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By R. T. Webber, R. B. Owen

The vapor phase deposition of molybdenum and tungsten from the hexacar-bonyls has been thoroughly investigated by Lander and Germerl, and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2'3 could be similarly deposited, but did not investigate this metal extensively. Recently, conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. Apparatus and Technique The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T² and T3 containing crystals of the carbonyl. T² is kept in a constant temperature bath (not shown), while T³ is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Se, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by Sb is used to determine the volume included by S4, S6, SB, Slot the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: (I) the specimen temperature, from room temperature to about 1000°C, (2) the carbonyl vapor pressure, from 40 to 220 microns, and (3) the hydrogen flow. In several runs, 0.8 to 1.8 PCt of hydrogen sulfide was introuced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1949

By Thomas T. Read

Mining, which is at least twenty cen-turies old, was at first, and long, wholly a practical art. Little more than two centuries have elapsed since the inception of the idea that general education and a knowledge of natural science would be of advantage to those engaged in the mining industry. Though schools of mining began to develop in Europe early in the eighteenth century the concept of educational preparation, for technical conduct of the industry was slow in winning general acceptance in the industry itself. John Hays Hammond, in his autobiography, recalls that when he sought employment with a mining company after he had graduated from Yale and Freiberg he had to assure its executive, before being even considered for employment, that he did not consider that he had learned anything about mining. This was as late as 1880. Existence in the industry of a prejudice against education of the academic type is perhaps an explanation why inadequate provision has been made by the mining industry for the continuing education of technical employees after they enter employment, although engineering education prior to engaging in industry has now won general acceptance. I am familiar with the existence of 'loop" courses for engineering graduates in metallurgical plants, of schemes for giving mining graduates "practical experience," and of the interest in vocational courses for workmen which sprang up in the period of labor shortage during and immediately following World War I (but which quickly died when the depression of 1921 again made experienced workmen available in sufficient supply), having been chairman of a committee appointed by the Mineral Industry Education Division to make a survey of existing provisions for post-employment training for engineers in our industry. The results of that survey, reported elsewhere, clearly indicate that it is inadequate as to amount; the aim of this paper is to present evidence for belief that it is also inadequate in quality. To avoid becoming too involved, no reference will be made here to post-employment vocational training for workmen, which is a subject differing so much from post-employment education for engineers as to require separate treatment. Neither will postgraduate education for metallurgical engineers be discussed, becadse a distinction must then be made between training for research work and for plant operation, whereas mining engineers engage almost exclusively in operations. Since the situation in the coal-mining industry has been discussed at several recent meetings, that also will be passed over, and what follows should be taken as a discussion applying exclusively to the metal-mining industry. Professional Development In the operations field (both in mining and metallurgy) the work to which a beginner is assigned is seldom closely related to previous academic education. The contrast is almost as great as between

Jan 1, 1943

By Thomas T. Read

Mining, which is at least twenty cen-turies old, was at first, and long, wholly a practical art. Little more than two centuries have elapsed since the inception of the idea that general education and a knowledge of natural science would be of advantage to those engaged in the mining industry. Though schools of mining began to develop in Europe early in the eighteenth century the concept of educational preparation, for technical conduct of the industry was slow in winning general acceptance in the industry itself. John Hays Hammond, in his autobiography, recalls that when he sought employment with a mining company after he had graduated from Yale and Freiberg he had to assure its executive, before being even considered for employment, that he did not consider that he had learned anything about mining. This was as late as 1880. Existence in the industry of a prejudice against education of the academic type is perhaps an explanation why inadequate provision has been made by the mining industry for the continuing education of technical employees after they enter employment, although engineering education prior to engaging in industry has now won general acceptance. I am familiar with the existence of 'loop" courses for engineering graduates in metallurgical plants, of schemes for giving mining graduates "practical experience," and of the interest in vocational courses for workmen which sprang up in the period of labor shortage during and immediately following World War I (but which quickly died when the depression of 1921 again made experienced workmen available in sufficient supply), having been chairman of a committee appointed by the Mineral Industry Education Division to make a survey of existing provisions for post-employment training for engineers in our industry. The results of that survey, reported elsewhere, clearly indicate that it is inadequate as to amount; the aim of this paper is to present evidence for belief that it is also inadequate in quality. To avoid becoming too involved, no reference will be made here to post-employment vocational training for workmen, which is a subject differing so much from post-employment education for engineers as to require separate treatment. Neither will postgraduate education for metallurgical engineers be discussed, becadse a distinction must then be made between training for research work and for plant operation, whereas mining engineers engage almost exclusively in operations. Since the situation in the coal-mining industry has been discussed at several recent meetings, that also will be passed over, and what follows should be taken as a discussion applying exclusively to the metal-mining industry. Professional Development In the operations field (both in mining and metallurgy) the work to which a beginner is assigned is seldom closely related to previous academic education. The contrast is almost as great as between

Jan 1, 1943

By Donald B. Hunter

The Ti-Be system up lo 10 wt pct Be with cortlmercialll' pure titanium has been determined using metal-lographic techniques. Beryllium forms the p eutec-toid type of dinqarz with titanium; the eutectoid occurs at 0.5 xt pct Be azd 1500 F, while an eutectic is foritled at 1887°F containing between 5 and 7.5 rt pct Be. The solubility of beryllium in a titanium does not exceed 0.05 zvt pct and the maximum solubility of Beryllim in 0 titanium is 1 wt pet. PREVIOUS work on the Ti-Be phase diagram indicated that additions of beryllium to titanium resulted in a marked lowering of the melting point,''' and it was also observed that the solubility of beryllium in both a and p titanium was retricted.- With the limited data available, McQuillan and McQuillan constructed a partial hypothetical diagram of the Ti-Be system,= assuming that beryllium formed the 0 eutectoid type of system with titanium. Subsequently Bedford published a tentative diagram of the entire Ti-Be system: although he did not investigate alloys containing less than 10 wt pct Be. This diagram included several compounds described by other authorities.'-l3 The following account describes work directed toward determining the form of the titanium-rich portion of the phase diagram up to 10 wt pct Be. MATERIALS AND METHODS Titanium sponge and a master alloy containing 25 wt pct Be were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 250-g compacts which were melted into buttons by arc melting under purified argon on a water-cooled copper hearth. Results of analyses for beryllium are shown in Table I but no determination of other elements was made at this stage. The alloys were hot-rolled at 1650°F to produce 0.1-in.-thick sheet. Alloys containing up to 1.5 pct Be were fabricated without trouble; samples containing 2 pct cracked initially upon hot rolling, but thereafter rolled satisfactorily to sheet. The 5, 7.5, and 10 pct were hot short and could not be rolled. Surface contamination was removed from samples by sandblasting and pickling in a 5 pct HF-35 pct HNOs solution. For metal log raphic examination, heat-treated specimens were mounted transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and electropolished at 20 v using a solution containing 600 ml of methanol, 60 ml of perchloric acid, 360 ml of butyl cellosolve, and 2 ml of Solvent "X". Difficulty was experienced in obtaining good electropolished surfaces with samples containing more than 1 pct Be, the degree of difficulty in-

Jan 1, 1967

By P. A. Beck, A. Merlini

Quantitative texture determinations were made for rolled and for rolled and annealed strips of 3, 6, and 10 pct Zn brasses. The main components of the rolling texture gradually shift over a wide composition range from the orientation characteristic of copper to that of 70-30 brass. At least the main features of the corresponding gradual changes in the annealing texture may be accounted for qualitatively on the basis of the oriented growth theory of annealing textures. All the oriented nucleation-type theories are notably less successful in accounting for the observed textures. EARLIER investigations by von Goeler and Sachs,' Dahl and Pawlek,' and Brick, Martin, and Angier" suggested that the annealing texture of copper is more sensitive to the addition of solute elements than the rolling texture. It was reported3 that the cube texture changes over into a brass-type recrys-tallization texture on addition of about 1 pct Zn, while the deformation texture changes only at about 5 pct Zn. Such behavior would be difficult to reconcile with any theory of annealing texture formation that relates the annealing texture to the deformation texture. In particular, the oriented growth theory of the cube texture" is based on a certain orientation relationship between the cube texture and the main components of the deformation texture which could not be reconciled with the reported behavior of low brasses. It was, therefore, of interest to re-examine these textures by means of the quantitative methods now available. The deformation and annealing textures of rolled a brasses with approximately 3, 6, and 10 pct Zn have been determined in terms of (111) and (200) pole figures. Experimental Methods The chemical analyses of the Cu-Zn alloys of commercial purity used in the present work are given in Table I. Chill-cast bars of the tabulated compositions were rolled and annealed according to the following schedule: I—rolling from 1.2 to 1.02 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 2— rolling from 1.02 to 0.867 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 3—rolling from 0.867 to 0.600 in. thickness, 31 pct reduction area, annealing 2 hr at 540°C; 4—rolling from 0.600 to 0.400 in. thickness, 33 pct reduction area, annealing 2 hr at 480°C. In the final straight rolling of 96.25 pct reduction area, the strips were reversed end to end after each pass. The final annealing temperature was determined for each alloy by annealing specimens of the cold-rolled strips in salt bath for 5 min at varying temperatures. The results of the hardness measurements are given in Fig. 1, where the final annealing temperature used for each alloy in determining the annealing texture is indicated by a cross.

Jan 1, 1956

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By D. R. Conlon, E. R. Brownscombe

Errors in measurement of reservoir pressure include: (I) gauge errors, and (a) interpretation errors. Gauge errors may be reduced by: (a) reading charts with a comparator microscope, (b) use of hard metal stylus points to give clear lines, (6) insuring temperature equilibrium, and (d) making multiple tests. Check calibrations are equally as important as check well tests. A statistical analysis of such check runs shows quantitatively the advantages of a standardized "zero pressure line'' and of the use of field calibrations made at bottom-hole temperature on the same chart run in the well. Interpretation errors include: (a) fluid heads, which should be corrected to the top of the perforations on the basis of well-fluid gravity and from the top of the perforation to the datum level on the basis of reservoir-fluid gravity, and (b) gradients around the well. Conventional shut-in periods may be entirely inadequate to overcome these, necessitating a reservoir study based on build-up curve data, reservoir history, core analysis and any other available information. Interest in engineering studies of the pressure changes in oil and gas reservoirs is increasing. This type of work yields important information and doubtless will be greatly extended in the future. One of the factors limiting the work, however, is the accuracy with which the reservoir pressures can be determined; for if the inaccuracies in the pressure measurements represent an appreciable percentage of the pressure changes, the engineer is seriously handicapped, and must delay the reservoir study until the reservoir pressure has changed a relatively large amount. This delay can greatly reduce the benefits of such studies, at least from the point of view of aiding the leasing, drilling and completion programs. Thus, from the point of view of reservoir analysis, it is frequently important to obtain the most accurate pressure data possible early in the history of any field—particularly for the gas-distillate fields now being developed. This paper deals with improvements in the measurement of bottom-hole pressures that permit pressures even as high as 4000 or 5000 lb. per sq. in. to be determined with gauge errors of only+ ±I to 2 lb. per sq. in. Since pressures out in the reservoir rather than in the bottom of the hole concern the reservoir analyst, differences between bottom-hole pressures and actual reservoir pressures are also considered. In general, errors in pressure measurement may be divided into: 1. Gauge errors: a. Errors due to inaccuracies in reading the pressure charts. b. Errors due to irreproducibility of the pressure element and recording system. c. Errors caused by failure to allow the gauge to reach temperature equilibrium. 2. Internretation errors: a. Errors caused by a fluid head between the gauge position in tubing and the pressure at the datum level in the reservoir. b. Pressure gradients in the reservoir.

Jan 1, 1946

By M. R. Hatfield, F. J. Vosburgh

IN a recent article,† it was shown that in the blast furnaces in Germany that are lined with carbon blocks no cooling plates are used, and that shower cooling is employed on the hearth and bosh sections. While one of the authors was in Germany he was told that one furnace was being operated without even the shower cooling on the bosh section, though the hearth section was shower-cooled. In discussion of this interesting situation with a number of blast-furnace operators in this country, it was made clearly and promptly evident that shower cooling was very unpopular, probably because of its messiness and its ineffectiveness. Both of the causes for the dislike of shower coolings are reasonable ones. Shower cooling can be and frequently is messy, but the present cooling of blast furnaces leaves much to be desired on that score. Shower cooling is ineffective as compared with plate cooling, so far as its usefulness in keeping the bricks cool enough not to melt or fall to pieces is concerned. However, the introduction of carbon linings changes the situation. No one is concerned with keeping a carbon lining cool, for no temperature in the blast furnace has any effect on carbon, which is just as stable at 3000°F. as it is at 70°F. The only concern is for the shell-to keep it cool enough for safety and comfort and for that shower cooling is sufficient. Of course, with only the shell to cool, instead of the shell plus all the refractory material, much less water would be required, and the necessity for constant attention to the flow would be lessened, as the hundreds of inlets and outlets would be eliminated. Probably half of the water used in cooling a blast furnace is used for cooling the shaft and tuyeres and the remainder for the bosh and hearth sections. However, in view of the dislike of shower cooling in the United States, and particularly because at least one German blast furnace is operated with no cooling of the bosh section, thought was given to the possibility that a carbon-lined blast furnace might be operated without any cooling of the entire carbon-lined portion. For that reason a series of experiments was performed to determine what might be the temperature of the shell of a blast furnace protected by a carbon lining and operated under varying conditions up to a maximum inside temperature of 3000°F. EXPERIMENTAL PROCEDURE A schematic diagram of the experimental setup is shown in Fig. I and a photograph of the entire assembly in Fig. 2. The heating element was a carbon tube nominally 2 5/8 in. o.d. by 2 in. i.d. by 30 in., used as a resistor. Power was furnished by a 15-kva. transformer operating

Jan 1, 1941

By R. F. Stilwell

There are three things that all coal consumers look for when they burn coal: (1) suitability for their particular requirements and burning equipment, (2) uniformity of shipments, and (3) quality as expressed by heating value and other chemical and physical tests. Suitability, or proper application, is determined generally from previous buying experience. It is a function of (1) the reliability and integrity of the shipper and distributor, (2) of a certain coal field or seam and of (3) uniformity and quality. Quality is limited by the location and geology of the seam and mine, the mining and preparation methods and equipment and the knowledge and ability of the personnel. Uniformity of shipments is in many ways the most important factor in coal selection. Lack of uniformity in chemical quality, size consist and treatment cause most of the customer complaints that arise from faults of the coal shipper. Lack of uniformity destroys suitability and quality standards, causing a large customer turnover, and greatly increases sales expense and reduces the net return to the operator. Oil and gas fuels are more uniform in quality than solid fuels, and there will be more gas and oil competition for coal markets after this war than before, because the size of their market is a direct function of the dimensions of their pipe lines, which have been greatly increased during the war. Present mechanical coal-cleaning equipment based upon gravity concentration has gone a long way toward giving us a coal of uniform ash content. The chart in Fig. I, by Hebley,1 shows the greater uniformity of the ash content of washed coal as compared with that of raw coal. Wide variation in the nature and amount of ash in the coal feed to the washer leads to a coal of non-uniform ash content. Mechanica1 cleaning equipment does not understand such terms as ash-softening temperature, coking properties, size consist and sulphur content. Unless the feed to the washer is uniform, the washed coal probably will not be uniform. Table I shows the ash, sulphur and ash-softening temperature of two mines in the Pittsburgh bed, both raw and washed, loaded over the same tipple; also No. 3 and No. 4 Pocahontas seams, both raw and washed, loaded from the same preparation plant. It is obvious that they must be blended or loaded separately if a uniform product is to be obtained. Why Is Blending Necessary? It was natural for the operators of captive mines producing by-product coals to recognize the necessity for blending raw coals of different quality and coking characteristics. They have had many years of experience with blending high, low and medium volatile coals at their oven plants. They have found that careful blending gives a coke of more uniform quality and better structure. Coals that could not be

Jan 1, 1947

By R. F. Stilwell

There are three things that all coal consumers look for when they burn coal: (1) suitability for their particular requirements and burning equipment, (2) uniformity of shipments, and (3) quality as expressed by heating value and other chemical and physical tests. Suitability, or proper application, is determined generally from previous buying experience. It is a function of (1) the reliability and integrity of the shipper and distributor, (2) of a certain coal field or seam and of (3) uniformity and quality. Quality is limited by the location and geology of the seam and mine, the mining and preparation methods and equipment and the knowledge and ability of the personnel. Uniformity of shipments is in many ways the most important factor in coal selection. Lack of uniformity in chemical quality, size consist and treatment cause most of the customer complaints that arise from faults of the coal shipper. Lack of uniformity destroys suitability and quality standards, causing a large customer turnover, and greatly increases sales expense and reduces the net return to the operator. Oil and gas fuels are more uniform in quality than solid fuels, and there will be more gas and oil competition for coal markets after this war than before, because the size of their market is a direct function of the dimensions of their pipe lines, which have been greatly increased during the war. Present mechanical coal-cleaning equipment based upon gravity concentration has gone a long way toward giving us a coal of uniform ash content. The chart in Fig. I, by Hebley,1 shows the greater uniformity of the ash content of washed coal as compared with that of raw coal. Wide variation in the nature and amount of ash in the coal feed to the washer leads to a coal of non-uniform ash content. Mechanica1 cleaning equipment does not understand such terms as ash-softening temperature, coking properties, size consist and sulphur content. Unless the feed to the washer is uniform, the washed coal probably will not be uniform. Table I shows the ash, sulphur and ash-softening temperature of two mines in the Pittsburgh bed, both raw and washed, loaded over the same tipple; also No. 3 and No. 4 Pocahontas seams, both raw and washed, loaded from the same preparation plant. It is obvious that they must be blended or loaded separately if a uniform product is to be obtained. Why Is Blending Necessary? It was natural for the operators of captive mines producing by-product coals to recognize the necessity for blending raw coals of different quality and coking characteristics. They have had many years of experience with blending high, low and medium volatile coals at their oven plants. They have found that careful blending gives a coke of more uniform quality and better structure. Coals that could not be

Jan 1, 1947

By I. W. Walling, F. B. Plummer

Bastin and others have demonstrated the presence of sulphate-reducing bacteria in oil wells producing salt water. Analyses show that at 125°F. bacteria alone reduce sulphates in East Texas salt water by only 3 per cent in 30 days, forming principally hydrogen sulphide and sodium or calcium hydroxide. The hydrogen sulphide reacts with soluble iron compounds to produce iron sulphide in the absence of oxygen, and ferric hydroxide where oxygen and air are present. Where iron or other metals and iron sulphide are already in the water containing bacteria, I00 per cent reduction of the sulphates is complete in 30 days or less; where magnesium is present, reduction is complete in 15 days. The effects of changes in temperature, of different bactericides, and of concentration of bactericides on sulphate reduction are described in detail and illustrated by tables and curves. The significance of sulphate reduction on corrosive properties of oil-field water is briefly discussed. Chemistry of East Texas Oil-field Water The chemical composition of the water in the East Texas field salt-water disposal pits is shown in Table I. This salt water corrodes pipes, pumps, and steel tanks excessively, principally because of its content of oxygen, hydrogen, sulphide, and carbonic acid. The carbonates in the water when exposed to air tend to give up carbon dioxide and to precipitate calcium carbonate in large quantities. This forms coatings in tanks, settling pits, and ditches, and soon, unless removed by acid treatment, will effectively clog an injection well and reduce the flow of water back into the ground. The iron compounds in the water, most of which are dissolved from tanks and pipes, are in the ferrous form, and when exposed to the air are oxidized from soluble ferrous carbonate to insoluble ferric hydroxide, resulting in the precipitation of a gelatinous precipitate that will clog oil-field sands effectively: 2Fe(HCO3)2 + O + H2O -> 2Fe(OH)3 + 4CO2 The sulphates in strong sulphate-bearing water may be attacked by swarms of sulphate-reducing bacteria and more hydrogen sulphide may be produced. The hydrogen sulphide reacts with soluble minerals in the water to form black sludges. A knowledge of the chemistry of each reaction in oil-field water is important to the oil-field engineer, since means must be devised to prevent the formation of harmful precipitates that clog injection wells and to prevent corrosion of tanks by harmful products of biochemical processes. Methods of Treating Water before Injection into Ground* The open system of handling the waste salt water in the East Texas field consists of aerating and chemically treating the water to precipitate the unstable iron,

Jan 1, 1946

By F. B. Plummer, I. W. Walling

Bastin and others have demonstrated the presence of sulphate-reducing bacteria in oil wells producing salt water. Analyses show that at 125°F. bacteria alone reduce sulphates in East Texas salt water by only 3 per cent in 30 days, forming principally hydrogen sulphide and sodium or calcium hydroxide. The hydrogen sulphide reacts with soluble iron compounds to produce iron sulphide in the absence of oxygen, and ferric hydroxide where oxygen and air are present. Where iron or other metals and iron sulphide are already in the water containing bacteria, I00 per cent reduction of the sulphates is complete in 30 days or less; where magnesium is present, reduction is complete in 15 days. The effects of changes in temperature, of different bactericides, and of concentration of bactericides on sulphate reduction are described in detail and illustrated by tables and curves. The significance of sulphate reduction on corrosive properties of oil-field water is briefly discussed. Chemistry of East Texas Oil-field Water The chemical composition of the water in the East Texas field salt-water disposal pits is shown in Table I. This salt water corrodes pipes, pumps, and steel tanks excessively, principally because of its content of oxygen, hydrogen, sulphide, and carbonic acid. The carbonates in the water when exposed to air tend to give up carbon dioxide and to precipitate calcium carbonate in large quantities. This forms coatings in tanks, settling pits, and ditches, and soon, unless removed by acid treatment, will effectively clog an injection well and reduce the flow of water back into the ground. The iron compounds in the water, most of which are dissolved from tanks and pipes, are in the ferrous form, and when exposed to the air are oxidized from soluble ferrous carbonate to insoluble ferric hydroxide, resulting in the precipitation of a gelatinous precipitate that will clog oil-field sands effectively: 2Fe(HCO3)2 + O + H2O -> 2Fe(OH)3 + 4CO2 The sulphates in strong sulphate-bearing water may be attacked by swarms of sulphate-reducing bacteria and more hydrogen sulphide may be produced. The hydrogen sulphide reacts with soluble minerals in the water to form black sludges. A knowledge of the chemistry of each reaction in oil-field water is important to the oil-field engineer, since means must be devised to prevent the formation of harmful precipitates that clog injection wells and to prevent corrosion of tanks by harmful products of biochemical processes. Methods of Treating Water before Injection into Ground* The open system of handling the waste salt water in the East Texas field consists of aerating and chemically treating the water to precipitate the unstable iron,

Jan 1, 1946

By Shiou-Chuan Sun

There are several postulations for the mechanism of slime-coating. Incel proposed the electrostatic hypothesis, del Giudice2 suggested the chemical theory; Bankoff3 reported that slime-coating is inhibited whenever the surfaces of the slime particles are ionized sufficiently for Brownian movement to occur, and is facilitated when they are not. These postulations were examined by experiments involving the Burton tube, the cataphoretic cell, and slime-coating. The techniques involved will be described elsewhere in this paper. The electrostatic hypothesis, supported by migration experiments in a Burton tube, was abandoned by del Giudice.2 Experiments of mineral migration in a Burton tube. after the idea of Ince with modification, indicated that this apparatus was inefficient for accurate observation. A cataphoretic cell was constructed. The experimental data, as shown in this paper, enable the correlation and advancing of this hypothesis. Del Giudice's chemical hypothesis considered that slime particles are attached to the galena surfaces by a cement formed as the result of a metathetical reaction between the sulphide and the slime particles. Applying this hypothesis, the calcite slime particles were cemented to the galena surface by the formation of a cementing lead carbonate. In a similar way, lead silicate was considered as the cement of quartz slime coating on galena. Experiments verifying this hypothesis were carried out according to the following procedure: Fresh mineral particles selected from the central part of the broken lumps and examined first under a microscope for ascertaining a clean surface were placed in a small beaker (1.5-in. dia. by 2.5 in. deep) half filled with one kind of slime pulp. The dilution of all slime pulp was 4:I and the particle size of slime was minus 400-mesh. After agitation for 5 min. the specimen was removed by a sharp-end tong and washed gently three times in three separate distilled water baths. It was dried before a small electrical fan and examined immediately under a microscope. A photograph was made of the observation. With reference to the published solubilities,' several of these experiments, which contradict the chemical hypothesis, are listed as following: I. The coating of fluorite slime on the galena surface was light but the coating of galena slime on the fluorite surface was heavy. In a similar way, the coating of quartz slime on the galena was fairly light, but the coating of galena slime on the quartz particle was heavy. According to the chemical hypothesis, using the same constituents and regardless of which is the slime, the density of the coating should be expected to be the same. This, however, as shown above, is not true. Moreover, fluorite (CaF2), having a solubility of 16 mg.4a per liter of water, should not be

Jan 1, 1943

By Shiou-Chuan Sun

There are several postulations for the mechanism of slime-coating. Incel proposed the electrostatic hypothesis, del Giudice2 suggested the chemical theory; Bankoff3 reported that slime-coating is inhibited whenever the surfaces of the slime particles are ionized sufficiently for Brownian movement to occur, and is facilitated when they are not. These postulations were examined by experiments involving the Burton tube, the cataphoretic cell, and slime-coating. The techniques involved will be described elsewhere in this paper. The electrostatic hypothesis, supported by migration experiments in a Burton tube, was abandoned by del Giudice.2 Experiments of mineral migration in a Burton tube. after the idea of Ince with modification, indicated that this apparatus was inefficient for accurate observation. A cataphoretic cell was constructed. The experimental data, as shown in this paper, enable the correlation and advancing of this hypothesis. Del Giudice's chemical hypothesis considered that slime particles are attached to the galena surfaces by a cement formed as the result of a metathetical reaction between the sulphide and the slime particles. Applying this hypothesis, the calcite slime particles were cemented to the galena surface by the formation of a cementing lead carbonate. In a similar way, lead silicate was considered as the cement of quartz slime coating on galena. Experiments verifying this hypothesis were carried out according to the following procedure: Fresh mineral particles selected from the central part of the broken lumps and examined first under a microscope for ascertaining a clean surface were placed in a small beaker (1.5-in. dia. by 2.5 in. deep) half filled with one kind of slime pulp. The dilution of all slime pulp was 4:I and the particle size of slime was minus 400-mesh. After agitation for 5 min. the specimen was removed by a sharp-end tong and washed gently three times in three separate distilled water baths. It was dried before a small electrical fan and examined immediately under a microscope. A photograph was made of the observation. With reference to the published solubilities,' several of these experiments, which contradict the chemical hypothesis, are listed as following: I. The coating of fluorite slime on the galena surface was light but the coating of galena slime on the fluorite surface was heavy. In a similar way, the coating of quartz slime on the galena was fairly light, but the coating of galena slime on the quartz particle was heavy. According to the chemical hypothesis, using the same constituents and regardless of which is the slime, the density of the coating should be expected to be the same. This, however, as shown above, is not true. Moreover, fluorite (CaF2), having a solubility of 16 mg.4a per liter of water, should not be

Jan 1, 1943

By P. Chaudhari, Michael B. Bever

The heat of solution at infinite dilution of selenium in bismuth, the heat of mixing of selenium and bismuth, and the limit of solubility of selenium in bis~rzuth have been determined at 573, 623; and 663°K by metal solution calorimetry. The heat of forrrzation of the compound Bi2Se at these temperatures has been determined from the heat effects associated with the precipitation of the compound from a saturated solution oj selenium and bismuth. The published information on the thermodynamic properties of the system Bi-Se is limited. The heat of solution at infinite dilution of selenium in bismuth at 623°K has been measured.' The heat of formation at 273 K1 and room temperature2 and the heat capacity at 80 K3 of the compound Bi2Se3 have been reported. An estimate of the heat of formation of the compound BiSe at room temperature has been published.2 Information on the phase relations in the system Bi-Se is available.' In the investigation reported here the following quantities have been determined at 573", 623", and 663°K: 1) the heat of solution at infinite dilution of selenium in bismuth, 2) the heat of mixing of selenium and bismuth in bismuth-rich solutions, 3) the limit of solubility of selenium in bismuth, and 4) the heat of formation of the compound BizSe. These quantities were determined by the addition of selenium to bismuth-rich solutions in a metal solution calorimeter. The determination of the heat of formation at the tem- perature of the calorimeter bath involved the precipitation of the compound from a saturated solution in the calorimeter. 5,6 This method differs from that commonly used which requires the addition of the compound and of a mechanical mixture of its components and yields the heat of formation at the temperature from which the additions are made (273 K EXPERIMENTAL PROCEDURE AND CALCULATIONS The solution calorimeter has been described in detail.' Pure bismuth (99.999+ pct) was used as the bath at the start of a run. The calorimeter was calibrated with small amounts of bismuth added from 273°K; the differences of the heat contents of bismuth at 273°K and the temperatures of the baths are listed in Table I. After the calibration, additions of hexagonal selenium (99.999+ pct) were made. Loss of selenium by evaporation was negligible. No unusual experimental difficulties were encountered.9 The differences in the heat contents10 of selenium at 273°K and the temperature of the bath, listed in Table I, were subtracted from the measured heat effects to give the "adjusted heat effects". The methods by which the heat of solution at infinite dilution, the

Jan 1, 1968

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K'. Making these changes.

Jan 1, 1942

By A. T. Beckwith

This paper concerns measurements of low-velocity air currents and investigations on mine ventilation by means of chemical smoke. The chemical smoke used is produced without flame and at ordinary mine temperatures, and therefore presents no ignition hazard in gaseous mines. Mining men who have worked in open-light mines are familiar with the use of tobacco smoke in determining the direction of air travel and approximately measuring low-velocity air currents. The use of chemical smoke is merely a refinement on the use of tobacco smoke and the flameless low-temperature source of chemical smoke has the additional advantage that it can be used in gaseous mines. Ventilation smoke apparatus, Fig I, is a simple device for producing dense white smoke. The apparatus as shown consists of a rubber aspirator bulb which is used to force air through a glass "smoke tube" containing a chemical substance that produces a dense white smoke on contact with air. The apparatus was developed by engineers of the U. S. Bureau of Mines.' It is inexpensive, weighs less than 3 oz, is easily carried in a pocket, and requires no skill to operate. Smoke apparatus is invaluable in practical mine ventilation work for: (I) measuring low-velocity air currents, (2) detecting air leakage, (3) observing airflow characteristics. This paper is written to show the merits of the apparatus, and is based upon findings through its extensive use, during the past six years, in mines operated by the Lehigh Navigation Coal Co. Inc. The Apparatus Certain chemicals, such as stannic chloride (SnCl4) and pyrosulphuric acid (H2S2O7) produce "white smoke" when exposed to air. Stannic chloride gives off vapors which on contact with moist air cause the formation of solid hydrates, of which SnCl4.5H20 is the most important. Pyrosulphuric acid decomposes when exposed to air with the evolution of sulphur trioxide (SO3) fumes, which become white upon contacting moisture in the air. A chemical, such as one of the above, is the active substance in a smoke tube. The glass tubes are hermetically sealed during manufacture, and are made ready for use by merely breaking off the tips at the conveniently located file cuts. When the smoke tube is connected to the aspirator, depressing the aspirator bulb forces air into contact with the chemical, and smoke discharges from the open end of the tube. A white solid (a hydrate if stannic chloride is used, or sulphur trioxide if pyrosulphuric acid is used) may occasionally form a cake in the outlet opening of a smoke tube. A small wire such as an ordinary paper clip can be conveniently employed to dislodge the cake should it seal the tube. When the assembled apparatus is not

Jan 1, 1949

By E. F. Sturcken, J. W. Croach

A grain orientation distribution function, P(u,F), was developed for use in predicting physical properties in oriented metals. Examples are given of the use of the function to predict thermal expansion coefficients in rolled uranium rods and plate. The P(u,F) function was synthesized from X-ray difpaction intensity measurements, Ii, norrnally used to plot inverse pole figures. The symbols u and F specify the angles that the crystallographic axes of the grain make with the normal to the sample surface and P(u, F) gives the number of grains oriented in each direction, (u,F). P(u,F) is obtained from a least squares fit of the Ii to an orthonormal set of spherical harmonic functions. The P(u, F) function was also used to define a quantity, J, which is a measure of the departure of the orientation distribution from unifomzity (or "randomness"). The J parameter may be used to follow, quantitatively, the amount of preferred orientation induced as a function of mechanical working or heat treatment. An example is given of the application of the J parameter to prefevred orientation studies of hot- and cold-rolled uranium rods and hot-rolled uranium plate. Because P(u,F) is derived from relative intensity measurements by the powder diffraction technique, it is applicable to material with large absorption coefficients and/or grain size and is particularly suitable for characterizing the preferred orientation of large numbers of samples such as fuel elenzents for a nuclear reactor. IN general the physical properties of an oriented metal depend on the direction in which the properties are measured. Hence to predict physical properties the grain orientation must be known as a function of the direction of the specimen. The conventional methods of expressing preferred orientation measurements are the pole figure1 and the inverse pole figure.2-8 Both methods are difficult to use for predicting physical propertiess because they are graphical and because they are stereographic projections and hence are not "area-true." In the present report a quantitative orientation distribution function, P(u,F), is synthesized from pole density measurements normally used to plot inverse pole figures. For inverse pole figure plots the pole densities, pi, are obtained by powder dif-fractometer intensity measurements of their reflections from a flat surface of the sample, normal to the direction of interest. Each pole density, pi, represents a single orientation, i, and is proportional to the volume of material with orientation, i; hence a set of pi gives an approximation for the general orientation for the sample direction measured. The expression8'7 for calculating the pole densities, pi, from the diffraction measurements was previously

Jan 1, 1963

By R. Casting, J. Philibert, and C. Crussard

APPARATUS described in this paper uses the properties of X-radiation, emitted by substances under electron bombardment, as a means of rapid chemical point analysis. The method is based upon the principles of emission X-ray spectrography pioneered by Moseley in 1913. A very finely focused beam of electrons—the electron probe—is projected on the surface of a sample, which has a very large area compared with the beam diameter, at the point where it is desired to know the chemical composition. The minute volume of the sample which is thus irradiated emits a complex X-ray spectrum consisting principally of the characteristic radiations of the elements present in the volume. Measurement of the wavelength and intensity of each component of this spectrum thus affords a simple method of determining the chemical identity and concentration of these elements. The volume of sample which is analyzed at each position of the beam is limited by the diffusion of electrons in the sample. For an accelerating potential of the electron beam of about 30 kv, which is a convenient value for producing the characteristic radiation, this diffusion extends over a diameter of about 1 µ normal to the beam, and about 2 µ in the direction of the beam. Thus a beam of 1 µ in diameter leads to a volume of about 2 µ in diameter being irradiated. The limits of the analyzed region are thus considerably smaller than those obtained by using spark or arc emission spectrometry, which must extend to about 50 µ at right angles to the beam, and those obtained in X-ray fluorescence analysis, where the penetration of the specimen is considerably greater. The apparatus itself consists of three main parts: an electron optical system. an X-ray spectrograph and an optical microscope. The electron opticai system consists of a tungsten cathode emitting the electrow and a pair of magnetic lenses which focus the electron beam on the specimen to be analyzed. The specimen is prepared in the usual way, as in optical micrography. The X-radiation, emitted at the focal spot where the electrons strike the sample, is analyzed with a curved crystal, Geiger-Müller counter, vacuum spectrograph. The light microscope, designed to observe the surface of the sample in the region to be analyzed, is provided with a reflecting objective placed on the axis of the second magnetic lens. Its magnification is X450. The quantitative determination of an element A in the analyzed region is made by measuring the intensity I, of a strong characteristic line of the element, as emitted from the sample, and then the intensity I (A) of this same line as emitted from a

Jan 1, 1958

By G. W. King, A. Bogrow, L. F. Marek

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948