Search Documents

By J. M. GLEDHILL

IT would doubtless have been felt by many but a few years back that there was little left to be said on the subject of crucible tool-steel, and that something akin to finality had been arrived at in its manufacture and general treatment. Probably such feeling was justifiable when it is remembered that the making of steel in crucibles is by far the oldest method known, dating back from time immemorial, it being indeed impossible to accurately trace its origin and earliest development; but it seems certain that carbon-steel was made and used thousands of years ago for cutting-tools. Proof of this may be seen by the marvelous carvings and workings on the intensely hard stone-work of the ancients, for it would be difficult to conceive by what means, other than with steel tools, such work could have been executed; and it is wonderful to contemplate that steel cutting-tools should have been used so long ago, whilst the principle of manufacturing them-that is, by fusion of iron and charcoal in crucibles-was then in a measure on the sane lines as we work on at the present day. Archaeologists have discovered that the Chinese made steel in crucibles long before the Christian era. " Wootz " steel fabricated in India centuries ago was crucible steel, as was also the celebrated Damascus steel, produced at the forges of Toledo, and, curiously, this latter steel furnishes' yet another proof that "There is nothing new under the Sun," for it is recorded that Damascus steel contained certain percentages of tungsten, nickel, manganese, etc., some of the very elements, in fact, contained in the present modern high-speed steel, so that a latent high-speed steel may be said to have existed

Mar 1, 1905

By Eric R. Jette, Earl S. Greiner

The constitution of the iron-rich iron-nickel-silicon alloys at 600ºC. has been determined by X-ray crystal structure methods. If the results are represented isothermally by a conventional equilateral triangular plot, the single-phase solid solution (body-centered cubic structure) of the iron-rich alloys at 600°C. is bounded by four two-phase areas. Three three-phase areas separate the respective two-phase areas. Three of the phases in the polyphase areas have the same structures as the corresponding phases in the binary iron-nickel or iron-silicon alloys. There are two phases, however, that have not been reported previously and whose structures have been tentatively identified in the present investigation. The solid solubility limit of the iron-rich solid solution at 600°C. was determined by comparing the lattice constants of this body-centered cubic phase in the single and polyphase areas. It has been shown that the lattice constants of ternary alloys may be represented by surfaces whose distances above the ternary plot (representing atomic composition) are proportional to the lattice constants of the respective alloys. Then the intersections of the surface for the single-phase alloys with those for the corresponding phase in the polyphase alloys, at the respective temperatures, are the solid solubility limits of the single-phase alloys at these temperatures. The data of the present investigation were evaluated by this method, although by a system of orthographic projection it was possible to represent the three-dimensional model in two-dimensional diagrams. This investigation has shown that the solid solubility of nickel in the body-centered cubic phase of the iron-rich iron-nickel-silicon alloys at 600°C. changes from 3.7 weight per cent (Owen and Sulley) in the binary iron-nickel alloys to 5.0 per cent in the ternary alloys containing 4.8 per cent silicon. Further additions of silicon increase the solid solubility limit of nickel to 16.0 per cent at 12.6 per cent silicon. From this point the limit decreases to 9.5 per cent nickel at 15.5 per cent silicon and is, of course, zero at 15.3 per cent silicon in the binary iron-silicon alloys.

Jan 1, 1943

By Earl S. Greiner, Eric R. Jette

The constitution of the iron-rich iron-nickel-silicon alloys at 600ºC. has been determined by X-ray crystal structure methods. If the results are represented isothermally by a conventional equilateral triangular plot, the single-phase solid solution (body-centered cubic structure) of the iron-rich alloys at 600°C. is bounded by four two-phase areas. Three three-phase areas separate the respective two-phase areas. Three of the phases in the polyphase areas have the same structures as the corresponding phases in the binary iron-nickel or iron-silicon alloys. There are two phases, however, that have not been reported previously and whose structures have been tentatively identified in the present investigation. The solid solubility limit of the iron-rich solid solution at 600°C. was determined by comparing the lattice constants of this body-centered cubic phase in the single and polyphase areas. It has been shown that the lattice constants of ternary alloys may be represented by surfaces whose distances above the ternary plot (representing atomic composition) are proportional to the lattice constants of the respective alloys. Then the intersections of the surface for the single-phase alloys with those for the corresponding phase in the polyphase alloys, at the respective temperatures, are the solid solubility limits of the single-phase alloys at these temperatures. The data of the present investigation were evaluated by this method, although by a system of orthographic projection it was possible to represent the three-dimensional model in two-dimensional diagrams. This investigation has shown that the solid solubility of nickel in the body-centered cubic phase of the iron-rich iron-nickel-silicon alloys at 600°C. changes from 3.7 weight per cent (Owen and Sulley) in the binary iron-nickel alloys to 5.0 per cent in the ternary alloys containing 4.8 per cent silicon. Further additions of silicon increase the solid solubility limit of nickel to 16.0 per cent at 12.6 per cent silicon. From this point the limit decreases to 9.5 per cent nickel at 15.5 per cent silicon and is, of course, zero at 15.3 per cent silicon in the binary iron-silicon alloys.

Jan 1, 1943

Discussion of the paper of S. E. Bretherton, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 1481 to 1487. S. E., BRETHERTON, San Francisco, Cal.:-Since preparing my paper, our chemist, F. L. Wilson, has been experimenting with Leadville, Colo., oxidized zinc ore and Leadville zinc sulphides containing lead, operating upon 40-1b. lots at a time. His results on Leadville sulphides are as follows: The raw ore contained a trace of gold, 5.04 oz. of silver, 19.1 per cent of zinc, and 7.24 per cent of lead. After roasting the ore contained a trace of gold, 5.72 oz. of silver, 0.75 per cent of copper, 21.7 per cent of zinc, and 8.29 per cent of lead. The loss in weight by leaching was 38.8 per cent. The extraction was 42.8 per cent of the copper, 80.6 per cent of the zinc, 7.1 per cent of the lead, 0.64 per cent of the silver, and no gold. The little .silver that is extracted would be thrown down with the copper when precipitating it from the zinc and both thrown hack into the residue to be smelted. There would be no trouble in smelting the residue with nearly all the sulphur eliminated and containing less than 7 per cent. of zinc. On zinc carbonates containing silicates the results are not satisfactory. H. O. HOFMAN, Boston, Mass. (communication to the Secretary*) :¬The paper by Mr. Bretherton upon the application of ammonia and carbonic acid to the recovery of zinc as oxide from roasted sulphide ore is of interest to me, as the first installation of the Schnabel process for the extraction of zinc from a mixture of zinc oxide, lead oxide (with some cupric oxide), and pellets of enriched lead, produced in steaming liquated zinc-silver-lead crust of the Parkes process, was made at Lautenthal, Harz mountains, where I was chemist. In that capacity I carried out numerous experiments on the Schnabel process, was active in the erecting of the plant, and later had charge of it. After the Lautenthal plant had been in operation for some time a similar one was built at Hoboken-les-Anvers, but both have been abandoned, as the wet process could not compete with the distillation of the liquated zinc-silver-lead crust, now used universally in the Parkes process.

Jan 11, 1913

By Walter Crafts, C. M. Offenhauer

IN a previous study' of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is a more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about r1to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, 1 per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to 1-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudomartensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously' that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By B. C. Allen

The solubility of chromium in liquid silver and that of molybdenum and tungsten in liquid tin have been determined by equilibrating Ike Liquid in a crucible of the solule metal. Generally the weight of solute in solulion was delermined both chemically and from crucible weight losses. The resulting weight percent solubilily of chromium in silver as a function of absolule temperature T is given by log w = -6660/T + 4.02 in the range 960° to 1445°C, and that of molybdenlttrl in tin by log w = —5050/T + 1. 79 in the range 1200° to 2200°C. The values appear unaffected by minor changes in solute composition. Calculations aye made of the parlial molar heal and excess entropy of mixing. The estimated solubility of tungsten in tin is 0.001 pct at 2000°C. Evidence is presented that molybdenwm dissolves in tin without compound for mation and that tungsten and tin form W10Sn. RECENT developments in coatings, heat transfer, and brazing require a knowledge of equilibrium solubilities in a variety of systems at elevated temperatures. Of particular interest are solid-liquid interactions in metal systems involving dilute solutions. This investigation was undertaken since little is known about the phase relations or solubility of chromium in liquid silver or of molybdenum and tungsten in liquid tin.1,2 EXPERIMENTAL WORK As indicated in Table I, high-purity metals or those of known impurity levels were used. Crucibles were machined from chromium, molybdenum, and tungsten bar stock 1.3 cm diam and 2.2 cm long. Chromium rod was prepared by arc melting and extruding iodide process crystals.3 The five chromium impurity alloys were in the form of 0.6-cm-diam swaged rod. A Cr-0.06N* alloy was prepared by exposure to NH3 at 1150°C in a closed quartz capsule for 24 hr. Because significant nitrogen was lost during annealing in argon at 1600°C,4 the estimated level was 0.01 pct N. Chromium and Mo,W crucibles were outgassed at 1200" and 1600°C, respectively, at 3 X 10-5 mm. The solvent was placed In crucibles of the solute metal- 6 g Ag in chromium, 0.4 g Ag in the five chromium impurity alloys, and 4 g Sn in Mo,W crucibles. The silver and tin series were outgassed at 900" and 110O°C, respectively, and held at the desired solution temperature in a tantalum resistance furnace under 1.05 atm 99.995 pct Ar. An equilibration time of 0.5 to 1 hr was chosen since 0.3-, I-, and 4-hr anneals at 1235°C for Cr-Ag yielded similar results. Temperatures were measured optically to +10°C under essentially black body conditions which were checked against the melting point of silver. The Cr-Ag and Mo-Sn,W-Sn series were respectively equilibrated at 990° to 1400°C and 1200" to 2000°C. Vaporization losses were generally held to <1 pct by the argon. In the 1800" and 2000°C anneals for 0.5 hr, the crucibles were placed in tightly sealed tantalum cans which kept tin losses to <5 pct. After the anneals, the specimens were furnace-cooled. One anneal was made on small Mo-0.02 C, Mo-0.5Ti-0.lZr, and tungsten crucibles containing tin at 2200°C. The metals were sealed in an electron-beam-welded tantalum can of minimum volume. After the anneal, tin was still present in each crucible, none of which was severely attacked. After equilibration, the saturated solvent metal was selectively removed from the crucible by acid leaching. Weight losses sustained by the crucibles were determined from the initial weight minus the final blank-corrected weight after acid leaching. Chemical analyses were performed on some of the samples. Hot 1:l HNO3-H2O removed silver from chromium with the blank running <0.1 mg or <0.002 pct on measured solubility. Tin was removed from molybdenum and tungsten by hot concentrated HC1 with the respective blanks amounting to -0.004 and -0.0004 pct in the presence of tin. The insoluble residues were weighed and checked for composition. The leaching solutions contained traces of the solute metals which were analyzed by colorimetric methods, Diphenyl Carbazide for chromium, Thiocyanate for molybdenum, and Dithiol for tungsten. The total of the two percentages found from the residue and leaching solution minus the blank gave the desired solubility values. On the basis of annealing empty molybdenum and tungsten crucibles, weight losses due to MoO3 or WO3 volatilization were found to be generally 10.4 mg and affect measured solubilities by <0.01pct. RESULTS AND DISCUSSION Chromium-Silver . Since no intermediate compounds are reported to form in the Cr-An system,&apos; crucible weight losses and chemical analysis of the entire melt should provide reliable measures of the chromium in solution. Values obtained by the two methods are in agreement as shown by the results for unalloyed chromium in Table II and plotted in Fig. 1. Furthermore, the results are consistent with those previously determined by melting equilibrated silver out of the crucible and analyzing calorimetrically for chromium.&apos; On the basis of limited thermal analysis data, the solubility of chromium in silver has been quoted as 8 pct at the monotectic temperature of -1445°C.1 This investigation indicates an extrapolated solubility of 1.38 pct which is believed to be more reliable. At the eu-

Jan 1, 1968

By Rich Akerman

as 1866, I wish to assure both these gentlemen that I had not seen the section when I designed mine, :md even if I had, I should not have then dared to put it forth as a standard for English rail makers; tind the soundness of my opinion has a simple but conclusive proof in the statement made concerning the extra price which was at that time required for their production. I need not say that I highly approve of the original Welch section, for it is in principle similar to the design which I made ufteen yeam subsequently; and from a professional point of view I would fully concecle to Mr. Welch the credit of first designing the modern steel-rail section. From com- mercial, matter of tict, and practical point of view, he was, however, before his time by many years; or to put it in another way, rail making was ten years behind its time when the new metal steel was first introduced for rails. If his design has been incorrectly identified with my name (as the sections are similar in principle, though they differ in thickness of flange and web), I beg to say (1st) that I much regret the misun- Understanding which has arisen through no fault of niine, aud (2d) that no confusion has been intentionally created by me. It is a pity that the section designed so long ago has not been made public at an earlier date, as it would make a really goal stand- and pattern, anil even now be quite equal to present requirements. In conclusion, I wish to say that I have never desired to claim any invention or novelty by the publication of my sections; they Were put forth as being such as English railmakers could and would produce at the ordinary market. price, and as being the best and most suitable to be so obtained. Had Mr. Welch or Mr. Holley put forward theirs ten or fifteen years ago, I should have been the first to recommend theru. In fact I should have been glad to see their narnes associated with rail patterns in their own country, in the same way as mine has been. PROFESSOR RICH. AKERMAN, STOCKHOLM, SWEDEN: i AGREE with your (Mr. Sandberg&apos;s) views that it is too early yet to stipulate only one definite chemical composition in the rails. Such a stipulation, I think, might he justified, if it were not for the manganese; but this metal changes the properties of the iron aud steel in tho same direc- tion ae carbon, silicon. and phosphorus, by increasing its tensile strength, stiffness, hardness, and brittleaess. If the iron and steel does not only contain carbon and manganese but also phosphorus,

Jan 1, 1881

By S. Wiederhorn

The energy and force of interaction between a crack and a slip band have been calculated. When the distance between the crack and the slip band is greater than the dislocation spacing of- the slip band, the force on the cgrack is perpendicular to the slip band. The energy needed to propagate a crack against this force can be lawe enough to pevmit crack propagation parallel to noncleavage planes. SEVERAL recent experiments have demonstrated the occurrence of crack-slip band interaction in ionic crystals having a NaC1-type structure. Stokes, Johnston, and Lil have studied the nucleation and growth of cracks in MgO. From their observations, they conclude that slip bands have the ability to halt and stabilize cleavage crack nuclei. Gilman2 has shown that a crack, propagating along a (100) cleavage plane in a previously deformed LiF crystal, tends, at certain points within the crystal, to switch to (110) planes. He reasons that plastic deformation reduces the cohesive energy of the (110) planes below that of the (1130) planes, making possible (110) crack propagation. Keh3 has demonstrated that when indentations are made in MgO, crkcks form along (110) planes at the indentations. Gilman2 attributes the formation of these cracks to plastic cieformation. There is some doubt as to the formation of cracks on (110) planes. Kuznetsov4 in his discussion of crack propagation in rock salt, shows that splitting along (110) planes requires 1.76 times as much energy as splitting along a stepped (100) surface. Therefore, the observed (110) cracking in LiF and

Jan 1, 1962

R. L. Fleischer (Department of Metallurgy, Massachusetts Institute of Technology)— The authors have presented valuable observations of oehavior of aluminum at intermediate and high temperatures. I should like to consider their interpretation of the appearance of cross slip plane traces in sample B-3 as partly due to "bending of the crystal due to grip constraint." Because bending moments might be set

Jan 1, 1960

By Charles P. Williams

The successful production of zinc white or oxide on a commercial scale in this country dates from the issue of the patent of Samuel Wetherill, for the preparation of the material (November, 1855), and

By Francis H. Crockard

DURING the past five years we have probably witnessed greater technological advances than in any similar period. Industry and science have steadily marched ahead. The makers of iron and steel products have watched with great interest the development of stream-lined trains, faster and safer airplanes, the entirely new science of air-conditioning and the widespread use of stainless steels. Since 1930, we have witnessed the erection of the world&apos;s largest suspension bridge, the largest and fastest ocean liner and the spectacular Boulder Dam, while even greater things are planned in these particular fields. Other industries, too, have been moving ahead rapidly. This advance in a few years has been caused primarily by the fierce competition of the depression. Now, more than ever, is the emphasis placed upon quality and service. Makers of southern merchant pig iron have been no exception and have been confronted with increasingly strict chemical specifications and with much greater stress on physical characteristics than ever before. For example, sulfur in the iron must be held very low, competition demanding that it be in the 0.020&apos;s and low 0.030&apos;s; silicon content must be held within a very narrow range, and definite requirements of phosphorus and manganese are an essential part of the specifications. Physical characteristics are becoming of increasingly greater importance. The introduction of triple-skimmed, slow-cooled iron several years ago was the first step in this direction. Now there are a few customers who buy iron by chemical analysis and physical appearance, having found that the analysis alone is an insufficient guide to their requirements.

Jan 1, 1935

By R. Taggart, D. H. Polonis, J. C. McMillan

Thin foil electron microscopy techniques have been used to study the micros tructure of a Ti- 7.5 wt pct vanadium alloy in the quenched and aged cond_itions. Selected area diffraction has identified a (1011) twinning mode accompanying the martens ite t9.an.sfo?rn~ation. Precipitation of the 0 phase during the aging of quenched alloys has been obsevced to occuv in the form of plates and needles with preferential growth along the (1120) direction in the a&apos; matrix. In the present work, the micro structures of quenched and aged alloys of the 0 isomorphous Ti-V system have been investigated by means of thin-foil electron-microscopy techniques. Most of the previous studies of martensitic phases in titanium-base alloys have utilized optical microscopy and X-ray diffraction techniques. The application of transmission electron microscopy is more recent, and only a few such studies have been reported.1-5 This paper is concerned particularly with the crystallographic nature of substructures formed in the martensitic a&apos; plates. The early stages of aging or tempering have also been examined to determine the modes of precipitation from the martensitic solid solutions. Such information is essential in studying strengthening mechanisms and in determining the feasibility of high-strength rnartensitic alloys based on titanium. Liu and Margolin6 reported several types of substructures within the martensitic plates of quenched Ti-Mn alloys. It was later suggested by Liu7 that the structure of martensitic plates might be very complex and not single crystals as normally assumed. The sub-markings could not be identified with the two possible habit-plane orientations {334}ß and {344}ß, and it was not positively determined whether they are associated with mechanical twinning. The recent studies by Armitage5 on titanium martensites in a variety of commercial alloys have indicated that twinning does not generally accompany the transformation. This observation is in accordance with the Mackenzie and Bowles model for the transformation in pure titanium8 which suggests that twinning is not to be expected. However, a number of other recent investigators have reported twinlike substructures in the martensitic plates of several titanium systems including commercia1 titanium,2,3 Ti-Cu,5,9 Ti-Ta,1 and the commercial alloy Ti-8A1-1Mo-1V. Blackburn* has reported that the structure of quenched Ti-8A1-1Mo-1V depends on the prior solution temperature. He identified two types of martensitic structures, one of which is described as a heavily faulted hcp or twinned fcc structure and the other an hcp structure with a high internal dislocation density. The latter type exhibited some twinning with a (1011) twin plane. EXPERIMENTAL PROCEDURES AND RESULTS The alloy used in the present work was a 7.5 wt pct V alloy that was prepared by conventional arc-melting techniques. This alloy composition was selected

Jan 1, 1968

By Richard Birk

Rf sputtered quartz has been successfully used in multilayer interconnects for MOS devices. The target potential was 2000 v peak to peak with a frequency of 13.56 Mc per sec. The sputtering rate was approximately 60A per min with an operating pressure of argon gas at 10 to 15 p. The dielectric strength is 8.0 x 10&apos; v per cm and the pinhole density is less than 2 x 10-2 per sq mm. Infrared absorption peaks for the Si-O vibrational bands we at 9.4, 12.4, and at 22.5 p. The etch rate of the sputtered SiO2 is 1200A per min. MOS devices have been fabricated using multilayer interconnects with no degradation of electrical characteristics. MULTILAYER interconnects require an insdating film between the metal layers which can be deposited below any potential eutectic temperature. Sputtered Si4, which can be deposited with substrate temperatures below 200°C, satisfactorily meets the multilayer insulation requirements and has been used to prepare MOS circuits with multilayer interconnects. The physical and electrical properties of rf sput-

Jan 1, 1969

By Francis Crockard

DURING the past five years we have probably witnessed greater technological advances than in any similar period. Industry and science have steadily marched ahead. The makers of iron and steel products have watched with great interest the development of stream-lined trains, faster and safer airplanes, the entirely new science of air-conditioning and the widespread use of stainless steels. Since 1930, we have witnessed the erection of the world&apos;s largest suspension bridge, the largest and fastest ocean liner and the spectacular Boulder Dam, while even greater things are planned in these particular fields. Other indus-tries, too, have been moving ahead rapidly. This advance in a few years has been caused primarily by the fierce competition of the depression. Now, more than ever, is the emphasis placed upon quality and service. Makers of southern merchant pig iron have been no exception and have been confronted with increasingly strict chemical specifications and with much greater stress on physical characteristics than ever before. For example, sulfur in the iron must be held very low, competition demanding that it be in the 0.020&apos;s and low 0.030&apos;s; silicon content must be held within a very narrow range, and definite requirements of phos-phorus and manganese are an essential part of the specifications. Physical characteristics are becoming of increasingly greater impor-tance. The introduction of triple-skimmed, slow-cooled iron several years ago was the first step in this direction. Now there are a few customers who buy iron by chemical analysis and physical appear-ance, having found that the analysis alone is an insufficient guide to their requirements.

Jan 1, 1936

By Anal J. Mehta, Theodore D. Tiemann

Growing demand for steel and increasing dependence upon foreign ore makes the need for developing the technology for treatment of low-grade iron ores greater than ever before• Representative of these added interests were the studies carried on at the University of Wisconsin• These studies included among others: anionic and cationic flotation, magnetic separation, roasting followed by magnetic separation, electrostatic separation, a hydrogen reduction process,6,7 and caustic digestion• The idea of removing silica by caustic extraction is not new•-1; The principle of concentrating siliceous iron ores by this method is based on the fact that silica is soluble in sodium hydroxide solution while iron oxides are essentially insoluble• For this process to be economically feasible, it is believed that some method of recovering silica from solution as a marketable by-product, with recycling of spent liquor is necessary. Precipitation of silica with carbon dioxide will allow subsequent causticizing of the spent liquor with lime• Caustic thus produced can be recycled for digestion• A flowsheet of the envisioned process is given in [Fig• 1] The purpose of this paper is to describe results obtained from the investigation of carbon dioxide precipitation of silica from sodium silicate solutions, which could be later applied to the caustic extraction process to treat low grade siliceous iron ores, particularly taconites.15 Theoretical Considerations The soluble silicates of sodium include sodium orthosilicate (2Na2O•SiO2), sodium metasilicate (Na20•SiO2), sodium disilicate (Na1O•2SiO2), and more highly siliceous products approaching Na2O•4SiO2• These materials have been described in detail by Vail•16 Stones has reported that the extraction of silica is not significantly affected by the amount of silica in solution until the Si02/Na20 ratio exceeds that of orthosilicate (Ratio = 1/2)• However, as the Si02/Na2O ratio exceeds that of metasilicate (Ratio = 1), silica extraction is significantly impaired• The present experimental work was confined to orthosilicate and metasilicate solutions, as to be successful the envisioned commercial process for the extraction of silica from siliceous iron ores would operate in this region. The mechanism of extraction of silica from aqueous sodium silicate solutions is complex in nature. For the carbon dioxide process-18 of core and mold making in which silica is also precipitated from sodium silicate solutions by gassing with carbon dioxide, the reaction of aqueous silicates with gaseous carbon dioxide has been represented by the equations: [ ] However, these equations are very much oversimplified• It has been shown that the reaction between aqueous sodium silicates and carbon dioxide gas is ionic in nature 18 Considering this fact and the mechanism for digestion of silica in aqueous sodium hydroxide, the overall conversion of aqueous sodium silicates to solid silica may be represented in ionic form by the following equations: [ ] Silicon in the silicate ion is shown here with a coordination number of 6• This may be in doubt, but it is known that ion (SiF°)-2 exists; it seems logical that the Si (OH) e 2 ion should be equally capable of existence•

Jan 1, 1977

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the &apos;a; and &apos;c,,&apos; edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.&apos; LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By B. Hyatt, E. Klokholm

The reesistivity of Cu-Pd alloys of 9.6 to 29 pct Pd alloys was measured after plastic deformzation in tension. For all compositions a continzting decrease in resistivity with increasing plastic strain was observed. By comparison with the results of Damask on a brass ad Cu3Au, it was deduced that these anonzalous decreases in resistivity are due to the decrease in short-vunge order caused by cold work. An anomalous decrease in the resistivity of cold-worked CU-Pd alloys was first reported by Jaumot and Sawatzky.&apos; They observed decreases in the electrical resistivity when disordered Cu-Pd alloys drawing at room temperature. Recently, a similar anomaly was reported by Aarts and Houston-Mac-Mi1lan2 in Ag-Pd alloys containing 10 to 45 pct Pd. The plastic deformation in this case was produced by tensile strain at liquid-nitrogen temperatures. For AE-Pd alloys the relative resistivity change becomes positive for tensile strains of about 20 pct.

Jan 1, 1960

By H. Hooykaas

A few years ago Marsal published a method of predicting oil recovery as a function of time for an edge-water-drive reservoir with several rows of wells.&apos; The method is based solely on oil- and water-production data obtained during a short period for the first row of wells and the gross productions (past and future) of all wells. This paper presents a streamlined version of the original publication and experimental evidence showing the reliability of this version. For this purpose scaled experirnents were performed in a large model (750 X 500 X 23 cm, 24.4 ft X 16.2 ft X 8.9 in.) in which edge-water-drive reservoirs with three rows of production wells were simulated. From the results of the experiments it is concluded that the method gives a fairly accurate prediction of the future production behavior of the reservoir and enables us to select the most profitable production plan. Results obtained with the method were always slightly conservative. INTRODUCTION The calculation method developed by Marsal aims at forecasting future reservoir behavior.&apos; It can be applied to floods in which a number of down-dip wells are rapidly going to water. Essentially it is a method for predicting the future behavior of the up-structure wells on the basis of the observed behavior of the down-structure wells. As such, the method is especially useful for predicting behavior of edge-water drives toward several rows of wells. The requirement to be met for justifying the approach is identity of production mechanism in all regions of the reservoir. The attraction of the method then lies in the fact that it applies even when we have no complete description of the prevailing production mechanism. The original publication was in the German language and for this reason, perhaps, did not attract widespread attention. In our opinion it deserves to do so because it does offer in a simple way results which are in fair agreement with observed data. The aim of the present paper is to bring the method to the attention of a wider audience. The method in its most simplified form is reviewed and experimental data in support of it are presented. PRINCIPLES To show Marsal&apos;s principle. we will first write the continuity equation for very simple conditions, linear flow (in the positive x-direction) in an incompressible porous body [cross-section A(x), porosity +(x)], saturated with incompressible fluids (oil saturation S). When the oil in this formation is displaced by water, injected at x = 0 (inlet face), we get where q(t) is the total gross displacement rate and f the fractional oil flow. The equation can be solved if we make the assumptions: (1 ) that the fractional oil flow (f) is a univalent function of saturation (S); and (2) that the function is the same throughout the porous medium. Then: f = f(S) Solving this equation with the method of characteristics, we obtain

Jan 1, 1966

By S. F. Shaw

The Sierra Mojada mining district is situated in western Coahuila, about 8 km. east of the Chihuahua state line, and about one-half way from the northern to the southern extremity of the state. It is at the terminus of the Mexican Northern R. R., 125 km. northeast of Escal6n, Chihuahua; also about, 240 km. due west of Monclova, Coahuila. The altitude is approximately 1500 m. above sea level. The Sierra Mojada valley is about 10 km. long, from east to west, with a width of 1 to 2 km. It is approached from the east through the Puerto del Oro, where the Mexican Northern R. R. enters the valley; the slope from west to east is gentle. The Sierra Mojada, of which about 300 m. is an almost vertical wall, bounds the valley on the south side; on the north side, the slope to the crest of Sierra Planchada is more gradual, rising only 200 or 300 m. above the valley. Water is relatively scarce in the district, and there are no running streams. The rainy season, usually beginning at the middle of June, lasts through July, and occasionally into August or September. In some years the rains fail entirely. The slope of the ground is such that nearly all the water immediately runs off. The arroyos along the flanks of the mountains are not very deep, but in heavy rains, sometimes approaching cloudbursts, a tremendous volume of water rushes down them, carrying large boulders. A certain amount of seepage collects in the agglomerate, lying below the conglomerate, and is retained in the local fractures. Some shallow wells have been sunk in this agglomerate, and one well over 150 m. deep was sunk on the Volcan ranch, supplying about 76 1. (20 gal.) per min. A considerable supply of water is collected in large earth reservoirs in and below the town of Esmeralda. In ordinary years this supply will last until January or February, after which the Volcan well has to be depended on until the next rainy season. Vegetation is scarce, aside from scanty scrub oak and other brush in the mountains, and a few mezquite, locust, pepper, and cottonwood trees

Jan 1, 1923

By S. F. Shaw

The Sierra Mojada mining district is situated in western Coahuila, about 8 km. east of the Chihuahua state line, and about one-half way from the northern to the southern extremity of the state. It is at the terminus of the Mexican Northern R. R., 125 km. northeast of Escal6n, Chihuahua; also about, 240 km. due west of Monclova, Coahuila. The altitude is approximately 1500 m. above sea level. The Sierra Mojada valley is about 10 km. long, from east to west, with a width of 1 to 2 km. It is approached from the east through the Puerto del Oro, where the Mexican Northern R. R. enters the valley; the slope from west to east is gentle. The Sierra Mojada, of which about 300 m. is an almost vertical wall, bounds the valley on the south side; on the north side, the slope to the crest of Sierra Planchada is more gradual, rising only 200 or 300 m. above the valley. Water is relatively scarce in the district, and there are no running streams. The rainy season, usually beginning at the middle of June, lasts through July, and occasionally into August or September. In some years the rains fail entirely. The slope of the ground is such that nearly all the water immediately runs off. The arroyos along the flanks of the mountains are not very deep, but in heavy rains, sometimes approaching cloudbursts, a tremendous volume of water rushes down them, carrying large boulders. A certain amount of seepage collects in the agglomerate, lying below the conglomerate, and is retained in the local fractures. Some shallow wells have been sunk in this agglomerate, and one well over 150 m. deep was sunk on the Volcan ranch, supplying about 76 1. (20 gal.) per min. A considerable supply of water is collected in large earth reservoirs in and below the town of Esmeralda. In ordinary years this supply will last until January or February, after which the Volcan well has to be depended on until the next rainy season. Vegetation is scarce, aside from scanty scrub oak and other brush in the mountains, and a few mezquite, locust, pepper, and cottonwood trees

Jan 1, 1923