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By E. E. Wark, I. W. Wark, J. Rogers. K. L. Sutherland

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts 'he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By E. E. Wark, J. Rogers, I. W. Wark, K. L. Sutherland

SOAPS have been used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xanthates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present eminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies.[t] A broad, semi quantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. THE PARAFFIN CHAIN SALTS The basic requirements for a "collector" in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polarnonpolar compounds is the paraffin chain salts: CH3(CH2) „X where X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -CO2Na, -SO3Na, -SO4Na, - PO4Na2, or an aminonitrogen group, the

Jan 1, 1946

By Charles E. Barker

Jan 1, 1985

By Bernard Kopelman

THE particle size of tungsten metal powder used to make tungsten wire for use in radio tubes and incandescent lamps must be closely controlled if the highly desirable feature of nonsagging is to be achieved. Our knowledge of factors affecting the particle size of tungsten powder has been limited by lack of any extensive literature on the subject. There are no publications in the English language discussing this problem in any but the most general terms. In this paper the published experimental information on this subject is reviewed. Based on the published data and some experimental data obtained by the author, a general theory of factors affecting the particle size of tungsten metal powder obtained by reduction of the oxides in hydrogen is offered. The various forms of the tungsten oxides and tungsten metal used in the experiments described were those prepared by com¬mercial processes, so that the experimental results obtained on a laboratory scale would be more directly applicable to actual commercial reduction conditions. The effects of time of reduction, temperature, and concentration of water vapor in the hydrogen were observed by counting microscopically the particle distribution obtained. Such a method is very time-consuming, but the data obtained by this method are more reliable and more fundamental than those obtained by any of the several instruments available for measurement of particle size. REVIEW OF THE LITERATURE Until the year 1912, tungsten powder was prepared commercially by reducing tungstic oxide in the presence of carbon or one of its compounds (such as glycerin or ethylene glycol), usually by firing the mixture in a closed fire-clay crucible. The resultant powder contained about 95 per cent tungsten.1 When reduction of tungsten oxides by H2 was introduced commercially, 2.1 several investigators became concerned with the equilibria between tungsten metal and its several oxides in an atmosphere of hydrogen and water vapor.4-13 While these many investigations were in fair agreement on the equilibria there arose considerable controversy as to the chemical composition of the oxide between W03 and W02, because of very poor agreement on the equilibrium constant of this intermediate oxide reduction reaction. The controversy on this intermediate oxide has been in progress for more than 10o years. Thus Malguti,14 in 1835, decided it was W02.56. In 1857, Riche" proposed the formula W308. Usler,16 in 1865, confirmed the existence of W308 and further proposed W4O11. In 1897, Desi17 agreed upon W308 but also found W5014.

Jan 1, 1946

By A. Perry Thompson

I- GeneRal Distribution, AppeaRance, and Relations ........ 563 11. Data fRom MicRoscopic Examination............... 568 1. Criteria for Distinguishing Primary from Secondary Minerals...... 568 2. The Leonard Vein Filling..................... 574 Quartz............................ 575 Pyrite............................ 575 Enargite............................ 576 Covellite............................ 578 Bornite............................ 581 Chalcocite........................... 583 Chalcopyrite.......................... 586 3. The Fault-Vein Covellite..................... 587 The Speculator Ore........................ 587 The East Gray Rock Ore.....,.............. 589 4. Other Occurrences of Covellite.................. 591 111. Conclusions........................... 592 1. The Replacement of Minerals..................592 2. The Character of Mineralizing Solutions .............. 594 I. General Distribution, Appearance, and Relations Mining in Butte has seldom encountered covellite in commercial quantities. The notable occurrences, extending vertically and laterally perhaps several hundred feet, presented scattered, bladed lenses of this mineral in a matrix of quartz, pyrite, enargite, bornite, and chalcocite. But under the microscope covellite is seen to be widespread in the Butte ores, though in such small quantity that megascopic examination will not discover it. In early mining operations covellite was found in the Gray Rock vein, a member of the Blue vein system. As described by Sales,' it persisted as an occasional ore mineral, associated with quartz, pyrite, tetrahedrite, bornite, chalcocite, and minor amounts of sphalerite, from the 700-ft. to the 1,200-ft. level of the East Gray Rock and Diamond mines. Crushed quartz-monzonite and later quartz completed the vein filling between

Jan 1, 1916

By W. H. Bassett, C. H. Davis

The late J. P. Sparrow, chief operating engineer of the New York Edison CO., carried out a series of practical tests on condenser tubes of several copper alloys and reported on the results to the Association of Edison Illuminating Companies at its meeting in September, 1913. In the preparation of these tubes the senior author had the pleasure of cooperating. Copper-zinc alloys in the proportions of 60-40,70-30,80-20, 90-10, and Admiralty metal, which is in effect 70-30 with 1 per cent. of tin, were tried. Monel metal and several copper-nickel alloys, and 8, 5, and 3 per cent. aluminum bronze were also tried. At the time of this report, the aluminum bronze had been in service for 4 1/2 years and seemed to be giving especially good results but later it began to fail and showed no substantial improvement over Admiralty metal. Monel metal was unsatisfactory and the nickel alloys apparently did not give better service than the Admiralty alloy. Previous to the publication of the report, and after considerable discussion, it was agreed that a test where tubes of different kinds could be under laboratory observation would be advisable, so the apparatus described here was set up in The American Brass Co.'s Waterbury Laboratory. This was fitted with tubes of copper, brass, bronze, nickel silver, cupro-nickel and other alloys, and the test started on Oct. 11, 1912. Salt water from East River, New York harbor, was barrelled and transported to the laboratory for the test. A fresh supply, completely replacing the water in service, was obtained at the end of each six months period. Plan of Procedure In general, the procedure was to inspect the tubes at short intervals and to remove those that had begun to leak. The tubes removed were carefully examined and a photographic and microscopic record of the

Jan 1, 1925

By AIME AIME

The following abstract of the minutes of the final Adjourned Annual Business Meeting, held Nov. 12, 1912, in the office of the Institute, 29 West 39th Street, New York City, is here presented for the information of the membership at large. On the announcement by the Secretary that there was a quorum present, President James F. Kemp called the meeting to order. The minutes of the Adjourned Annual Business Meeting of Oct. 7, 1912, were read and approved. (Sec p. xi,Bulletin No. 71, November). Prof. Jos. W. Richards, in behalf of the Special Committee of the Board of Directors and the Council (Messrs. Richards, Kirchhoff, and Rand), withdrew the two proposed amendments to the Constitution offered by the said Committee at the Adjourned Annual Business Meeting of Oct. 7, 1912. (See Bulletin. No. 70, October, 1912, p. vi., and Circular Announcement No. 8, Oct. 15, 1912, p. 15.) Professor Richards presented a syllabus of the proposed amendments to the Constitution and By-Laws prepared by the Special Committee. Several members present discussed various sections of the proposed Constitution, and the Committee advised that the suggestions would he duly considered before submitting the final document, which would be duly presented and sent to the membership at large at least 30 days before the next Annual Business Meeting, Feb. 18, 1913. Professor Richards presented a resolution, seconded by Mr. Kirchhoff, making a change in the present Certificate of Incorporation, so that it would conform to the proposed changes in the Constitution and By-Laws; said resolution was unanimously adopted. Professor Richards presented another amendment to the Constitution, which had been purposely omitted from the printed list, but had been requested by many members, namely, the creation of a " Class of Fellows." This question was freely discussed at the Cleveland meeting (see Bulletin No. 71, November, 1912, p. 1348), and in view of the diversity of opinion it was-decided to present it in separate form for separate action of the membership at large at the Annual Business Meeting, Feb. 18, 1913. In answer to question, the President announced that the proposed amendments to the Constitution and By-Laws presented by Messrs. Corning and Stone at the Adjourned Annual Business Meeting, Oct. 7, 1912, and published in Circular Announcement No. 8, Oct. 15, 1912, were still on record. Professor Richards presented a syllabus of the proposed amendments to the By-Laws, and several sections were discused by members present, but no action of record was taken. Mr. Charles F. Rand read a letter from Mr. L. K. Armstrong, Sec-retary of the Spokane Local Section of the Institute, referring to the proposed amendments to the Constitution, and he announced that many of Mr. Armstrong's suggestions were, in one form or another, already incorporated in the proposed amendments submitted by the Special Committee. A special vote of thanks was passed to Dr. Albert R. Ledoux for the valuable assistance rendered by him to the Special Committee in the preparation of the proposed amendments to the Constitution and By-Laws.

Dec 1, 1912

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

By Pei-Yung Huang, Carle R. Hayward

IN order to understand more fully the actual state of copper lost in copper reverberatory slags, a systematic study on the various reactions between certain metallurgically important copper compounds and synthetic copper reverberatory slags was undertaken by the authors in the Massachusetts Institute of Technology from 1942 to 1945.1 This paper, being only a part of the work completed, is published first because it furnishes the first experimental evidence of the formation of copper ferrite from reactions between cuprous oxide and copper reverberatory slags. CHOICE OF SLAG COMPOSITION The choice of the composition of the synthetic reverberatory slags to be used was much deliberated. Commercial copper reverberatory slags, neglecting minor constituents, average:2.3 45 to 47 pct FeO; 38 to 42 pct Si02; 5 to 6 pct CaO; 5 to 6 pct A1203. Since the ternary system CaO-FeO-SiO2 has been much more thoroughly studied4 and is much simpler than the quaternary system CaO-FeO-Si02-A1203, it was decided to use calcium oxide only instead of calcium oxide and alumina in the synthesis of the slags. Fortunately the composition of the average copper reverberatory slag with calcium oxide substituted for alumina lies in the region of the phase diagram clarified by the investigators. A survey of the phase diagram (Fig I) suggested two compositions: (I) the com¬position near the invariant point S, which is made up of 46 pct ferrous oxide, 37 pct silica and 17 pct calcium oxide; (2) the composition near the invariant point K with 45.5 pct ferrous oxide, 43 pct silica and 11.5 pct calcium oxide. Composition S has the advantage that the percentages of ferrous oxide and of silica almost exactly coincide with those of the average reverberatory slags, and that of the lowest melting point (1093° ± 3°C) in the whole ternary system. The calcium oxide content, however, obviously is high. Since we have already substituted calcium oxide for alumina, and since calcium oxide is more basic than alumina, the resulting slag is decidedly too basic. Composition K has a slightly higher melting point (1105° ± 3°C) and a higher silica content, but this is preferred because the slag is saturated with respect to tridymite and thus should not corrode siliceous refractories. Besides, it is less basic than composition S. The final slag composition, therefore, was chosen to

Jan 1, 1947

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By M. E. Grimes

A method of predicting uranium extraction rate in underground bacterial leaching of as-blasted ore has been developed. The method is based on the hypothesis that extraction is directly proportional to the volume of a piece of ore that is penetrated by the leaching agent, and that each piece of ore, regardless of size, has been penetrated radially from the external surface to the same depth at a given leaching time. Consequently, given an initial size and assay distribution, extraction should be predictable for a given penetration. Two laboratory bacterial leaching tests under simulated stope leaching conditions were carried out for a periods of 89 and 96 weeks. On completion, the residual ore was screened and analyzed. The information so obtained was employed to provide an elapsed time base for the penetration model, from which predictions of future extraction were made. The finding of solubilized uranium trapped within apparently sol id ore pieces was unexpected. However, it is not recoverable except after crushing, and hence does not affect calculations of underground leaching .

Jan 1, 1974

By Marston G. Fleming

CRITICAL pH has been defined by Wark1 as that pH value below which a mineral will float and above which it will not float in solutions containing a given concentration of collector but free from other depressants or activators. - The relationship between mineral, collector concentration, and pH is expressed in the form of a critical pH curve determined by the captive bubble method and is generally regarded as being fundamental to the system involved. The mechanism of alkali depression is currently in dispute, two general theories having received authoritative support. The view expressed in Taggart&apos;s chemical theory of flotation2 is that in the presence of a critical concentration of hydroxyl ions, all the metal ions available at the surface of the mineral are present as anions of the form [M (OH)x]-y. The formation of the necessary metal xanthate is thus precluded and, furthermore, any metal xanthate coating previously formed, at a lower pH, will be dissolved. Gaudin3,4 and the Melbourne school under Ware hold that alkali depression is caused by the preferential adsorption of hydroxyl ions by the mineral surfaces. This paper describes an investigation of the mechanism of alkali depression in each of the three systems: cerussite-aqueous carbonate-xanthate, cerussite-xanthate, and galena-xanthate. Alkali Depression of Cerussite by Control of Carbonate Ion Concentration Wark and Cox6 have shown that in the presence of Na2CO3 a higher concentration of xanthate is required to effect bubble contact with a cerussite surface than in carbonate-free solutions. To examine this depression of cerussite by sodium carbonate, a series of captive bubble tests was carried out on cerussite specimens in solutions containing 100 mg per liter of potassium ethyl xanthate and varying concentrations of sodium carbonate. The pH was adjusted by the addition of dilute hydrochloric acid. For purposes of comparison a standard critical pH curve was determined for cerussite with potassium ethyl xanthate in solutions containing no added carbonate. In the latter case pH adjustment was made with sodium hydroxide. The experimental method employed in both series was broadly similar to that described by Wark and Cox;7-9 a number of refinements suggested by Sutherland10 were adopted, and the procedure was further developed and modified to suit the particular requirements of the investigation. The relationship between pH and the concentration of potassium ethyl xanthate necessary to induce bubble contact at cerussite surfaces is shown in Fig. 1. The relationship between pH and the concentra- [ ] tion of sodium carbonate necessary to prevent bubble contact at cerussite surfaces in the presence of 100 mg per liter of potassium ethyl xanthate is shown in Fig. 2. Comparison of the. two curves shows that at a collector concentration of 100 mg

Jan 1, 1952

By R. K. Iyengar, G. C. Duderstadt

An investigation was carried out to determine the effect of Ca-Si additions on the dissolved oxygen content of liquid steel. An apparent equilibrium was reached after holding the melt for some time when the total oxygen content of the melt was identical with the dissolved oxygen. Results of the investigation show that for deoxidation with silicon and manganese the apparent equilibrium is reached after 8 to 12 min and the oxygen content of the melt is in good agreement with values reported in the literature for similar steel compositions. Ca-Si additions decrease the dissolved oxygen content appreciably below that obtained with Si-Mn deoxidation. It is postulated that some calcium dissolved in liquid steel at the time of its vaporization combines with dissolved oxygen to form CaO which then fluxes the manganese silicate, thereby lowering the activity of the deoxidation products. Slow flotation of calcium silicate inclusions is attributed to their slower growth rate. An addition of aluminum (to yield <0.005 pct Alsol) prior to introduction of Ca-Si improves the kinetics of removal of resulting deoxidation products. WITH the introduction of continuous casting of billets and blooms, application of calcium-containing alloys for deoxidation purposes has gained new interest. More so than in conventional ingot casting, the degree of control of the dissolved and total oxygen contents in steel for continuous casting can determine the success or failure of the operation because these affect both surface (pinholes) and internal quality of the billets. Of the available deoxidizers, only silicon has so far found wide application. However, in the typical range of application (0.20/0.30 pct Si), it is too weak a deoxidizer to suppress pinhole frequency to the level desirable for all but the least demanding appli-cations (approximately 10/50 pinholes per sq ft, de-pending on degree of subsequent reduction). On the other hand, Vincent&apos; has shown that it requires ap-proximately 0.007/0.008 pct A1 soluble in the steel to suppress pinhole formation to <10 pinholes per sq ft. In view of the difficulty of consistently maintaining this aluminum level and the associated problem of tundish nozzle constriction2 when aluminum is added to the ladle, steelmakers have searched for other de-oxidation alloys to circumvent the problem. Calcium-containing alloys offer such a possibility. When employed as a partial substitute for silicon, CaSi (30 pct Ca/60 pct Si) additions are reported to yield adequate pinhole contro1.3 Its use simultaneously preserves the "fluidity" of the steel and ensures good castability.4 Oxygen contents as low as 0.007 to 0.014 pct have been obtained with CaSi additions varying between 3 to 8 lb per ton.5-7 Due to the high degree of vaporization of calcium at the temperature of molten steel and the different methods used to introduce it into the liquid, the reported results show considerable scatter and lack of consistency. According to several investiga- deoxidation tors, the flotation characteristics of CaSi products are not as favorable as those found for alumi-num but are similar to those established for silicates with low alumina content.678 Thus, cleanliness ratings were improved when CaSi was replaced by a com-bination of Si + A1 followed by CaMnSi additions.5,9 In view of the lack of a comprehensive description of the deoxidation potential of CaSi alloys, a study was undertaken of the effect of CaSi additions on oxygen content in comparison to Si + Mn and Si + Mn + Al. The alloy chosen for this study contained 63 pct Si, 32 pct Ca, <3 pct Al, and 2.5 pct Fe. EXPERIMENTAL PROCEDURE The experiments were divided in three groups as shown in Table I. In each group, the CaSi addition was increased successively while maintaining the melt composition constant. The experiments in the third group were designed to determine the effect of prede-oxidation with small amounts of aluminum. Ingot iron, containing 0.02 to 0.03 pct C and 0.03 to 0.05 pct Mn, was melted in a 100-lb magnesia crucible. Pig iron was added to the melt under air in an induction furnace to attain the desired carbon content of 0.05 to 0.15 pct and thereby control the initial oxygen content of the melt between 0.04 and 0.015 pct. After removal of the slag, the furnace was sealed and argon was introduced through an opening in the graphite cover, Fig. 1. When the desired temperature was reached, electrolytic manganese was added to the melt and pin samples were taken (7 mm silica tubing) to establish initial oxygen content. To obtain maximum efficiency, CaSi and metallic silicon were introduced in a sealed steel pipe into the bath. This procedure assured minimum loss of calcium through vaporization as the deoxidants were always released at the bottom of the melt. Samples were taken at regular intervals and quenched in water. Temperature of the bath was measured with a Pt/Pt-10 pct Rh thermocouple. Portions of the pin sample were used for oxygen analysis; five determinations per sample were made to obtain average oxygen content. Oxygen analyses were made by the inert carrier gas fusion method with frequent cross checks with the vacuum fusion method.

Jan 1, 1970

By H. A. Bedworth

ALLOYS of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry1 proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche3 and Corson.4 The constitution of the system has also been recently investigated by Matuyama,5 and in the laboratories of the American Brass Co. by Smith.6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of, the constitution of copper-silicon alloys, the solubility reaches its maximum value, 6.7 per cent. silicon, between 721° and 782° C. At 852° C. the solubility is 5.25 per cent., while at 400° C. it is only 4.1 percent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent. silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929

By C. R. Sandberg, L. S. Gournay, R. F. Sippel

The effect of fluid-flow rate and fluid viscosity on oil-water relative permeability determinations was studied using the "dynamic flow technique." In this work relative per-nleability curves were obtained for homogeneous small core .samples from several sandstorle outcrop form-utions. Radio-tracers were used for the determination of fluid saturation and for the detection of saturation gradients. Cobalt-60 in the form of cobaltous chloride was used as a water-phase tracer in some of the experiments. Iodine-131 in the form of iodobenzene and Mercury-20-3 in the form of mercury diphenyl were used as oil-phase tracers in other experiments. Flow rates for each phase were varied within a range of 2.5 to 140.6 ml/hr. Oil-phase vis-cosities under flowing condition,> were varied from 0.398 to 1.683 cp. The relative permbilities ob-tained were found to he solely a function of saturation and independent of flow rare, provided there was no .Saturation gradient induced in the core sample by "boundary effect." Even though equilibrium with re-sped to flowing conditions was obtained at the lower flow rates, where a saturation gradient exists, this equilibrium is of a "contingent"-type rather than the "steady-state" equi-librium implicit in the relative per-meability concept. The only effect of increasing the oil or non-wetting phase viscosity was to decrease the flow rate required for the elimina-tion of the boundary effect. Fairly good agreement between experimentally determined and calculated values of the boundary effect was obtained when the non-wet-ring oil phase was the only Flowing phase. INTRODUCTION In the characterization of reservoir rock, as well as in the solution of reservoir production problems, it is most desirable to have reliablc rela-tive permeability measurements for the rock and fluids of interest. Many techniques have been developed for the laboratory determination of the relative permeability of both large and small core samples. In varying degree, difficulties attend the use of all of the methods. Each of the methods requires the metered flow of fluids of known viscosity through the core sample under conditions wherein the pressure drop in the individual flowing phases can be measured or closely approximated. Since the relative permeability is a function of the saturation and distribution of the flowing fluids, some means of obtaining such information is also required. The laboratory determination of the relative permeability of a sample should give the same relative permeability saturation relationship that would exist if the sample were in place in the oil reservoir. The attainment of this objective is complicated by the fact that the use of small core samples for laboratory measurements is usually necessary. As a result, errors in measuring the relative permeability arise from boundary effects at either the fluid input or output ends of the sample; no significant boundary effect is anticipated at the sides of the sample normal to direction of fluid flow. At the input end of the sample a boundary effect exists if the flow fluids are not com- mingled as they would be in the reservoir. At the output end of the sample a boundary effect exists as a result of discontinuity of the capillary properties of the system. Here the flowing fluids leave the small flow channels and enter a collecting system having much enlarged flow channels. Thus, there is a tendency for the wetting phase to be retained by the core sample because of the attraction of the core sample for the wetting fluid. No reference is made to these boundary effects in either Darcy&apos;s equation or in the relative permeability concept. As a consequence the saturation effect peculiar to the input end of the core sample may cause an error in the effective permeability measurement, since some portion of the core sample must be utilized for commingling of the flow fluids. At the output portion of the core sample a saturation gradient or a saturation change along the axis of flow results. Since relative permeability is a function of fluid saturation, this saturation gradient may cause a variable permeability measurement, especially since extent and character of the saturation gradient can vary with fluid-flow rate. The most convenient method of minimizing the boundary effect, especially at the output end of the sample, is to flow the fluids of interest through the core sample at such high rates that the capillary forces arc insignificant as compared to the viscous forces involved in the fluid flow. Since recent work of a preliminary nature has indicated that fluid dispersion in the porous medium increases with the flow rate, the high flow minimizes the boundary effect at the input end of the core sample by enhancing the mixing of the fluids.

By T. L. Fritzlen

Extrusion of aluminum alloys in this country is performed mainly by direct extrusion, therefore this paper is confined only to factors affecting the rate of extrusion by this method. Many factors affect the rate of extrusion of aluminum alloys. It is the purpose of this paper to present a discussion on the factors that are subject to technical control. Most of them are closely related, so that a clear-cut distinction between them is rather difficult. However, an attempt will be made to evaluate the effect of each factor separately, as far as possible. The most important factors only will be considered, and these will be discussed in detail under three general headings: (I) characteristics of the equipment, (2) size and structure of the ingot, and (3) temperature of ingot, cylinder, and other parts. It is a well established fact1 that the pressure and the speed of extrusion are related and are exponential functions of one another. Therefore, whenever a certain condition tends, for instance, to increase the pressure required for extrusion, it will reduce the extrusion speed if the pressure is maintained constant. For this reason, in this paper the effect of various conditions is expressed either in regard to their effect on the pressure required or the extrusion speed. Another established fact is the relation- ship between the temperature of the material being extruded and the pressure required to extrude. According to Schi-shokin,= this relationship is of the exponential type, and as the temperature is increased the pressure required is decreased. It would seem from the preceding that the greatest rates of extrusion can be obtained by the use of higher temperatures. However, as is well known, other factors intervene to limit the rate of extrusion of aluminum alloys when increasing the temperature. These factors will be discussed in detail later. Characteristics of the Equipment The capacity of the press determines * the maximum unitary pressure that can be applied for any given cylinder diameter. Pressures used for extrusion of aluminum alloys range from approximately 50,000 lb. per sq. in. to 150,000 lb. per sq. in., dependent upon the alloy and the size of the shape extruded. Higher pressures could be used to advantage, but existing steels limit pressures employed in the production of extrusions. Numerous mechanical characteristics of the extrusion press affect extrusion rate. The most important characteristics of the press itself are: (I) sensitivity of the main pressure valve and accuracy of pressure gauges, (2) accuracy of equipment to heat the cylinder uniformly and to control cylinder temperature, and (3) accuracy of means of measuring the speed of extrusion. The variables subject to control during the extrusion operation are pressure, temperature, and speed, and it is evident that the preceding characteristics

Jan 1, 1946

By T. L. Fritzlen

Extrusion of aluminum alloys in this country is performed mainly by direct extrusion, therefore this paper is confined only to factors affecting the rate of extrusion by this method. Many factors affect the rate of extrusion of aluminum alloys. It is the purpose of this paper to present a discussion on the factors that are subject to technical control. Most of them are closely related, so that a clear-cut distinction between them is rather difficult. However, an attempt will be made to evaluate the effect of each factor separately, as far as possible. The most important factors only will be considered, and these will be discussed in detail under three general headings: (I) characteristics of the equipment, (2) size and structure of the ingot, and (3) temperature of ingot, cylinder, and other parts. It is a well established fact1 that the pressure and the speed of extrusion are related and are exponential functions of one another. Therefore, whenever a certain condition tends, for instance, to increase the pressure required for extrusion, it will reduce the extrusion speed if the pressure is maintained constant. For this reason, in this paper the effect of various conditions is expressed either in regard to their effect on the pressure required or the extrusion speed. Another established fact is the relation- ship between the temperature of the material being extruded and the pressure required to extrude. According to Schi-shokin,= this relationship is of the exponential type, and as the temperature is increased the pressure required is decreased. It would seem from the preceding that the greatest rates of extrusion can be obtained by the use of higher temperatures. However, as is well known, other factors intervene to limit the rate of extrusion of aluminum alloys when increasing the temperature. These factors will be discussed in detail later. Characteristics of the Equipment The capacity of the press determines * the maximum unitary pressure that can be applied for any given cylinder diameter. Pressures used for extrusion of aluminum alloys range from approximately 50,000 lb. per sq. in. to 150,000 lb. per sq. in., dependent upon the alloy and the size of the shape extruded. Higher pressures could be used to advantage, but existing steels limit pressures employed in the production of extrusions. Numerous mechanical characteristics of the extrusion press affect extrusion rate. The most important characteristics of the press itself are: (I) sensitivity of the main pressure valve and accuracy of pressure gauges, (2) accuracy of equipment to heat the cylinder uniformly and to control cylinder temperature, and (3) accuracy of means of measuring the speed of extrusion. The variables subject to control during the extrusion operation are pressure, temperature, and speed, and it is evident that the preceding characteristics

Jan 1, 1946

George E. Collins, Nacoochee, Ga. (communication to the Secretary): The results tabulated below were obtained at the Reynolds mill, White county, Ga. They were noted, not with a view to investigating the point discussed by Mr. Clark, but in course of a test on a working scale to determine the com parative saving from a given free-milling ore on copper and silvered plates respectively. In every case the bullion assayed was the result of a separate clean-up on a considerable quantity of ore. The ore varied widely in grade and in other respects, but the runs bracketed in the table were made at the same time, in adjoining batteries, and on similar types of ore. In a * Result modified by the addition to the bullion-shipment of a little impure bullion left over from previous clean-ups.. On these occasions, the strips of copper were removed from the tables, and: their lower surfaces were cleaned. Hence the higher yield reported.

Jan 1, 1900

By Eugene Guccione

FOREWORD-Back in October of last year, I approached three of the largest commercial banks in the country to solicit an article about the role of commercial banks in mine financing. "We&apos;ll be delighted to cooperate with you in any way we can," was the stock response. As the September 1975 deadline approached, however, every bank officer I had contacted almost a year earlier informed me that he couldn&apos;t write such an article be- cause of "prior commitments," "an excessive workload," or "vacation schedule," etc. This was not a total surprise. Any commercial banker will be truly delighted in talking with you, if you have a good mining prospect, a good reputation, a good batting average in your business-and if he has the capital you want to borrow. But what happens when banks themselves are illiquid? Much as they would like to help you, they simply can&apos;t. And most of them clam up.

Jan 9, 1975

By John Birkinbine

In the preparation of the paper upon " The Operation of Warwick Furnace, Pennsylvania, from August 27, 1880, to September 1,1885," presented at the Pittsburgh meeting, I purposely refrained from offering theories to explain the peculiarities of furnace operation, on the ground that it was better for those actively engaged in blast-furnace management to present records of operations, than for one more directly interested in blast-furnace engineering and construction to venture upon the sea of speculation as to causes. The manager of an iron-works naturally feels that he knows as much about his particular furnace or furnaces as any one else, and as Mr. Cook, after his close attention to and study of the Warwick furnace, was at that time unwilling to present theories, I felt a disinclination to assume more acumen than the manager.

Jan 1, 1887