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By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By L. D. Ricketts

Discussion of the paper of L. D. RICKETTS, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 100, April, 1915, pp. 711 to 737. FREDERICK LAIST, Anaconda, Mont.-I am going to tell you of some of the results we have been getting in Anaconda during the past two or three months in a large plant which was finished in May. We commenced work in Anaconda a year and a half ago on the construction of a leaching plant which was to have a capacity of 2,000 tons per day. The plant was to treat tailings from the concentrator, containing about 12 1b. of copper to the ton. During the past year we changed our plans and decided to use the flotation process on the tailings from the concentrator, which contained no oxidized copper, and apply the leaching process only to tailings which had accumulated in a large dump below the works. This dump contains about 15,000,000 tons of tailings, and since some of the copper in it is oxidized, we felt that the application of the flotation process would result in the loss of too much of the oxidized copper, particularly as time went on. In starting up we had a number of difficulties to overcome, as is usually the case. They were not of a serious character. The results obtained, so far, have been decidedly encouraging. During July the plant treated a total of 50,000 tons of tailings, or an average of 1,610 tons per clay. The extraction was about 83 per cent., which, on material of the grade treated, meant a. tailing assaying under 0.1 per cent. copper. The acid consumption was about 65 lb. per ton, and the fuel percentage in. roasting was about 4 ¼ . We expect to cut the fuel percentage in the next month or two to about 3 per cent., the high percentage during July being clue to starting up and shutting clown furnaces. We find that iron builds up in the solution to a marked degree. This is not a serious platter with us, because we have cheap sulphuric acid and can reject solution whenever it gets too foul. The extraction of silver has been remarkably good in the large plant. It has averaged better than 75 per cent. It seems that so long as we maintain salt in the solution to a percentage of 10 per cent., the extraction is good. We allowed the salt to fall off in order to find how low a percentage we could use. At about 7 per cent. the silver extraction fell to 65 per cent. This was to be expected, because silver chloride is soluble in strong brine, but not in weak brine.

Jan 12, 1915

By W. Rosotoker

Using an expression for the free energy of a homogeneous phase as a function of composition, a relationship is derived which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. Comparisons between observed and calculated phase boundaries in the systems Fe-Ni, Fe-Mn, Fe-W, Ti-Mo, and Ti-Cb are presented. IT is the purpose of this paper to illustrate how the general free energy equations for two phases in equilibrium may be used to derive an expression which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. The free energy per gram atom of a disordered solid solution may, for many purposes, be represented by the equation:' F = ½NZ [C-V,, + (1-C) VbB + 2C (l-C)V] + K(T) +RT[C-lnC+ (l-C)ln(l-C) ] [1] where N is Avogadro's number; Z, the coordination number; C, the concentration of the solute element in atomic percent; the subscripts refer to concentrations at phase mixture boundaries; VAA, VBB, and V,, are the bond energies between like and unlike adjacent atoms, respectively, at the interatomic spacing characteristic of the phase. The bond energies are usually assumed to be independent of small changes in the lattice parameter occasioned by solute additions and variations in temperature; V = VAB ---------------—— ; K(T) is the sum of the heat con- tent and heat entropy; R, the molar gas constant; and T, the temperature in degrees Kelvin. The free energy of a homogeneous phase is there- fore the sum of an internal energy, a specific heat, and a configurational entropy term, respectively. The compositions of two phases in equilibrium at a given temperature are governed by the minimum total free energy principle. Graphically, this is represented by the points of tangency of the tangent common to the free energy vs. concentration curves of the two phases. Analytically, this may be expressed as: ( df) = (df) [2] dc dc Expanding both sides using eq 1, the following equation is obtained after convenient readjustment of the terms: RT In[(ca)(1-c)]-½N (Vaa-Vbb)(Za-Zb) +NV [Za(l-2Ca)-Z,(l-2C,)] [3] The following assumptions have been made at this point: 1—The specific heats of the two phases are independent of composition variations within the range under consideration. Accordingly, the K(T) terms disappear on differentiation. 2— (Vaa)o = (VAA); (VBB). = (VBB); Va = V, Theyjustification for these assumptions can lie only in the successful application of the resultant equation. It may be noted that Zener2 has used assumption 1 in the calculation of the boundaries limiting the (a+j3) phase mixture in the Cu-Zn system.

Jan 1, 1952

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

The Inspiration ore body was discovered in 1904, but a 50 -ton mill which was installed to treat the disseminated copper ore promptly failed. The original Inspiration Company then gave way to another, backed by W. B. Thompson, which found 40 million tons of ore. Control then passed to Anaconda and Dr. Louis Ricketts took charge as consulting engineer. He abandoned the mill which had been partially built (to the horror of the stockholders, according to Ira Joralemon) and spent a year and a million dollars experimenting with flotation. The first large copper flotation plant was then built and recovered 50% more copper than had previous gravity mills. It, of course, was highly successful and became the forerunner of modern flotation plants. Inspiration is distinctive as the first fully integrated copper operation in the United States. Three open pits supply sulfide ore to the concentrator and mixed oxide and sulfide ore to a vat leaching and electrowinning operation with leached ore also being sent to the concentrator. In addition, dump leaching supplies pregnant solution for scrap iron precipitation. Inspiration has recently constructed an electric furnace smelter and also operates a continuous casting and rod plant. The new primary 54 in. by 74 in. crusher was completed in May of 1972 and replaced an older unit which was in the way of the open pit development. It is of an unusual circular silo design, which permits dumping 0 from two positions at 90 from each other. One dumping position is in line with the spider, while the other one is at right angles to it. A box girder splitter bar hung from the dump pocket slopes downward from the second dump point, across the spider cap, and rests on the pocket bottom. This splitter was not installed to protect the spider but was to aid in distributing wet ore being dumped from that position to both sides of the spider. Any large amount of wet ore delivered to one side of the spider would pack in the crusher cavity. The round front wall of the 18 ft (5.5 m) deep pocket is unlined except for light steel protection at the top, while the straight back wall is lined with vertically positioned railroad rails. Water for dust suppression is sprayed into the pocket through a cluster of 3/8 in. (9.5 mm) nozzles at the back of the pocket. About 5 gpm (19 lpm) of water are mixed with 90 psi (620 kPa) air upstream of the nozzles to produce a fog which is effective in dust control. The 54 in. Allis -Chalmers gyratory is placed mostly within one quadrant of the circular enclosure to permit placement of the apron feeder on the lowest level in the proper position to transfer crushed ore to the

Jan 1, 1978

By R. W. Gurry

THERMODYNAMIC calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a. better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganeie, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B203 in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1943

THE Institute assembled in the Court-House, on Tuesday evening, May 22d, and was called to order by Vice-President E. B. Coxe. After announcement by the Local Committee of the programme for excursions, the Secretary read the following annual report of the Council The Council, in presenting to the Institute its annual report, has to record a most eventful year in the history of the Institute. Three meetings, as usual, have been held, two in Philadelphia and one in New York. At the Philadelphia meetings in June and October, there were present many distinguished foreign engineers, some of whom contributed communications to the Institute, and took part in its discussions. Sixty-seven papers have, in all, been presented to the Institute, which will be published in the fifth volume of Transactions. There has been an accession to the membership of 1 honorary member, 11 foreign members, and 162 members and associates; -8 have resigned, 6 have died, and 30 have been dropped from the roll, after due notification, for non-payment of dues. The membership now comprises 5 honorary members, 60 foreign members, and 644 members and associates, in all 699. As worthy of especial mention in the work of the year are the Discussions on Technical Education in connection with the American Society of Civil Engineers, and the report of the-International Committee appointed by the Institute to consider the nomenclature of iron and steel. The Discussions on Technical Education have been published in a separate volume, and comprise a valuable and suggestive collection of the views of practical engineers and educators. The report of the International Committee, composed of Messrs. Akerman, of Sweden; Bell, of England; Tunner, of Austria; Gruner, of France; Wedding, of Prussia; and Holley and Egleston, of the United States, has received the careful attention of engineers and metallurgists of all countries, and has met . with very general acceptance. Of the work of the Centennial Committee in Philadelphia the members are generally familiar, from personal experience, and from the detailed report of the committee at the last meeting of the Institute. But the record of the service rendered by this committee would he incomplete without mention of the numerous letters of thanks and formal expressions of obligations received by the Institute from individuals, societies, and governments abroad. The wise and generous spirit in which the work of the committee was planned, and the laborious and self-sacrificing manner in which it was carried out, call for emphatic expressions of thanks from the Institute. The gifts of Centennial exhibits to the Institute, largely as testimonials for services rendered, has necessitated the appointment of a Museum Committee for

Jan 1, 1878

By J. Chipman, N. J. Grant, R. Rocca

D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—With reference to eqs 7 and 8, at what temperature do they apply John Chipman (authors' reply)—That was 1600°C. Dr. Babcock—You have l x 10-4 as the component for the lime and 1 or 4x10-. Now, is it by dividing one into the other you get the 400? That is assuming equivalent activity on the part of oxygen, sulphur, and magnesia. Dr. Chipman—Yes, they are calculated for 1600. Now, the first one for CaO was calculated before we had a glimpse of Dr. Rosenqvist's paper." If you take his calculation you get 14,000 cal which is very good agreement, but our calculation would be superseded by Dr. Rosenqvist's new data. Dr. Babcock—The state you assume those to be in is the liquid state, as near as you can measure? Dr. Chipman—Naturally it is based on the solid CaS, but if you add the effect of fusion on both sides it just about balances out, so the ratio would be about the same. B. M. Larsen (U. S. Steel Co., Kearny, N. J.)—If we knew the activity of sulphur in the slag instead of merely the percentage, we might be able to find some conflicting factors that balance one another out, and find that the FeO or oxygen pressure effect is really present over the whole range. Dr. Chipman—I am fairly sure we would. The activity of sulphur in the slag and the activity of CaO in the slag, if we just knew those quantities, would enable us to save a lot of this computation and assumption and all the approximations we are doing now. Mr. Larsen—Two other points perhaps should be included: 1—an independent effect of manganese in helping the desulphurization; and 2—the number of mols of constituents or number of mols of ions or whatever there is in the slag could vary with these compositions in such a way that you get dilution effects. Dr. Chipman—You can figure all that in if you want to and it might improve the degree of approximation a little bit. Maybe enough to justify the labor of calculation, inaybe not, but we did not do it. L. S. Darken (U. S. Steel Co., Kearny, N. J.)—The authors have tackled a very complicated problem in trying to tie together in one picture the desulphurizing problem over the wide range of basicity and oxidation level from that of the open hearth to that of the blast furnace. At the present state of our knowledge of slags such an ambitious undertaking necessarily involves the adoption of numerous hypotheses. Their formulation (eq 11) for the higher FeO range

Jan 1, 1952

By R. S. Busk

TWO groups of binary alloys were prepared. The first group consisted of those elements relatively soluble in magnesium: Li, Al, Zn, Ga, Ag, Cd, In, Sn, Hg, T1, Pb, and Bi. These are predominately Group B elements. The second group consisted of most of the remaining metallic elements, all of which are relatively insoluble in magnesium: As, Au, Ba, Ca, Ce, Cu, Ir, La, Mn, Ni, Pd, Pt, Rh, Sb, Si, Te, Ti, W, and Zr. These are all Group A, transition, or rare earth elements. Alloys of the first group were prepared by melting sublimed magnesium and elements as pure as obtainable in a graphite crucible, using a standard flux1 for protection. The melts were poured into a small graphite mold to produce 3xY4 in. diam slugs. Spectroscopic analyses were made of each slug. In all cases, the total impurity content was less than 0.05 pct. The slugs were then heat treated 5°C below the eutectic temperature until complete solution, as judged metallographically, was obtained. Filings from the center of the slugs were compacted at room temperature into 1/2 in. long x 1/4 in. diam cylinders, sealed in pyrex under 1/2 atm of purified argon, annealed at the heat-treating temperature for 1 hr, and quenched in water. After the X-ray diffraction patterns were made, each compact was analyzed chemically for the solute. It was found that the Mg-Li alloys reacted during filing to reduce the Li in solid solution. For this series of alloys, the slug was cold worked, annealed in purified argon, the surface dissolved in dilute HC1 to a depth of about 0.005 in., and the X-ray exposure made on the fresh surface. This procedure resulted in sharp, continuous lines and in true values for the lattice parameters. The alloys in the second group were prepared in the same way except that about 1 wt pct of each solute was added. Since the solubility limit was exceeded, not all the solute dissolved. These alloys were analyzed spectroscopically only to confirm the presence of the solute. The diffraction patterns were of the back-reflec-tion type using the characteristic copper radiation* and a flat cassette. Both the film and the specimen were rotated. The specimen temperature was maintained at 25" ± 1°C. The films had sharp lines; their diameters were measured directly to 0.01 cm. The parameters were calculated from the line diameters using a modified version of Cohen's extrapolation method.2 his method effectively eliminates systematic errors such as film shrinkage, inaccurate alignment, and non-precise film-to-speci-men distance. The random errors were minimized

Jan 1, 1951

By R. Schuhmann

The expression "unit process " comes up with increasing frequency in discussions among metallurgists and mineral engineers, especially among those concerned with training the next generation. The unit process approach characterizes a significant advance along the road from metallurgy as an empirical art to metallurgy as a branch of engineering. The purposes of this paper are to define and list the unit processes in specific terms, to indicate the scientific and engineering principles basic to all the unit processes, and finally to show how these ideas have been applied to a reorganization of instruction in chemical metallurgy. Unit Operations and Unit Processes Metals are extracted from ores and other raw materials by stepwise procedures. In general, each metallic element is extracted by a different procedure. For many of the metals there is a choice of several flowsheets. However, the procedures all have steps in common. In fact, the many different flowsheets are all made up of a relatively small number of steps which are combined in different groups and sequences. For example, crushing, screening, roasting, sintering, melting, and gaseous reduction are steps which each appear in the Bowsheets for extracting the majority of the metals. The individual steps or flowsheet units can be designated as unit operations or unit processes. These terms are well established in the field of chemical engineering, as the American Institute of Chemical Engineers' definition of chemical engineering shows: " Chemical engineering is that branch of engineering concerned with the development and application of manufacturing processes in which chemical or certain physical changes of materials are involved. These processes may usually be resolved into a coordinated series of unit physical operations and unit chemical processes. The work of the chemical engineer is concerned primarily with the design, construction, and operation of equipment and plants in which these unit operations and processes are applied. Chemistry, physics, and mathematics are the underlying sciences of chemical engineering, and economics its guide in practice."'1a In this definition, the distinction between unit operations and unit processes is that the unit operations are physical while the unit processes are chemical. Table I gives a list of the principal unit operations and unit processes of chemical engineering, taken from Shreve.1b Table 2 lists the principal unit operations and unit processes used for metal extraction. The division between unit operations and unit processes is similar to the chemical engineers' distinction and also correspollds approximately to the division of labor bctween mineral dressing and chemical metallurgy which has been customary in the past. Furthermore, it will be noted that in the proposed classification the unit processes primarily involve chemical reactions and/or changes in state of aggregation; the unit operations primarily do not involve either bulk

Jan 1, 1949

By David R. Mitchell

THE mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during war-time, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for separating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concentrating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435,000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PYRITE PRODUCTION According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By Joseph J. Yancik, Leonard L. Felts, George B. Clark

LITTLE information has been published concerning the actual or useful amount of energy obtained from explosives when they are used for blasting. To provide more data on this subject, 8-in. neet cement cubes were blasted in a steel plate box and the breakage energy evaluated by comparison with drop crusher results using Rittinger's,1,2 Kick's: and Bond's' theories. Theories by Bond and Wang," Lineau," Hatch,' Roller,' and others0-11 were not considered applicable. Those used in this investigation may be expressed mathematically as follows: Rittinger Theory E = KrS2, pet,—--------------- [1] 40 d1 d0 Kick Theory TV 1 1 E = =K, [S pct. log1/d+ 100 log d0] [2] 40 d1 L. L. FELTS, Junior Member AIME, was formerly a Graduate Assistant, University of Illinois. G. B. CLARK, Member AIME, was formerly Professor of Mining Engineering, University of Illinois, and is now Chairman, Dept. of Mining Engineering, Missouri School of Mines and Metallurgy. J. YANCIK, Junior Member AIME, is a Graduate Assistant, Missouri School of Mines and Metallurgy. This paper, TP 4213A. is revised from a thesis submitted by L. L. Felts in partial fulfillment of the M.S. degree in Mining Engineering, University of Illinois, 1954. Discussion may be sent (2 copies) to AIME before May 31, 1956. Manuscript, Dec. 27, 1954. Bond's Third Theory E = Kb [S pct. log1/d1+ 100 log d0] where E — energy used in breakage, d, = average diameters of screen fractions of broken cement particles, pct, = percent weight of diameter d;, and 2 pct, = 100 pct. The above equations were employed to determine values of Kr, Kk, Kb for particle size distributions similar to those obtained from the blasting curves. These values were in turn used as a means of approximating the specific energy of the blasted material. The efficiency of crushing by blasting was then determined by dividing this specific energy by the maximum available work of the explosive per gram of cement. Knowledge of the failure of solids under static loads is developing very rapidly. Their failure under impact loads has been investigated and reported in the literature only to a limited extent. Theories of failure' hnder static loading include 1) the maximum stress theory, 2) the maximum strain theory, 3) the theory of constant elastic strain, 4) theory of maximum shearing stress, and 5) Mohr's theory of strength. All of these have elements of usefulness in establishing an applicable theory for blasting. For highly strained and compressed material such as that surrounding a detonating charge of high explosive, the Mohr theory and its implications appear to be the

Jan 1, 1957

By J. H. Brophy, J. Wulff, H. W. Hayden

The mickel-activated sintering of tungsten occurs in two stages of densification. A kinetic analysis of the second stage has been based on an appropriate model of the process. As in the first stage, the rate-controlling mechanism for the second stage is also the solution of tungsten in the nickel carrier phase. The transition from the relatively rapid first-stage results from the spherozdization of pores and the initiation of grain growth. Finer grain size due to higher-nickel content leads to more rapid and higher degrees of densification 1 HE sintering of tungsten is accelerated by small additions of nickel, cobalt, and iron.' Experimental evidence in detail has shown that nickel-coated, hydrogen-reduced tungsten powder may be sintered to more than 90 pet of theoretical density at l100o C.2, 3 Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the "solution-precipitation" step postulated when the carrier phase is a liquid,4 although in the Ni-W case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in microstruc-tures at the temperatures under consideration. It has been shown that this stage corresponds to a process which is rate controlled by a phase boundary reaction.3 More recent evidence has been presented5 showing that after the initial rapid stage of sintering, densification continues in the final stage but at a slower rate, although no mechanism for this stage of densification was defined. An analysis of later stages of densification in solid state sintering has been presented,6 but it is not directly applicable in the present case of activated or carrier phase sintering. It is the purpose of this investigation to study the final stage of nickel activated tungsten sintering in greater detail The effect of varying nickel content has been examined, and a possible kinetic mechanism defined. EXPERIMENTAL PROCEDURE AND RESULTS Commercial hydrogen-reduced tungsten powder from Wah-Chmg Corp., having a nominal particle size of1 µ and a B.E.T. specific surface area of 5500 sq. cm per g was mixed with aqueous solutions of hydrated nickel nitrate in proportions sufficient to produce nominal compositions of 0.25, 1, 3, and 5 wt pet Ni. This solution was then evaporated to dry-ness at approximately 150" C for 15 hr. Following evaporation, the resulting powder cake was broken with a mortar and pestle and reduced in hydrogen at 800oC for 1 hr. Following reduction, the powder

Jan 1, 1962

By Herbert A. Stein, John B. Murdock

AN analysis of perlite expansion furnaces must be based upon one consistent theory which explains how and why perlite does expand when heated. There is more than one such theory, so to establish a basis for the rest of this paper, the authors will outline one theory and the data that support it before going into the construction details of different furnaces. JOHN B. MURDOCK, Associate Member AIME, is President, and HERBERT A. STEIN is Secretary, of the Perlite Corp., Phoenix, Arizona. San Francisco Meeting, February 1949. TP 2736 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Jan. 3, 1949. Why Perlite Expands: Perlite is known to contain some dissolved or combined fluid, probably water, which is lost when the material is heated to fusion. It is generally agreed that when particles of this volcanic glass are heated to fusion in such a way that vaporization of this water into steam takes place at the same time as the glass becomes soft, the steam puffs up each particle into a mass of glass foam. It is a simple matter to expand perlite under a blow torch for demonstration purposes, but in commercial installations, the problem is made more complicated by the necessity of making efficient use of both raw material and fuel, and producing an expanded aggregate conforming to close specifications for size distribution and density, using many different types of perlite rock. The ability of a given operation to fulfill these requirements depends upon the proper handling of four variables. They are: (1) the nature of the perlite rock used, (2) the heating time taken to get the perlite particle up to its highest temperature, (3) the size of the particle, and (4) the maximum temperature the particle reaches. Types of Perlite Rock: Perlite may be classified in many ways, but the characteristics most easily correlated with its behavior in furnaces are its softening temperature, its effective water content, and its "liveliness." Actually there is a close correlation among these three characteristics so it is possible to describe a perlite using any one of them. Lively perlites always have low softening temperatures and high effective water contents, whereas the deader perlites have higher softening temperatures and lower effective water contents. These softening temperatures run from 1400°F to above 2000°F and the effective water contents run from over 2 pct down to 0.2 pct. Included in the category of lively glasses are the green pitchstone from the Edgar claim in Superior, Ariz., the red pitchstone on the Animas highway south of Lordsburg, N. Mex., and a gray glass from Beatty, Nevada. Examples of intermediate perlites (in order of decreasing liveliness) are the Guzman-Lobb perlite with obsidian

Jan 1, 1951

By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By W. R. Seyfried

The problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations. An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper. The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reagent for re-use. The Process as Planned In April 1941, a group of chemists and engineers of the Chemical Construction Corp. became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the company, first drafted a process in July of that year—five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant. By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or lour-grade bauxite would be roasted at 700 to 800°C (1292° to 1472°F). (b) The roasted ore would then be leached with hot aqueous ammonium bi-sulphate to form a slurry. In this way the

Jan 1, 1949

By Herbert A. Stein, John B. Murdock

AN analysis of perlite expansion furnaces must be based upon one consistent theory which explains how and why perlite does expand when heated. There is more than one such theory, so to establish a basis for the rest of this paper, the authors will outline one theory and the data that support it before going into the construction details of different furnaces. JOHN B. MURDOCK, Associate Member AIME, is President, and HERBERT A. STEIN is Secretary, of the Perlite Corp., Phoenix, Arizona. San Francisco Meeting, February 1949. TP 2736 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Jan. 3, 1949. Why Perlite Expands: Perlite is known to contain some dissolved or combined fluid, probably water, which is lost when the material is heated to fusion. It is generally agreed that when particles of this volcanic glass are heated to fusion in such a way that vaporization of this water into steam takes place at the same time as the glass becomes soft, the steam puffs up each particle into a mass of glass foam. It is a simple matter to expand perlite under a blow torch for demonstration purposes, but in commercial installations, the problem is made more complicated by the necessity of making efficient use of both raw material and fuel, and producing an expanded aggregate conforming to close specifications for size distribution and density, using many different types of perlite rock. The ability of a given operation to fulfill these requirements depends upon the proper handling of four variables. They are: (1) the nature of the perlite rock used, (2) the heating time taken to get the perlite particle up to its highest temperature, (3) the size of the particle, and (4) the maximum temperature the particle reaches. Types of Perlite Rock: Perlite may be classified in many ways, but the characteristics most easily correlated with its behavior in furnaces are its softening temperature, its effective water content, and its "liveliness." Actually there is a close correlation among these three characteristics so it is possible to describe a perlite using any one of them. Lively perlites always have low softening temperatures and high effective water contents, whereas the deader perlites have higher softening temperatures and lower effective water contents. These softening temperatures run from 1400°F to above 2000°F and the effective water contents run from over 2 pct down to 0.2 pct. Included in the category of lively glasses are the green pitchstone from the Edgar claim in Superior, Ariz., the red pitchstone on the Animas highway south of Lordsburg, N. Mex., and a gray glass from Beatty, Nevada. Examples of intermediate perlites (in order of decreasing liveliness) are the Guzman-Lobb perlite with obsidian

Jan 1, 1951

By T. W. Lippert

In these opening remarks, I will endeavor to give a background of continuous casting of metals. Only passing attention will be given to the different processes to be described by the authors whose papers are on the program, as they are far more familiar than I am with their subject matter. Suffice to say that over the past several years the brass, copper, aluminum and magnesium industries have shifted practically completely from conventional static molds to continuous casting machines. The Aluminum Company of America alone has more than 60 continuous machines in operation. The product as continuously cast is superior metallurgically, less scrap loss is involved, costs are generally lower, and the equipment requires little floor space. A continuous machine, operating as it does with deadly constancy, is a ravenous consumer of molten metal, and in most plants one or two machines are well able to handle large banks of melting and refining furnaces. In steel, interest in continuous casting is today more serious than ever before in history, and there is every reason to believe that continuous machines may secure a minor place in the ferrous industry, particularly for tool and alloy analyses. In the past, steel has been commercially cast continuously, and today many tons of steel are being turned out in this manner. It has been said that the cradle of every science is surrounded by dead theorists— and certainly there are innumerable examples of this in the metals industries. An excellent illustration, for instance, is the continuous rolling of metal, a tantalizing objective that for decades on end exhausted . the efforts of a long line of famous, infamous and unknown inventors. Finally, in 1922, John B. Tytus, of the American Rolling Mill Co., brought forth what now seems such an obviously simple scheme— a concave roll face, each stand of progressivcly less concavity. And out of this one change in design sprang today's wide continuous mill rolling steel sheet Ioo in. wide at 2000 ft. per minute. Another excellent example is the con- . tinuous casting of liquid metal into an intermediate form, preferably one requiring little subsequent breakdown. First, the casting of liquid metal alone was fascinating enough. Then someone passed the cast metal directly into a rolling mill, and shortly thereafter this continuously rolled strip was passed directly into a stamping machine. This leitmotiv of a continuous flow of metal from the liquid phase to a consumer end product, fast and inexpensive, and all housed within a small space, was enough to drive some 200 or so inventors into frenzy over the past hundred years. All the ideas, however, like mayflies, had only their brief afternoon of existence. They were born and they died on paper, as constant exemplification of that great void that always exists between mental production and commercial production.

Jan 1, 1945

By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By J. J. Arps

This paper reviews the methods currently in use for estimating primary oil reserves and discusses the principles on which these methods are based. Particular emphasis is placed on how these methods change with the type of information available during the life cycle of an oil property. This paper contains various novel estimating methods and shortcuts heretofore unpublished. INTRODUCTION Estimating oil reserves is one of the most important phases of the work of a petroleum engineer since the solutions to the problems he deals with usually depend on a comparison of the estimated cost in terms of dollars, with the anticipated result in terms of barrels of oil. His recommendations to management regarding the best course of action are therefore normally based on the most favorable balance between these two. Specific engineering problems which require such a knowledge of recoverable oil reserves and a projection of future rates are: [a.] the exploitation and development of an oil reservoir; [b.] the construction of gasoline plants, pipelines and refineries; [c.] the division of ownership in unitized projects; [d.] the price to be paid in case of a sale or purchase of an oil property, and the magnitude of the loan which it will support; [e.] the proper depreciation rate for the investment in oil properties; and [f.] evaluation of the results of an exploration program. This discussion will be confined to the various methods and tools which are currently in use for estimating oil reserves to be obtained during the primary phase of an oil-producing reservoir and for a projection of the future production rates. Reserves which may be obtained by secondary recovery methods or fluid injection programs and gas and gas condensate reserves will not be discussed in this paper. Unfortunately, reliable oil reserve figures are most urgently needed during the early stages when only a minimum amount of information is available. Management's interest in the oil recovery from a property—aside from its use for accounting purposes—usually declines when the property approaches its economic limit, just at the time when the reliability of the estimates is at its best. To illustrate this general idea a chart is presented (Fig. 1) showing the three periods in the life of an imaginary oil property. Time is shown on the horizontal axis, while the cumulative production and estimated ultimate recovery are plotted vertically. No particular units are used and this schematical chart is not to scale. During the first period, before any wells are drilled on a property, any estimates will of necessity be of a very general nature, based on experience from similar pools or wells in the same area, and usually expressed in barrels per acre. This will

Jan 1, 1957