Search Documents

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

By Gernot Kostorz

In a recent paper, Raffo and itcheell1 compared solid solution hardening of various bcc alloy single crystals at room temperature and concluded that the expression for localized elastic interaction between dislocations and solute atoms2 that gives the critical resolved shear stress (CRSS) 7,: to = Z . µE3/2 C1/2 where c = concentration, e = misfit parameter, (µ = shear modulus, Z = numerical constant Fig. 1—The slope dT0/dc1/2 for niobium alloy single crystals deformed at 570°K plotted against the misfit parameter € = In' I + 1616 I. from Ref. 6, •estimated from Ref. 7. Table I. Plateau Hardening and Alloy Parameters for Niobium Alloys dT0/dc1/2, kg/mm2 Solute Ref. 6 Tantalum 3.7 ± 0.3 1.9 0.73 + 0.06 9 0.0 ± 0.5 15 Vanadium 16.1 ±1.4 - 0.69 i 0.01 9 -7.4 ± 0.5 16 Tungsten 12.5 ? 1.5 20.9 0.92 i 0.05 10 -5.0 t 0.4 17 Rhenium - 25.9 1.24 11.12 -8.5 ± 0.4 I5 Molybdenum - 14.6 1.04 13,14 -4.6 s†±?˜µ?fF?? 0.5 17 Hafnium - 13.9 0.37 12 4.8 ± 0.5 17 Table 11. Solid Solution Hardening and Alloy Parameters for Tantalum Alloys i)' dTo/dc1/2 kg/mm2, dTp/dc1/2 kg/mm2, Ref. 22 1006 Solute ˜570°K Ref. 7 See Text Ref. 25 Rhenium 44.3 32.5 0.65 -8.5 Tungsten 32.1 24.3 0.34 -4.6 Molybdenum 29.3 19.1 -0.19 -5.9 Niobium 5.8 5.5 -0.43 0.I

Jan 1, 1970

By Carl Heinrich

I HAVE read with particular interest that portion of the discussion by Anton Eilers referring to the high-lime (and also high-alumina) slags made by August Raht in 1881, while smelting the Horn Silver ores at Franklin, Utah. The two analyses of such slags, furnished by Mr. Raht to Mr. Eilers are: Horn Silver Slags Oxygen(b) Oxygen(b) Average of I and. II Slag I percentage Slag II percentage Oxygen Si02 33.9 18.1 .35.0 18.7 34.50 18.40 FeO 26.8 6.0 25.4 5.7 26.10 5.80 CaO 26.1 7.5 24.9 7.1 25.50 7.30 BaO 3.2 (a) 0.3 3.2 0.3 3.20 0.30 A1203 10.8 5.1 9.3 4.4. 10.05 4.75 100.8 37.0 97.8 36.2

Jan 10, 1916

Domestic: Middle West-,11.. B. Newcombe Eastern District-J. French Robinson1 Kansas-Henry A. Ley 2 Oklahoma-Henry A. Ley 3 Texas, except Gulf Coast and Panhandle-M. G. Cheney 5 Texas Panhandle-W. E. Hubbard and H. E. Crum 6 Gulf Coast-L. P. Teas 7 South Arkansas, North Louisiana and Mississippi-H. K. Shearer 8 Foreign Mexico-V. R. Garfias and C. 0. Isakson 9 Canada-Line M. Farish 10 Venezuela-C. W. Hamilton 10 Colombia-J. T. Duce 12 Peru-O. B. Hopkins 12 Trindad-Williaim J. Millard 13 Dutch East Indies-Fred B. Ely 13 Rumania-I. I. Gardescu . .. . 14 India-Eric J. Bradshaw 14

Jan 1, 1931

By Carl Henrich

I have read with particular interest that portion of the discussion by Anton Eilers referring to the high-lime (and also high-alumina) slags made by August Raht in 1881, while smelting the Horn Silver ores at Franklin, Utah. The two analyses of such slags, furnished by Mr. Raht to Mr. Eilers are: (a) Not determined in this analysis. (b) Not given in Mr. Eilers' paper. Oxygen ratio, A1 as base. I. 0 in acid: O in base:: 18.1:18.9:: 0.96:1 11. 0 in acid :O in base:: 18.7:17.5::1.06:1 Average: 18.4:18.15=1.01:l Oxygen ratio, AI as acid. I. O in acid: O in base: :23.2:13.8:: 1.68:1 11. O in acid: O in base::23.1:13.5:: 1.76:1 Average: 23.15:13.4 = 1.73:l By assigning to alumina the the of a base, Mr. Eilers deduces the formula 3Feo.-2SiOa + 4Cao.2SiO². The nearest approach to a simple formula expressing the average composition of these slags, which I can figure, is 9RO.Al2O3.6SiO2. Allowing a ratio of 4Feo : 5Cao, we have for this formula:

Jan 1, 1917

By Virgil Miller, F. B. Petermann, S. F. Ravitz

The Cle Elum nickeliferous iron deposit is in Kittitas County, Washington, in a rugged, mountainous region about 23 miles north of the town of Cle Elum. The Biewett Pass deposit, which is similar in character and occurrence, is in Chelan County, about 18 miles east of the Cle Elum deposit. A more or less continuous ore zone may extend between the two deposits, since iron ore is reported to have been discovered at Iron Mountain, which lies directly between them. The ore probably was formed by meta-morphism of laterite resulting from Ieach-ing of serpentine derived from peridotite. It consists largely of magnetite grains distributed through a matrix of limonitic material containing a small amount of hematite and chromite. Many of the chromite grains have shells and inclusions of magnetite. The magnetite grains range in size from 1200-mesh to 1/4-in., the average size being 48 to 65-mesh; the chromite grains range from 20 to 150-mesh. The gangue minerals are olivine and serpentine with a small, amount of chlorite, and appear both as very thin bands in the ore and 's minute fragments in the limonitic matrix. The nickel is present as minUte inclusions of a nickel silicate mineral within the magnetite and gangue par- ticles, varying in size from 1500 to about 280-mesh. Detailed analyses of 3000-lb. lots of Cle Elum and Blewett Pass ore are given in Table I. TABLE i.—Analyses of Ore Samples Per Cent Ore from Constituent cle Elum' Blewett Pass Cr....................... 2.23 2-12 Ni...................... 1.43 0.9s Fe...................... 52.9 41.4 SiOz.................... 5.6 13.4 CaO.................... 0.3 0.8 MgO................... 4-1 7-5 AI2O3................... 7.0 2.g P...................... 0.022 0.034 S....................... O.O1 o.oa Mn..................... I.I 0.4 Ba..................... nil co..................... o.oa 0.02 CU..................... 0.02 0.03 As...................... 0.03 Au..................... nil Ag°..................... O.58 Pt...................... ml Fe++.................... 8.9 5-9 Fe+++.................. 44-0 35-5 « Ounces per ton, 1 sr,cte,so,","&&$ally absent: B, W, M~, T~, V, ~i, Bi, Pb. Sb. Sn. Be, In, Hg. Zn, Zr. Cd. Preliminary Tests Attempts to beneficiate the ore by ore-dressing methods, including various 'cornbinations of sink and float, tabling, jigging, flotation, and magnetic separation, were consistently unsuccessful. A wide variety of roasting and leaching tests were made on both raw and reduced ore, but in most of the tests little or no nickel was extracted, and in none did the extraction exceed 50 Per cent. No nickel could be volatilized as the carbonyl. by treating reduced ore with carbon monoxide. Fairly good sepa-

Jan 1, 1944

J. E. JOHNSON, JR., New York, N. Y. (communication to the Secretary*).-The discussion of Mr. Henrich's paper took place at a meeting from which I had the misfortune to be absent, and has just come to my attention. I do not wish to let the subject pass without contributing to it a little information which has come into my possession. In 1912, I published a brief note in the Transactions on The Effect of Alumina in Blast-Furnace Slags, giving in tabular form three typical slags used in iron blast-furnace practice, one of them the high alumina slag of, which Professor Richards speaks. That table is reproduced herewith. TABLE 1.-Composition of Slays. 1 3 3 4 5 6 7 CaO by Neutral Ratio Ratio Ratio Al2z03, SiO2, Differ- Substan- Cat Ca0 a A1203 Ratio Per Per ence, ces, CaO Cent. Cent. Per Per Al2O3 + Sioz Sit: SiO2 Cecil_ Cent. Virginia practice 6.5 36.0 54.0 3.5 1.27 1.6S 1.50 Lake-ore practice 13.5 33.0 50.0 3.5 1.08 1.92 1.51 Special experiment... 36.0 24.7 36.8 3.5 0.59 2.90 1.44 It supplies what seems to me convincing evidence that, for the purposes of the iron blast furnace, alumina can be regarded only as a neutral substance, dissolving in the slag and materially altering its viscosity, but not affecting its chemical activity. In subsequent experience with charcoal furnaces, I found the same rule to hold; that the chemical effect of alumina could be disregarded, providing the ratio of the lime and magnesia to the silica were kept constant. This is exactly the experience which Messrs. Dwight and Mathewson had in copper- and' lead-smelting furnaces. I have never seen any evidence or argument adequate to support the contention of Professor Richards-that the alumina acted as a base in the charcoal iron furnace and as an acid in the coke furnace, and that the function of alumina in iron-furnace slags is inherently different from that in copper- and lead-furnace slags-and I am compelled to differ absolutely with his conclusions in that respect.

Jan 9, 1917

By Arthur F. Taggart

THIS paper proposes two units (believed to be new) for designating, respectively, capacity and efficiency for primary and intermediate crushers. CAPACITY Operators know that the tonnage of rock that can be put through a particular crusher in a given time depends primarily upon the crusher setting (open setting for jaw and primary gyratory types; closed setting for cones and rolls), and secondarily on the lithological character of the feed, its maximum size, the amount of fines that it carries, its moisture content, and the method of feeding. The proposed capacity formula states a relationship between all of these factors in one empirical equation, as follows: TR = TR80KK'K" [I] in which TR, called "reduction tons per hour" is the new capacity unit; T = tons of feed per hour requiring crushing; R50 = "80-per cent reduction ratio"; and K, K', and K" are constants that approximate quantitatively lithological character, moisture content and method of feeding, respectively. T is the hourly weight of material in the feed that is coarser than the coarsest discharge of the crusher. (For marked departures from the normal specific-gravity range-2.5 to 2.7-T should be adjusted to corresponding volumes.) In the crushers under consideration, discharge from the crushing zone is limited by the minimum dimension of a particle. Passage of the particle through a square-mesh screen is limited by its intermediate dimension. Sheppard' has shown that the ratio of maximum: intermediate: minimum average dimensions of broken rock fragments may be taken as about I.5: I: 0.6 for nonslabby rocks such as are normally crushed, while for slabby rocks, such as thin-bedded sedimentaries, foliated schists and gneisses, and the blocky metamorphics, the ratio is of the average order I.3:I:0.3, with the possibility of an even smaller relative value for the thickness. Gaudin2 finds the corresponding ratio for -150 + 200-mesh pyrite to be I.4: I : 0.6. The hourly tonnage of crusher-plant feed, therefore, should be diminished by the amount thereof that would pass a square-mesh screen of which the aperture is S times the crusher setting, where S is a shape factor with the value I.7 for rocks that break exceptionally cubic; 2 for ores and rocks that exhibit no appreciable tendency to slabbiness; and 2.5 to 3, or, in exceptional cases, even larger, when the tendency to slabbiness is marked. R80 is the quotient of the theoretical square-mesh aperture that would pass 8o per cent of the feed, divided by the aperture that would pass S0 per cent of the product. It is best determined from screen tests.

Jan 1, 1941

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 W. S. Holt, E. T. Tkac, R. A. Grange

QUANTITATIVE knowledge of the time element involved in austenite transformation in a particular steel provides a sound basis for understanding and planning heat-treatment. Such knowledge is conveniently obtained by measurement of austenite transformation as it occurs at each of a series of temperature levels. The results of these measurements usually are summarized in the form of the now familiar isothermal transformation diagram (I-T diagram, TTT diagram, or S-curve). Although a considerable number of such diagrams already have appeared in the literature, there remain many compositions of commercial importance for which no I-T diagram is available. The diagram for many such steels may be predicted from published data with sufficient accuracy for most practical purposes, but for others no satisfactory prediction can be made because the effect on austenite transformation of one or more of the important alloying elements present is not well enough known. Such a steel is Nitralloy, Type 135-Modified, which, containing about 1.25 per cent aluminum, differs from any whose I-T diagram has been published. This paper presents results of a study of the isothermal transformation behavior of a sample from a commercial heat of this aluminum-chromium-molybdenum steel, together with pertinent supplementary data including the equilibrium transformation temperatures (Ae3 and Ae1), the temperature range of martensite formation, and the end-quench hardenability. These data are directly applicable to the heat-treatment of this type of steel and are of interest in revealing some of the fundamental effects of aluminum as an alloying element in steel. MATERIAL All specimens were prepared from a 13-in. diam bar forged from a 5 by 5-in. billet from a commercial heat made in an electric arc furnace. The composition of the bar was; C, 0.41 per cent: Mn, 0.57: P, 0.016: S, 0.005: Si, 0.24: Ni, 0.17: Cr, i.57: MO, 0.36: Al, 1.26. The forged bar was normalized from 1750°F (955°C) and then tempered for one hour at 1200°F (650°C), this tempering treatment having been given to facilitate the machining of specimens. EQUILIBRIUM TRANSFORMATION TEMPERATURES In hypoeutectoid steel the minimum temperature at which austenite is completely stable, Ae3, and the maximum temperature at which austenite is completely unstable, Ae1, are of great significance in heat-treatment. Since these temperatures are dependent upon com-

Jan 1, 1946

By C. J. Huffman

MAGNESIUM alloy tubing and hollow shapes are finding increasingly wider usage in practical applications today. Square and rectangular tubing and hollow shapes find [ ] greater diversification in use than standard round tubing. Typical applications are roller conveyors, ladder rungs, spools, furniture, tank car loading tubes, athletic equipment, and business machine parts. In general, the amount of tubing and hollow shapes produced represent a minor portion of the magnesium extrusion business. The magnesium alloys in which tubing and hollow shapes are being produced together with typical properties are presented in Table I. MI A alloy is a low cost alloy possessing good welding and stress corrosion characteristics together with moderate formability and corrosion resistance. It is widely used for low strength applications. AZ31 B, alloy is used for moderately stressed applications and possesses good corrosion resistance and formability with fair welding characteristics. AZ61 A alloy has slightly higher physical properties than AZ31 B alloy together with good formabil- [ ] ity and corrosion resistance but slightly poorer welding characteristics. AZ80 A, ZK60 A-F, and ZK60 A-T5 alloys are used where the maximum in physical properties is required. AZ80 A alloy possesses fair corrosion resistance but with formability and welding characteristics inferior to' the other alloys. ZK60 A-F and ZK60 A-T5 alloys, while only recently offered for com¬mercial use, are finding favor due, to the higher permissible extrusion rates. These alloys possess greater toughness than AZ80 A alloy and, while of moderate formability at room temperature, are very formable at 300° to 500°F. The major portion of tubing and hollow shape production at the present time is in AZ3I B alloy. Magnesium alloy tubing is commercially available in the as-extruded condition or, in the case of ZK60 A-T5, in the as-extruded and aged

Jan 1, 1951

By Arthur F. Taggart

This paper proposes two units (believed to be new) for designating, respectively, capacity and efficiency for primary and intermediate crushers. Capacity Operators know that the tonnage of rock that can be put through a particular crusher in a given time depends primarily upon the crusher setting (open setting for jaw and primary gyratory types; closed setting for cones and rolls), and secondarily on the lithological character of the feed, its maximum size, the amount of fines that it carries, its moisture content, and the method of feeding. The proposed capacity formula states a relationship between all of these factors in one empirical equation, as follows: Tr = TR80K'K" [I] in which Tr, called "reduction tons per hour" is the new capacity unit; T = tons of feed per hour requiring crushing; R80 = "80-per cent reduction ratio"; and K, K', and K" are constants that approximate quantitatively lithological character, moisture content and method of feeding, respectively. T is the hourly weight of material in the feed that is coarser than the coarsest discharge of the crusher. (For marked departures from the normal specific-gravity range—2.5 to 2.7—T should be adjusted to corresponding volumes.) In the crushers under consideration, discharge from the crushing zone is limited by the minimum dimension of a particle. Passage of the particle through a square-mesh screen is limited by its intermediate dimension. Sheppardl has shown that the ratio of maximum: intermediate: minimum average dimensions of broken rock fragments may be taken as about 1.5:=:0,6 for nonslabby rocks such as are normally crushed, while for slabby rocks, such as thin-bedded sedimentaries, foliated schists and gneisses, and the blocky metamorphics, the ratio is of the average order I.3:I:o.3, with the possibility of an even smaller relative value for the thickness. Gaudin2 finds the corresponding ratio for —I50 + 200-mesh pyrite to be I.4: I:0.6. The hourly tonnage of crusher-plant feed, therefore, should be diminished by the amount thereof that would pass a square-mesh screen of which the aperture is S times the crusher setting, where S is a shape factor with the value 1.7 for rocks that break exceptionally cubic; 2 for ores and rocks that exhibit no appreciabie tendency to slabbiness; and 2.5 to 3, or, in exceptional cases, even larger, when the tendency to slabbiness is marked. R80 is the quotient of the theoretical square-mesh aperture that would pass 80 per cent of the feed, divided by the aperture that would pass 80 per cent of the product. It is best determined from screen tests. If, as is usual with primary crushers, a sizing test of feed is not available, the

Jan 1, 1943

By Arthur F. Taggart

This paper proposes two units (believed to be new) for designating, respectively, capacity and efficiency for primary and intermediate crushers. Capacity Operators know that the tonnage of rock that can be put through a particular crusher in a given time depends primarily upon the crusher setting (open setting for jaw and primary gyratory types; closed setting for cones and rolls), and secondarily on the lithological character of the feed, its maximum size, the amount of fines that it carries, its moisture content, and the method of feeding. The proposed capacity formula states a relationship between all of these factors in one empirical equation, as follows: Tr = TR80K'K" [I] in which Tr, called "reduction tons per hour" is the new capacity unit; T = tons of feed per hour requiring crushing; R80 = "80-per cent reduction ratio"; and K, K', and K" are constants that approximate quantitatively lithological character, moisture content and method of feeding, respectively. T is the hourly weight of material in the feed that is coarser than the coarsest discharge of the crusher. (For marked departures from the normal specific-gravity range—2.5 to 2.7—T should be adjusted to corresponding volumes.) In the crushers under consideration, discharge from the crushing zone is limited by the minimum dimension of a particle. Passage of the particle through a square-mesh screen is limited by its intermediate dimension. Sheppardl has shown that the ratio of maximum: intermediate: minimum average dimensions of broken rock fragments may be taken as about 1.5:=:0,6 for nonslabby rocks such as are normally crushed, while for slabby rocks, such as thin-bedded sedimentaries, foliated schists and gneisses, and the blocky metamorphics, the ratio is of the average order I.3:I:o.3, with the possibility of an even smaller relative value for the thickness. Gaudin2 finds the corresponding ratio for —I50 + 200-mesh pyrite to be I.4: I:0.6. The hourly tonnage of crusher-plant feed, therefore, should be diminished by the amount thereof that would pass a square-mesh screen of which the aperture is S times the crusher setting, where S is a shape factor with the value 1.7 for rocks that break exceptionally cubic; 2 for ores and rocks that exhibit no appreciabie tendency to slabbiness; and 2.5 to 3, or, in exceptional cases, even larger, when the tendency to slabbiness is marked. R80 is the quotient of the theoretical square-mesh aperture that would pass 80 per cent of the feed, divided by the aperture that would pass 80 per cent of the product. It is best determined from screen tests. If, as is usual with primary crushers, a sizing test of feed is not available, the

Jan 1, 1943

By C. R. Kuzell

STAFF: Editor, Gerhard Derge Carnegie lnstitute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: C. C. Long, President; John Chipman, Past-President; J. S. Smart, Jr., Vice-President, T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMiTTEE OF THE METALLURGICAL SOCIETY: D. J. Carney, Chairman; Robert Maddin, Past-Chairman; J. H. Hollomon, J. H. Jackson, H. H. Kellogg, T. B. King, F. C. Langen-berg, D. L. McBride, W. O. Philbrook, J. S. Smart, Jr., R. L. Smith, J. D. Sullivan, and F. L. Vogel Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: H. H. Kellogg, Chairman; T. 8. King, Post-Chairmon; R. P. Hermsdorf, W. A. Krivsky, R. E. Lund, C. L. McCobe, Poul Queneou, A. 5. Russell, M. E. Wadsworth, and W. D. Wilkinson. Institute of Metals Division: R. L. Smith, Choirman; P. A. Beck, I. I. Bessen, J. O. Betterton, Jr., R. S. Davis, J. J. Gilmon, R. 8. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurlond, J. J. Heger, M. Hermon, J. N. Hobstetter, H. H. Johnson, Jr., I. R. Krarner, W. C. Leslie, R. A. Meussner, R. R. Nosh, G. E. Pellissier, T. N. Rhodin, A. U. Seybolt, L. L. Seigle, I. S. Servi, P. G. Shewmon, L. Slifkin, J. K. Stanley, C. D. Starr, and J. Washburn. Iron and Steel Division: F. C. Longenberg, Chairmon; H. L. Bishop, C. W. Sherman, J. 8. Wagstaff, and E. Whittenberger. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for nan-AIME members in United States and North, South, and Central America; $25, foreign; $5 far AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1960 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York ...Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts ... Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 218, Number 4

Jan 1, 1961

By M. B. Bever, A. K. Jena

Equations for the heat effects of additions of mixtures of multicomponent phases to a solution have been derived in terms of the enthalpy interaction coefficients. By these equations and the measured composition dependence of the heat effects on addition of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions, values of the enthalpy in-teraction coefficients in tin-rich solutions at 541°K have been obtained. Analysis of these results in terms of the regular solution theory and the quasichemical theory suggests that near the melting point of the solvent association in the solution becomes important. SEVERAL recent papers have discussed the nature of dilute solutions on the basis of measured enthalpy interaction coefficients. l-3 These coefficients contribute to the understanding of the constitution of solutions and can be used for the evaluation of thermo-dynamic data of multicomponent systems. Their experimental determination, however, is laborious. This communication reports values of the enthalpy interaction coefficients of silver, cadmium, and gold in liquid tin-rich solutions obtained from the measured heat effects of additions of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions. These measurements were made in the course of the determination of the heats of formation of Ag-Cd solid solutions reported in a concurrent publication.4 THE HEAT EFFECT OF AN ADDITION TO A SOLVENT This analysis is concerned with the addition of a mixture of multicomponent phases from the temperature To to a solvent of known composition at temperature T. If Nmixture << Nsolvent, where N designates the gram-atoms involved, the heat effect per g-atom of mixture added can be expressed as (HT - HT )i = difference in heat contents of component element i in the mixture at T and To Q = heat effect on solution of the mixture at temperature T Also1 Q = S Xi [2] where ?Hi ,T,x = relative partial enthalpy per g-atom of i in solution at temperature T and composition of the solution x x = average of the atom fractions of the added material in solution before and after the addition The relative partial enthalpy ?Hi per g-atom of an element i in a dilute solution composed of a solvent 1 and the solutes j = 2, ... m is related to the interaction coefficients by the following equation5 ?Hi - ?Hi-?Hi,x1-1 + S n1ixj+ . . . +S...S...S nrixn2... Xnji...Xnmm+... [3] vhere Xj = atom fraction of solute j in the solution nri = the rth order enthalpy interaction coefficients, which can also be represented by the more general designation5 L(i)n2,n3...nm and nj may have any positive integral value or zero. For identification of various rth order interaction coefficients, nri is written as nn2i2,...nij,...nmm. Eqs. [1], [2], and [3] combine to give the following general equation for the heat effect on addition of a small quantity of a mixture to a large quantity of a dilute solution n = _?ga ?Ha,To + ? Xi(HT - HT o)i a. i + ?xi?Hi,X,i?1 + ??xnjixj + . . . + ???. . .?. . .?xinrix2n2. . . xnji. . . xnmm+ . . . [4] The first term on the right-hand side of this equation is the heat of decomposition at the addition temperature of the phases present in the mixture, the second term is the heat required to raise the temperature of

Jan 1, 1970

By G. Derge, Ling Yang, John Henderson

Self-diffusion coefficients of aluminum have been measured by the capillary reservoir technique in liquids of the CaO-SiO2-Al2O3 system containirg equimolar portions of CaO and SiO2, in the temperature range 1400o to 1520oC. For the melt containing 6.0 mole pct Al2O3 the results can be expressed by the equation D = [(4.3 * 0.3) x 104] exp [(-85,000 * 17,500)/RT]cm~sec-&apos;; for the melt containing 12.5 mole pct Al2O3, by the equation D = (5.4 i 0.2) exp [(-60,000 * 10,00O)/RT] cm2sec-: A concept of the constitution of these melts has been developed which proposes that the ratios O/(Si +Al) and Al2 O3/CaO determine the dominant species present. In recent years considerable work has been done on the system CaO-SiO2-A12O3 with a view to elucidating the structure of liquids of this system. Conductivity,&apos; electromotive force, 3 density,4 and activity5 measurements have all contributed to an understanding of the problem, but as yet there is no entirely satisfactory theory that can account for all the observed experimental results. In principle, measurements of self-diffusion coefficients should give further information which is not obtainable in other ways. Self-diffusion coefficients for calcium, silicon,6 and oxygen7 have been measured. The present investigation extends the series of self-diffusion coefficient measurements to include aluminum and develops a concept of constitution for liquids of this system which is compatible with all the observed experimental results. EXPERIMENTAL The technique used in the measurement of the self-diffusion coefficient of aluminum was the capillary-reservoir method,8 A126 being incorporated in the melt contained in the capillary and inactive aluminum in the reservoir melt. This method was chosen because it minimizes convection currents&apos; in the diffusion zone. It has the further advantage that the boundary conditions are such that a slight modifica- tion of Anderson and saddington&apos;s8 solution of Fick&apos;s Law yields an equation which requires measurements only of the length and the initial and final average specific activities of the solidified melt within the capillary. where t is the diffusion time, Co is the average specific activity of the melt contained in the capillary at t = O, C is the average specific activity of the melt contained in the capillary at t = t, 1is the length of the capillary, and D is the self-diffusion coefficient. The equation is of somewhat different form than those previously applied to high temperature diffusion studies because the specific activity of the melt in the reservoir was negligible both before and after diffusion. The diffusion apparatus is shown schematically in Fig. 1. It consisted of a silicon carbide resistance furnace containing the inactive melt in a graphite crucible, internal dimensions 7/8 by 4 in., enclosed in a 1 1/4- by 1 1/2- by 30-in. McDanel tube. A 3/8-in. McDanel thermocouple sheath to which graphite radiation shields and a graphite protection tube were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube the capillaries could be lowered into or raised out of the melt. Temperature was measured with a Pt-Pt 13 pct Rh thermocouple which was calibrated periodically against a standard couple. The furnace temperature was controlled to ± 5°C through the thermocouple immersed in the melt. Temperature variation over the depth of the melt was less than ± 3°C. The inactive melts were prepared from pure native quartz, assaying better than 99.9 pct SiO2, A.R. grade A12O3 and A.R. grade CaCO,. The same quartz and CaCO3 were used in preparing the active melts, the

Jan 1, 1962

By A. M. Kivari

Operations at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials. Closed-circuit grinding, classification, hy-droseparation, flotation, agitation, and thickening are familiar terms at this cement plant. These methods make it possible to process refractory limestone into suitable materials for the mallufacture of modern cements. Construction of the plant, having originally a design capacity of 7000 bbl. of cement per day, was started in June 1939, and the first clinker was ground on the following Christmas Day. At present the capacity is about 12,000 bbl. of finished cement per 24 hr., most of the production being low-heat cement. † About 3I30 tons of limestone, 620 tons of clay and I00 tons of gypsum are required daily for this output. Occasionally iron oxide is added to the clay to obtain the desired composition. This, together with the gypsum, is purchased from outside sources. up to the present time, the ccrporation has produced low-heat, normal, moderate-heat, moderate-sulphate-resisting, high-early-strength, oil-well, modihed-oil-well, and plastic cements. Most of the present production is for Shasta Dam, near Red- ding, Calif., the total demand being 5,800,000 bbl. of cement. Following are some of the cement require ments of the Shasta Dam specifications: Per Cent Chemical composition: Loss in ignition.......... 2.25 Insoluble residue......... 0.75 SO3.................... 2.25 MgO................... 5.&apos;&apos; Uncombined lime in clinker (CaO)......... I.25 Percentage of iron oxide to alumina ratio....... I.5 Compound composition: Tricalcium silicate (3CaO.SiO2)........... Not more than 35 Dicalcium silicate (zCaO.SiO2)........... Not less than 40 and not more than 65 Tricalcium aluminate (3CaO.Al2O3).......... Not more than 7 Tetracalcium aluminofcr- rite (4CaO.Al²O³.Fe²O³) Not more than 20 Fineness: The average specific surface in the bin sampled shall be not less than 1800 sq. cm. per gram and no individual sample less than 1600 sq. centimeters. Compressive strength: The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2.75 parts fine testing sand, by weight, shall be equal to or greater than the following:

Jan 1, 1942

By A. M. Kivari

Operations at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials. Closed-circuit grinding, classification, hy-droseparation, flotation, agitation, and thickening are familiar terms at this cement plant. These methods make it possible to process refractory limestone into suitable materials for the mallufacture of modern cements. Construction of the plant, having originally a design capacity of 7000 bbl. of cement per day, was started in June 1939, and the first clinker was ground on the following Christmas Day. At present the capacity is about 12,000 bbl. of finished cement per 24 hr., most of the production being low-heat cement. † About 3I30 tons of limestone, 620 tons of clay and I00 tons of gypsum are required daily for this output. Occasionally iron oxide is added to the clay to obtain the desired composition. This, together with the gypsum, is purchased from outside sources. up to the present time, the ccrporation has produced low-heat, normal, moderate-heat, moderate-sulphate-resisting, high-early-strength, oil-well, modihed-oil-well, and plastic cements. Most of the present production is for Shasta Dam, near Red- ding, Calif., the total demand being 5,800,000 bbl. of cement. Following are some of the cement require ments of the Shasta Dam specifications: Per Cent Chemical composition: Loss in ignition.......... 2.25 Insoluble residue......... 0.75 SO3.................... 2.25 MgO................... 5.&apos;&apos; Uncombined lime in clinker (CaO)......... I.25 Percentage of iron oxide to alumina ratio....... I.5 Compound composition: Tricalcium silicate (3CaO.SiO2)........... Not more than 35 Dicalcium silicate (zCaO.SiO2)........... Not less than 40 and not more than 65 Tricalcium aluminate (3CaO.Al2O3).......... Not more than 7 Tetracalcium aluminofcr- rite (4CaO.Al²O³.Fe²O³) Not more than 20 Fineness: The average specific surface in the bin sampled shall be not less than 1800 sq. cm. per gram and no individual sample less than 1600 sq. centimeters. Compressive strength: The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2.75 parts fine testing sand, by weight, shall be equal to or greater than the following:

Jan 1, 1942

By T. H. Alden

BaCKOFEN, Avery, and Turner have shown"2 that the large tensile elongation in superplastic metals is correlated with a high strain-rate sensitivity of the flow stress. At present, the reported superplastic materials are complex eutectic or eutectoid systems with a large solubility range in at least one of the terminal phases. This note describes the behavior of a solid-solution alloy (at 22°C)5,= Sn-1 wt pct Bi, which has been processed in order to produce a fine grain size.2,3,6 The chill-cast, 1/2-in.-diam ingot was homogenized for 1 week at 130°C, extruded at O°C to 0.083 in. diam, quenched within 15 sec, and stored at -196°C. Samples were warmed to room temperature 16 hr prior to mechanical testing or metallography. During tension testing at room temperature, it was found that the flow stress reached a steady-state value which depended on the imposed elongation rate and was independent of strain to an error of about ±5 pct. In Fig. 1 is plotted log a vs log e where a is the measured steady-state flow stress and i the imposed strain rate. These quantities were calculated using "instantaneous" area and length to an accuracy in the sample diameter of ±5 x 10-4 in. The log a-log 1 curve is sigmoidal. The strain-rate sensitivity, which may be given by d log old log 6,&apos; has a maximum value of about 0.48 between i = 5 x 10-4 and 5 x 10-3 per min. The value is well above frequently measured values for metals at creep temperatures (0.1 to 0.3) and comparable to the rate sensitivity for Pb-Sn solder: which has been shown to be superplastic.2,3 Note, however, that below or above the strain rate of 10-3 per min the rate sensitivity of Sn-1 pct Bi decreases and at high rates is more nearly like that of conventional metals. The grain size of this material is relatively uniform, Fig. 2, and may be specified by an average linear intercept i.&apos; Grain growth occurs at room temperature but after 16 hr, L = 5. Tensile elongation was measured on finer-grain-size specimens, which had been at room temperature 15 min prior to testing. After 15 min, the samples are fully recrystallized. Three strain rates, 5 x 10-3, 10-2, and 2.5 x 10-2 per min, were employed for which the measured elongations varied from 425 to 500 pct. These results would seem to justify the term superplastic, applied to this alloy, although the ductility is inferior to that of the Sn-Bi eutectic.3 The Sn-1 pct Bi alloy, which is a single-phase material with equiaxed, fine grains, is an excellent one on which to make an estimate of the Nabarro-Herring9 creep rate. According to the model of Avery and Backofen2 a substantial part of the deformation must be accomplished by N-H creep in the strain rate-temperature regime in which d log a/d log 1 = 0.5. The maximum N-H creep rate is given by9 L2kT where v is the atomic volume and D the self-diffusion coefficient. For this test v = 3.O x 10-23 cu cm, D = 1.4 e-23,300/RT = 2.5 x 10-l7 sq cm per sec,7 L = 5x 10+4 cm, T = 295°K, and a = 2000 lb per sq in. = 1.38 x 10&apos; dyne per sq cm. The calculated creep rate is E= 4 x 10-11 per sec which may be compared with the measured creep rate at this stress, Fig. 1, of 6.7 x 10-5 per sec. The N-H creep rate is seen to be negligible. Earlier consideration2 of this question was in error because incorrect diffusion coefficients were used. The assistance of R. R. Russell in metallography is acknowledged gratefully.

Jan 1, 1967

By W. H. Morris

I have been requested to present a paper on the slag from the basic Bessemer process, as prepared for fertilizing. Since Professor W. B. Phillips presented at the Birmingham meeting, in May, 1888, an able paper* on this subject, as it had been developed up to that time, there is little for me to add. Perhaps later practice may be best expressed by the homely proverb, " The proof of the pudding is in the eating." As the Pottstown Iron Company is the only concern manufacturing basic Bessemer slag in this country, the writer&apos;s personal experience in the use of it may be interesting. Our slag averages: P2O5, 21.37; SiO2,, 5.10; MgO, 5.90; Al2O3, 4.01; MnO, 5.56 ; FeO, 12.00; Na2O and K2O, 0.80; CaO, 45.26; total, 100.00. This gives over 76 per cent. of phosphoric acid and lime. In using this material for several years past on my lawn and garden, I have found it better than anything else I have ever tried ; and I am sure that any of you who had seen my green grass last month (January), wherever the ground was bare from snow, as bright as in early fall, would be forced to acknowledge the advantages of this soil-enricher. The grass on my private lawn, and around the company&apos;s office, is green the whole winter; and we have raised very good sod, by the use of this phosphate, where, without it, we were unable to get the grass to grow either from seed or by repeatedly sodding. The same statement applies to garden-truck; when the soil was first broken up, a good crop of vegetables was easily raised. My own gardener has had several premiums from Philadelphia seedsmen (notably, last year, the first premium for sugarcorn raised in the first part of July, being the first sample sent them). Our method of applying this material is to grind the slag very finely, so that at least 60 per cent. of it will go through a 150-mesh screen (i.e., say, 22,500 meshes to the square inch), and 90 per cent. through a 100-mesh screen (i.e., 10,000 meshes to the square inch). This fine grinding seems to be the main condition of success.

Jan 1, 1893