known phenomenon, and is readily understood. One has but to. put a file into the forge fire and watch it burn when heated high enough. The melting point of steel being higher than cast iron, heavy pieces may dig way into the bed before being completely melted away, the last por-tions being directly exposed to free oxygen from the blast. Another situation not to be forgotten is the oxidizing effect of carbon dioxide at high temperatures. A serious oxidation of the steel is quite conceivable if in the zone of maximum carbon dioxide and minimum carbon monoxide-free oxygen being entirely absent. Hence the well understood practice of never melting a mixture with much steel unless the bed is kept exceed-ingly high; or again the above-mentioned malleable practice. Mr. Stork mentions the impossibility of deoxidizing a heat. after the steel contained has been oxidized. This is true to a great extent with the ordinary deoxidizers, such as silicon and manganese, but can be brought about by vanadium, titanium, magnesium, etc. Proper melting, however, makes this unnecessary.

Jan 10, 1919

By B. M. Larsen, T. E. Brower

IN two previous papersl,2 dealing with the carbon-oxygen reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity 0[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm,; that is, if [C] X [O] is taken as 0.00222, 0[O] = [O] - 0,00222/[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.' This quantity 0[O] proves to be substantially independent of carbon content over the range 0.08 to 1.2 per cent, as well as of the basicity of the slag, and is nearly always within the limits 0.015 to 0.025 per cent when the bath is boiling normally and is in what we have termed a steady state. Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, 0[O], on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in ?[O] level following addition of Spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. VARIABILITY OF EXCESS OXYGEN IN NORMAL OPEN-HEARTH OPERATION The preceding general statements refer to the average value of ?[O] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining oxygen from the gas phase above it, or from added ore, faster than it is losing oxygen to the metal; yet when the bath starts to boil vigorously, the opposite condition may prevail for some time. The consequence of this lag is a variation of ?[O], the interpretation of which in a single heat may not be immediately obvious, This condition is illustrated in Figs. I and 2. In Fig, I, ?[O] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small ore feed causes only a small rise in 0[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1946

By B. M. Larsen, T. E. Brower

IN an earlier paper1 we discussed a simple, rapid method of taking samples of liquid steel and analyzing them for oxygen, which, though possibly not absolutely accurate (as is likewise true of all other methods), certainly yields results that are satisfactorily consistent. Accordingly, samples from hundreds of heats in different shops were analyzed for oxygen, with results sufficient in number to be handled statistically and permit estimation of some general trends. Measurements were made in acid as well as in basic open hearths, throughout the refining period, to learn how stirring, blocking, adding ore or lime or sand, affects the oxygen content of the bath; we also followed the changes brought about by tapping, teeming, and deoxidizing. Some of these results, discussed in an earlier paper.2 bring out the dominant role of the carbon-oxygen reaction in regulating degree of oxidation both of metal and of slag, also the marked variability of concentration of dissolved oxygen [0] in excess of that which would be in equilibrium with carbon and with carbon monoxide at a partial pressure of one atmosphere. As a logical beginning on this complex problem, we take up in the present paper the variability of this excess oxygen, ?[O], when other factors are as constant as they ever are in open-hearth operation; namely, toward the end of the refining period, when the bath may be regarded as in the comparatively steady state it approaches in absence of disturbing factors. This condition was chosen because by that time the significant reactions, except carbon oxidation, between slag and metal have come to substantial equilibrium; this facilitates interpretation of the complex situation and thus permits more definite conclusions to be drawn. This excess concentration of oxygen, ?[0], in the metal is needed, of course, to make the steelmaking process go at a reasonable rate; alternatively it may be regarded as a measure of the virtual pressure increment above one atmosphere, or of the degree of supersaturation, of carbon monoxide in the metal. According to our measurements, the excess concentration ?[O] in liquid steel varies from about 0.009 to 0.035 per cent oxygen by weight. It is quite sensitive to change of conditions, being altered temporarily by operations such as stirring with green poles, additions of ore, lime, or sand; but as the disturbance works itself out, it resumes a level within the intermediate range characteristic of the steady state. The conditions most common in average furnace practice are covered by the following : [ ] as in a reasonably steady state-that is, when it is boiling normally, is at proper temperature with a well-shaped slag, and has been free from disturbing effects during the preceding half hour-?[O] returns from

Jan 1, 1946