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By Thomas M. Drown

The process for determining phosphorus in iron now in most general use in the laboratories of iron and steel works, is, I think, the one proposed bv Mr. Emmerton." In this process the solution of the iron for precipitation by ammonium molybdate is effected by treating the iron with nitric acid, evaporating to hard dryness in a dish, taking up with hydrochloric acid and driving off the greater portion of the hydrochloric by nitric acid. This procedure accomplishes, first, the destruction of all the carbonaceous matters; and, second; it renders all the silica insoluble. Experience has proved the former—the complete oxidation of the carbon—to be absolutely essential; but the explanation usually given, namely, that unless the carbon compounds are destroyed they will have a solvent action on the yellow precipitate, I am inclined to

Jan 1, 1890

By G. Pizzi, G. M. Ciucci, G. L. Chierici

The use of the material balance equation to estimate the volume of hydrocarbons originally present in a reservoir, whose producing mechanism is partly due to water drive, has been discussed in the literature by several authors. There is no general agreement upon the possibility of obtaining reliable results by this method. Gas reservoirs in contact with an active aquifer are considered in this paper. Theoretical considerations based on the cybernetic principle of uncertainty (which states that the internal structure of a system cannot be uniquely determined from its observed external behavior) lead to the conclusion that the volume of gas originally present in a reservoir of this type cannot be uniquely determined from its past history. The range of values which encompasses the actual value of the reserves varies from case to case and must be determined by either numerical or analogical methods. Results obtained for six gas fields are reported. All these fields were produced with small fluctuations in their production rates, as is common practice for gas reservoirs; no gas storage fields were considered. Results obtained show that reserves values in a range of 1 to 2, associated with appropriate aquifers, allow the matching of the reservoir past history with mean-square deviations less than the experimental errors involved in pressure and produclion measurements. Similar results have been found in several other partial water drive gas reservoirs. From these results it is concluded that gas reserves cannot be uniquely determined from the past performance of partial water drive reservoirs, at least in cases where the reservoir has been submitted to small fluctuations in the production rates, and pressure data of normal accuracy are available. INTRODUCTION A number of authors have analyzed the problem of estimating the reserves originally present in a partial water drive reservoir from its past pressure-production performance. Literature which deals with this subject can be grouped, according to their conclusions, as follows. 1. A reliable value for the reserves can be obtained even if reservoir data (pressure and cumulative production) are affected by errors within the normal range.'-' 2. A reliable value for the reserves can be obtained only if reservoir data are very accurate'- or if past production performance has been subjected to abrupt variations in the production rate."' 3. No unique value for the reserves can be obtained from reservoir past production performance. This conclusion has been based upon theoretical considerations" and verified in several field cases. The purpose of this paper, which deals only with partial water drive gas reservoirs, is to test the above conclusions against actual field cases. Some theoretical considerations on this problem are also presented. THEORETICAL CONSIDERATIONS As the behavior of a gas reservoir communicating with an aquifer depends on both the aquifer and the reservoir characteristics, the physical system to be studied is the combined gas reservoir plus aquifer. The information which is available for studying the performance of such a system is the well production rates and bottom-hole pressures, all given as functions of time. The external behavior of the reservoir-aquifer system is therefore described by 2n input variables (Gp, Wp,) and n output variables (p,), n being the number of wells in the reservoir. In reservoir engineering it is common practice to consider the reservoir as a whole, disregarding the internal distribution of pressures and of producing wells. This practice is equivalent to substituting the above multi-variable system with a single-variable system, where the average reservoir pressure is the only output variable and the cumulative production G,(t) and W,(t) are the input variables. The internal structure of such a system, defined by initial gas reserves G, aquifer shape and dimensions, boundary conditions and petrophysical parameters distribution throughout the aquifer, is unknown. Therefore, from a cybernetic point of view the system is a "black-box It has been demonstrated" that for a blackbox the indetermination principle holds. Accordingly, the number of different internal structures (or set of parameters) which can account for the observed external behavior is infinite. As a consequence, the initial reserves cannot be uniquely determined from the reservoir past performance. When W,(t) is known, the determination of G from

By K. V. S. Sastry, V. P. Mehrotra

A laboratory investigation was carried out to study the influence of asphalt, bentonite, and corn starch binders on the pelletization kinetics of coal fines and on the quality of the resulting pellets. Pellet quality was evaluated in term of the compression strength, impact resistance (drop test), abrasion resistance, and resistance to severe weather conditions. The amount of binder addition did not significantly influence the pellet growth kinetics. However, the pellet quality varied markedly depending upon the type and the amount of binder wed. Experimental results are explained on the basis of the mechanism of interaction between the coal particles and the binders. Of the three binders tested, corn starch proved to be the best in all respects but for the resistance to water penetration. Finally, a combination of corn starch (imparting strength) and asphalt emulsion (imparting resistance to water penetration) was found to yield the best quality coal pellets.

Jan 1, 1983

By Cyril Wells, Robert F. Mehl

The purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2o C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made2. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsenl that variations as great as 30' C. exist in the reported data on the A3 temperatures in iron-carbon alloys. Fortunately, the Aa temperature in pure iron is now known to be 910" C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato5 on both hypoeutectoid and hyper-eutectoid steels. Esser made a dilatometric and magnetic study of iron and iron-carbon alloys containing 0.06 to 0.86 per cent C, for which a high purity is claimed. Presumably the electrolytic iron was reasonably pure, but the alloys contained considerable impurities, on the average totaling 0.35 per

Jan 1, 1937

By John T. Dickman, Ralph E. O’Dette

Chemical Abstracts Service (CAS) is in the process of evolving a computer-based information system which will process all of the material selected for abstracting in the area of chemistry and chemical engineering and its related fields such as the earth sciences and technologies. This system is already operational to some extent and is expected to be fully utilized by 1971. The objective of CAS is to make chemical and related information more readily available, more usable and more used. Chemical Abstracts handle some 5000 abstracts weekly from 13, 000 journals and patents from 25 nations. These cover all of the 80 CA subject sections which relate to chemistry and also extend into areas of interest to geologists, mineralogists, and mining engineers. In this way, CAS fulfills its objective of complete coverage of its major fields, informative abstracting, and indexing to maximum specificity. The concept of a computer-based information system is that of a single machine-language data base into which the results of intellectual analysis of the literature are entered and from which computer programs produce a variety of publications and services applicable to the needs of a wide range of users.

Jan 1, 1969

By A. H. Daane, R. L. Myklebust

The yttrium-manganese system has been investigated by thermal, metallographic, and X-ray diffraction methods. There are three intermetallic compounds present: YMn2 which melts congruently, YMn4, which undergoes syntectic decomposition, and YMn,, which undergoes peritectic decomposition. The compound YMn4 is ferromagnetic at room temperature with a Curie temperature of 214°C. There are eutectics at 25.2, 60.9, and 82.0 wt pct Mn which melt at 878°, 1100°, and 1075°C, respectively. Crys-tallographic data are given for YMn4, and YMn12 . The terminal solid solubilities are low. In a general program of study of yttrium metal in this laboratory some alloy systems of this metal with elements of the first transition period have been examined. This work was originally instigated by experiences in cladding yttrium with jackets of some protective metals such as Inconel for high-temperature service in air.' In some cases a low-melting phase was observed to form between the Inconel and the yttrium resulting in failure of the samples. In characterizing this reaction, a survey was made of the systems of yttrium with chromium, manganese, iron and nickel,, and it was found that a eutectic was formed between these metals and yttrium on the yttrium-rich side of the system. This present study of the Y-Mn system was carried out to examine in more detail the alloying nature of yttrium, and to correlate trends that have been observed in previous related studies. It was observed by Voge13 that in the systems of lanthanum, cerium, and praseodymium with each of the metals in the first transition series, the tendency to form compounds diminished in the order nickel, cobalt, and iron while no compounds were formed with manganese, chromium, or titanium. Beaudry and Daane4 observed a similar behavior in the systems of yttrium with some members of the first transition series except that the tendency for compound formation was greater. Both the Y-Ti5 and Y-Cra systems consist of simple eutectics, while in the Y-Fe,7 Y-CO, and Y-Ni4 systems, there are four, eight, and nine compounds, respectively. In addition to the above trends, the similar atomic radii and electronegativities of yttrium and thorium invite a comparison between their alloying behaviors with a common element such as manganese. In crys- tallographic studies, Florio et al.' have identified three intermediate phases in this system which are ThMn2, Th6Mn23, and ThMn,,. Gschneidner and Waber10 have examined published information on alloy systems of the rare-earth metals and have correlated this information with current alloying theory. From their study, they predicted that the Y-Mn system would contain one intermetallic compound. On the basis of this prediction, the trend in the alloying behavior of yttrium with the elements of the first transition series and the alloying behavior of thorium with manganese, one might expect from one to three intermetallic compounds to form in the Y-Mn system. A consideration of Hume-Rothery's rules of alloying based on size-factor, electronegativity, and valency suggested a small terminal solubility and possible compound formation. The present study was undertaken to confirm these predictions of low terminal solid solubility and compound formation and to establish the general alloying behavior of yttrium with manganese. EXPERIMENTAL Materials. The manganese used in this investigation was obtained from the Foote Mineral Co. as electrolytic plates of 99.9 pct stated purity; the yttrium metal was prepared in this laboratory. Table I gives the analyses of these materials. For the solubility studies at the yttrium-rich end of the alloy system, distilled yttrium, whose major impurity was 200 ppm Ti, was used. Preparation of Alloys. The alloys were formed by comelting the two metals in an are-melting furnace under an atmosphere of argon. The buttons thus formed were inverted and remelted three to five times to promote homogeneity. Due to the high vapor pressure of manganese, it was assumed that the weight lost during are-melting was all manganese. This assumption was based on the very good agreement observed between calculated compositions and chemical analyses of several alloys. The compositions of the dilute alloys used for solid solu-

Jan 1, 1962

By Charles W. Dickson

CONTENTS. [ ] I.THE RELATION OF NICKEL TO PYRRHOTITE. Introduction. The Sudbury district is to-day one of the two great sources of nickel in the world. The peculiar geological relations of

Jan 1, 1913

By E. W. Engle

Fox several years the Fansteel Products Co. has been engaged in the production and development of various of the rarer metals. It is at present engaged in the commercial production of tantalum, tungsten, and molybdenum in a very high state of purity. The information contained in this paper is partly a general compilation from various sources and partly information obtained as a result of recent years of work in the laboratory of this company. Tantalum, tungsten, and molybdenum form a group peculiar to themselves among the commercially available metals. Their very high melting points (tantalum 2770° C., tungsten 3350° C., and molybdenum 2550° C.) set them apart so far as the metallurgical processes for their production are concerned. Further, when properly prepared and treated they will stand a somewhat unusual degree of cold work, that is work below the temperature at which marked crystal growth takes place. Such cold-worked metal may show a high tensile strength; tantalum to 130,000 lb. per sq. in., tungsten to 490,000 lb., and molybdenum to 260,000 lb., in the form of fine wire. In physical appearance, these metals are not unlike some steels; they may be better described by saying that polished tantalum some¬what resembles lead; polished tungsten, iron; and polished molybdenum, nickel. The polished surfaces of all three remain untarnished in ordinary air. Air containing corrosion-producing impurities will, in general, show molybdenum the least resistant to corrosion and tantalum the most resistant. Molybdenum has, however, a high degree of resistance to corrosion by hydrochloric acid, a property that should render it of commercial interest. On the other hand, it is markedly attacked by some of the weaker organic acids.

Jan 3, 1925

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.'" Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence.

Jan 1, 1955

By John A. Meech, J. G. Paterson

Activated carbon is a strong adsorbent for amyl xanthate, capable of removing from solution up to a quarter of its own weight in xanthate. In selective flotation system where depression is unstable, separation efficiency increases with activated carbon additions. The improvements observed are brought about by two mechanisms. First, by removing stripped and residual collector ions from solution, competition between depressant and xanthate is reduced and depression is stabilized. In addition, the texture of the froth phase at high pine oil concentrations is modified by activated carbon such that better drainage between the air bubbles takes place, alleviating the mechanical entrapment of depressed mineral particles. In treating a bulk copper/lead concentrate produced from GECO ore, selectively between galena and chalcopyrite is increased when activated carbon is used. Although the rate of flotation of galena is marginally lowered by activated carbon, a small extension in the duration of flotation allows the lead recovery to increase by 19% at the same recovery of copper. An addition rate of 0.75 kg/ton (1.5 lb/st) of bulk concentrate is suggested as optimum from this testwork. However, the actual level used in the mill is dependent upon the residual concentrations of collector and frother in the bulk concentrate pulp.

Jan 1, 1979

By C. E. Mills

STUDIES of ground movement and subsidence resulting from mining operations cover a broad field. It is also a very important consideration and one that eventually affects nearly every mining operation of any extent. The damage to surface buildings, removal of mine surface plants and replacements of main hoisting shafts must reach an astounding expenditure were these cost figures available over a period of years. Were the subject one of mathematical formula and dependent only on the angle of draw of the walls or country rocks, the problem would be relatively simple. Consideration must be given to depth and extent of workings; structural conditions of the orebodies and enclosing country rock; physical properties of these same rocks, including schistosity, bedding, jointing, slips, dikes, faults, and other structural weaknesses. The method of mining, extent of openings, supporting pillars, and amount of moisture or water underground are other pertinent factors. With such a large number of variable factors, it is apparent that the subject of subsidence is one that must be based largely on experience and results at other mines where conditions are somewhat comparable. In presenting this paper, it is the intent to describe the progressive results of past ground movements at the United Verde, to bring out physical conditions largely responsible for this movement, but to refrain from theorizing on the ultimate extent of subsidence resulting from future mining operations.

Jan 1, 1934

By R. V. Ramani, G. W. Luxbacher

Computer simulation of mine ventilation system is rapidly becoming an essential tool in mine planning and design. This Paper examines the utilization of ventilation simulation techniques to evaluate the number, shape, size and layout of mine entries in a typical coal mining system. Since the mains and sub-mains serve primarily for transportation and ventilation and the ventilation system is critically important to the health and safety of the workers, there exists a great need for optimal designs in this area. Evaluation criteria could include, among others, minimization of power costs, shaft requirements and leakage. Constraints of this optimization problem include health and safety regulations and production and mine infrastructure requirements.

Jan 1, 1980

By N. Brown

From the theories of flow and fracture it is shown that the difference in reciprocals of the transition temperatures (OK) is a quantitative measure of temper ernbrittlement. Experimental data are given which support this conclusion. STUDIES of temper embrittlement have been made with various viewpoints; some involved a study of the kinetics of the reaction,',2'" others were concerned with changes in the mechanical properties," . and still others investigated the structural differences between the embrittled and unembrittled states by means of the microscope," -ray ,' measurements of electrode potential," and electrical resistivity." In all these studies, the difference in impact properties was the criterion for distinguishing between the embrittled and unembrittled states. By common agreement the difference in transition temperatures is now taken as a measure of the degree of embrittlement, and this measure is used as the quantitative measure upon which studies of the phenomenon are based. Vidal and Jolivet"' suggested that the degree of embrittlement was the same whether measured by impact or by a slow bend test. Their conclusion was based on tests at constant temperature. Jaffe and Buffum" using the impact and slow bend test showed that, for a given degree of embrittlement, the difference in transition temperatures varied with the method of testing. Hultgren and Chang" showed that the difference in transition temperature produced by the V-notched Charpy impact test was not the same as the value produced by the keyhole-notched impact test. This is a very fundamental point because there can be no true measure of temper embrittlement unless it is invariant with respect to the test method. Theory The purpose of this analysis is to show how the transition temperature depends on the stress distribution and the state of the material. The criterion for fracture may be stated as follws: where iF is some function of the principle stresses and F is a critical condition depending on the state of the metal. Similarly yielding occurs when Where is another function of the prin-ciple stresses and Y is a critical value depending on the state of the material. There is some controversy as to the exact form of the function f,.(u,, u,, us) but most experimental data give the following criterion:= where 8, and 6, = 21 or 0. Combinations of 6, and 8, give the various criteria such as the normal stress, the hydrostatic tension, and the maximum shear stress laws. Agreement is general that the octahedral shear stress law adequately describes the yield condition. where the bracketed factor will be called the design factor and depends on the stress distribution. Whether the metal decides to yield or fracture is given by the condition that The effect of temperature and strain rate upon Y has been studied by various investigators, It has been shown by MacGregor and Fisher" that

Jan 1, 1955

Discussion of the paper of A. P. WATT, presented at the St. Louis meeting, October, 1917, and printed in Bulletin No. 130, October, 1917, pp. 1476 to 1563. THE CHAIRMAN (0. M. _BILHARZ, Miami, Okla.).-Mr. Watt's reference to sorting or hand-picking of the ore in the lead district, which is being introduced at Mine La Motte, is especially interesting. I believe, from my former experience in the district, that hand-picking should be practised to some extent by all the companies in the Lead Belt. I know that a great many thousand tons containing only very small amounts of lead are passed through the mills, which, of course, is not to the advantage of milling machinery. That procedure may be Warranted at times of high prices, but I think that hand-picking should ordinarily be adopted to some extent: ERNEST GAYFORD, Salt Lake City, Utah.-On page 1525, speaking of the settling of slime previous to treatment either on slime tables or by flotation, Mr. Watt states: "The settling area allowed per ton of dry slime varies from 11 to 16 sq. ft.-an average for the district would be about 13 sq. ft. of settling area per ton of dry slime. This figure applies when the, discharge contains 20 per cent. solids." Mr. Ramsey, of the Dorr company, is here and I would like to ask him whether a settling area of 13 sq. ft. per ton of dry slime per 24 hr. is not considerably above the average area of Dorr settling tanks, and whether 20 per cent. solids is not above the general dilution for that' capacity? I should also like to know what is the general average on slimes of that character. E. R. RAMSEY, Denver, Colo.-An allowance of 13 sq. ft. per ton does seem rather large. I am not familiar with the settling characteristics of the dolomitic gangue, but as an average over the country, I should say that 6 or 7 sq. ft. would be nearer correct for discharge at that consistency. L. A. DELANO, Bowie Terre, Mo.-We have had an opportunity to try our tanks at the highest capacity, and-find that by thickening the slime to 30 per cent. solids we average 12 sq. ft. per ton of dry slime. ERNEST GAYFORD.-DO you find any definite ratio between the thickness of the discharge and the settling capacity of the tank? Do you consider that the tank has a larger capacity if the discharge is 3 to 1 than if it is 50 per cent. solids? L. A. DELANO.-I think it has greater capacity with the thinner discharge. It depends a good deal on the density of feed to the tanks; in our case the feed contains 2.5 per cent. solids.

Jan 1, 1918

By Oliver C. Ralston, Foster Fraas

INTRODUCTION ELECTROSTATIC methods of separation are used only when some peculiar advantage is gained. Such cases are minerals that are not separable by differences in specific gravity or magnetic response and that are desired in particles as large as 10-mesh, a size on which flotation separation is inefficient. This paper covers several separations of this type and others. It includes studies in the electrostatic behavior of kyanite, sillimanite, and zircon, simple silicates that cannot be called either acid or basic but are more nearly neutral. Kyanite and sillimanite are both desired in 10-mesh size and are difficult to beneficiate from low-grade ores to give that type of concentrate. A separation of garnet from diopside was studied because this mixture had been removed from a wollastonite product by drying and magnetic separation, and no special or extra-preparation for electrostatic separation was necessary. THE SEPARATOR The separator used in these tests is of the nonhomogeneous field type shown in Fig I[a]. It consists of a 11.4-cm-diam rotating metal roll 2 at ground potential over which the dry mixture of minerals is fed. The roll serves as one electrode of the separating field, and the other electrode is that of 3, a smaller 5-cm-diam rotating metal cylinder which is held at a high direct-current potential. In this paper the term "electrode" will be confined to the electrode at 3, roll 2 being designated only as "roll." [ ]

Jan 1, 1947

By Campbell Hunter

PETROLEUM is found in almost every province in Persia. On the northern frontier, along the southern shore of the Caspian Sea, it is found near Anzelli and Shakhtesar and gas at Khoremabad. Oil is also found at Gumush Tepe, northwest of Astrabad, on the southeastern shore of the Caspian Sea. Further inland, to the south of Astrabad, oil is found at Schahkuh-i-balae, also on the margin of the Khorasan desert at Semnan, 115 mi. (35 m.) east of Teheran. Along the western frontier, from northwest to southeast, oil is encountered at Ouschachi, north of Lake Urumieh; in the province of Azerbaijan, at Zohab, Khanikin, and other places in the district of Kormanshah in the province, of Ardelan. Further south, in the province of Luristan, oil is found east of Mendeli and in the Pusht-i-kuh districts. Considerable quantities of oil are also obtained from Schuster, Maidan-i-Naphtun, Ram-Hormuz, Beheban, which are almost on a straight line, running northwest and southeast along the foothills of the Bakhtiari Mountains. At Ahwaz, in the province of Arabistan, oil has been found along another range of hills whose axis also lies in a northwest-southeast direction. In the Fars province, boring for oil has taken place at Daliki, and indications of oil are found at Kheri, Fasa, Darab, and other places. A gas show is also recorded at Kuhi-Sung-Atush in this province, 30 mi. (48 km.) east of Darab. In the south of Persia, oil is encountered on. Qishm Island, also at Ahmedi and other places north of Bunder Abbas. On the southeastern frontier, oil is found on the Sarhad range of hills. Thus, oil indications have been noted over a distance of approximately 1100 mi. along the western and 700 mi. along the northern frontiers of Persia.

Jan 2, 1920

By W. R. Crane

While professiorlally engaged in the oil- and gas-fields of Kansas, in measuring the pressure and flow of gas-wells, and studying the phenomena attendant upon the production of both oil and gas, I noticed in the flow of gas a peculiar and interesting feature. That there are actual lines of flow in liquids (non-compressible fluids) discharged through an orifice, or a short section of pipe, is shown by the external shape of the discharge—the vena contracts. Such lines of flow are not observable in the discharge of gas from an orifice. It can hardly be questioned that they exist. That they are not apparent is probably due to the very small weight of the gaseous particles, which climinishes the momentum of their movement in a given direction, acquired before they issue from the orifice, and also to the expansion of the gases, which would exert a powerful influence in overcoming any such tendency in their flow. Gas flowing from an orifice, supplied by a large reservoir or blowing-engine, exhibits almost the reverse of what is noticed with liquids. Namely, the gas assumes the form of an inverted truncated cone, of large angle: with its apex-end at the orifice. (See BB, Fig. 1.) This external ahape assunled by the flow of gas shows, however, marked differences under varying conditions of volume and pressure. For instance, a large volume of gas under high pressure, flowing through a 2- or 3-in. pipe, as in the case of a natural gas-well, assumes a more definite conical form, the angle of which increases as the pressure falls. Moreover, outside of the well-defined inverted cone is a thin conical heath or zone of gas, A A, the angle of which is considerably greater than that of the main cone, and increases with +1UNIVERSITY OF KANSAS, LAWRENCE, KANSAS.

Jan 1, 1905

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps : 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. .These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the molecules will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1964

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

By T. L. Joseph

THE invention of the Bessemer converter process in 1856 added great impetus to the manufacture of steel and is one of the outstanding contributions to process metallurgy. Although the process of refining pig iron by passing air through the molten metal bears the name of Henry Bessemer, it should be mentioned in passing that William Kelley of Eddysville, Ky., worked on the process as early as 1847. Kelley was granted a patent on the process in 1857, inasmuch as he was able to prove priority in discovery.1 After considerable litigation in 1865 the respective interests of Kelley and Bessemer were combined. On Sept. 10, 1856, Robert Mushet of England obtained his first patent on the application of manganese to cast steel. Mushet anticipated trouble in purifying iron by passing currents of air through it. His patent specified that steel made in this way often contained flaws and was red short or cold short. Mushet understood the refining of pig iron into steel well enough to realize the difficulties likely to be encountered from oxidation of the iron. Mushet was not only an inventor but he was also an investigator. He understood the principle of selective oxidation which takes place in the converter process, arid he realized therefore that the remedy for over-oxidation was attainable if a suitable metal could be found at a reasonable cost and in sufficient quantities. His first experiments were made in small crucibles holding a few ounces of metal. Later his work was conducted on a larger scale and with complete success. Manganese had been used in making steel a quarter of a century before the converter

Jan 5, 1927