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By Joseph S. Malesky

The discovery and development of explosives mark one of the most important findings in the history of civilization. Without explosives our vast economic enterprise concerning the mining of coal, copper, iron, aluminum, and various other ores could not function. Explosives are used in all kinds of construction works, in the razing of old buildings, blasting of trenches, driving of tunnels, and in many other instances common to our everyday life. For these reasons explosives are rightfully referred to as the forerunner of progress. An explosive may be defined as a substance (usually a mixture) that, when flame or shock is applied, yields readily to rapid combustion or oxidation, accompanied by the formation of such relatively large quantities of gases as to produce much violence and pressure which, in turn, react against their surroundings and cause what is termed an explosion. By their very nature the action of explosives is destructive and disruptive of adjacent materials. Decomposition of explosives can occur through deflagration, which is rapid burning or combustion, as in the case of black powder, or through detonation, which is an almost instantaneous disruption, as in the case of dynamites and blasting agents. HISTORY OF BLASTING WITH EXPLOSIVES At one time workmen obtained stone blocks for building by grooving the rock with crude picks, driving wooden wedges into niches in the rock, and pouring water on the wedges; the swelling of the wood forced out the blocks. As late as the 17th century, fires were placed against the face of rock to crack it, and water was sometimes dashed on the heated rock to shatter it by sudden cooling. The progress of our country is synonymous with advancement of the improved manufacture and extended use of explosives. Coal had been

Jan 1, 1981

By D. G. Westlake, D. T. Peterson

The saturation solubility of thorium dihydride in thorium was studied by saturation of samples and subsequent analysis. The solubility increased from about 1 at. pct at 300°C to above 20 at. pct at 800 °C. Over this temperature range the log of the solubility was a linear function of the reciprocal absolute temperature for thorium of good purity. The heat of solution of thorium dihydride was found to be 7.9 kcal per atom of hydrogen in crystal bar thorium and 6.6 kcal per atom of hydrogen in Ames thorium, The important effect of hydrogen on the physical and mechanical properties of many metals is receiving increasing recognition. The basic physical and chemical data necessary to help explain the observed effects of hydrogen on the mechanical proper ties of metals are all too often not available. The solubility of hydrogen in thorium metal was determined to provide a portion of this basic data for the thorium-hydrogen system. The absorption of hydrogen by thorium metal and the formation of thorium hydrides was studied by several investigators, beginning in 1891, and their work is summarized in Gmelin's Handbuch.1 No effort was made to determine the extent of solid solubility in the metal in these early investigations and the impure metal available made interpretation of the results uncertain. Nottorf2 reported the results of a careful study of pressure-composition isotherms for the thorium-hydrogen system. The principal interest in this work was in the composition and dissociation pressures of the thorium hydrides. Mallett and campbel13 reported the pressure-composition isotherms for the thorium-hydrogen system up to the composition of thorium dihydride. The saturation solubility of thorium dihydride in thorium was reported to be 13 at. pct at 650°C and 23 at. pct at about 900° C. Mallett and Campbell used thorium metal which had been prepared by the calcium reduction of thorium tetra-fluoride or thorium oxide. The results obtained with thorium of these two types agreed within the experimental error. PROCEDURE AND MATERIALS Procedure—The method used to determine the solubility was to saturate a sample of thorium with hydrogen and analyze a portion of the saturated sample. This method was chosen rather than a determination of pressure-composition isotherms since it was much less time consuming and could be applied at temperatures at which the equilibrium hydrogen pressure was too low to measure. The

Jan 1, 1960

By Henry D. Hibbard

FoR the purpose of this paper all steels will be divided into two divisions: effervescing and non-effervescing. This classification must be borne in mind as many statements true of one class are not true of the other. Effervescing steels are those that effervesce in the molds, evolving large volumes of gases, which, in escaping, throw up a spray of molten particles of steel and give the molten metal in the mold a rapid stirring or churning motion until it freezes, or, at least, becomes pasty. This effervescing is intended and proper. The non-effervescing steels, which are more or less completely killed, should not evolve any gas in the molds. Many years ago the writer proposed to call the two classes of steels evolution and solution steels, depending on whether the gases in the molds are evolved or kept in solution, but the present designations seem to be better. In America, at least, effervescing steels are in a class by themselves and include steels made for boiler, tank, and ship plates, steel pipe, soft steel wire, wire nails, soft machincry, and structural steels. These are all low-carbon steels with less than 0.40 per cent. carbon. Low-carbon steels that do not effervesce but are killed are also made; these are put into ingots and castings but they are outside the limits of this paper. Effervescing steel is cast into square or slab molds, either top or bottom poured. Most of the effervescing steel is made in the basic open-hearth furnace, though much is made by the acid Bessemer process and a little is made in the acid open-hearth. It is not made by the crucible or electric-furnace process, in which the volume of gas required cannot be produced in the steel and evolved from it in the mold to give the effervescence desired. Any steel ingot, when teeming is finished, is of a certain size or volume. Leaving out of consideration for the moment the lessening of the over-all dimensions of the ingot through contraction due to loss of heat, the ingot may be placed in one of three classes: It may settle, losing in volume; it may stand, that is, remain constant in volume; it may rise, that is, increase in volume. Into which class an ingot will fall depends on the gases of the steel,

Jan 1, 1920

By E. J. Whittenberger, F. N. Rhines

The formation of casting porosity is viewed as a nucleation and growth process with solidification shrinkage and gas precipitation as cooperative driving forces. Experimental evidence evaluating the individual contribution of each force confirms the major premise that microporosity is nucleated by gas precipitation. Additional data disclose the effects of the identity and quantity of gas, the temperature range of freezing, and the freezing rate upon the amount and distribution of porosity in light metal castings. POROSITY, as it commonly occurs in metal castings, has been ascribed to the contraction that accompanies the freezing of the metal, to the evolution of dissolved gases from the liquid during cooling and freezing, and, most frequently, to a combination of the two.'" "Pipe" formation is universally associated with solidification shrinkage; spherical "gas holes" are understood to be retained bubbles of gas; but the origin of microporosity, which usually exhibits an irregular or scalloped outline when viewed in cross-section, remains a subject of continuing debate.", ' The present research constitutes an endeavor to show what parts are played respectively by shrinkage and gas evolution in the initiation and growth of micropores and what factors determine their number, size, shape, and distribution. A preliminary outline of the mechanism of cavity formation in castings will serve to coordinate the experimental findings that will be reported and will at the same time provide a general theory of the origin of casting porosity. Basic to the mechanism of cavity formation that will be proposed are the following established facts: 1—that liquid metals and alloys contract gradually during cooling down to the freezing range, where a relatively large contraction, known as the "solidification shrinkage," takes place (exceptions in bismuth and gallium being noted);' 2—that the capacity of liquid metals and alloys for dissolving gases diminishes with cooling until, in the freezing interval, a large decrease takes place (various exceptions being noted and excluded from present consideration) ;.: and 3—that freezing proceeds counter to the direction of heat flow, the freezing front most commonly being composed of a system of tapering dendrite stalks and side arms which are coarser the lower the freezing rate and which protrude into the liquid for a distance that is greater the longer the freezing temperature interval of the alloy and the smaller the thermal gradient.' The mechanism by which voids are generated

Jan 1, 1953

By Juan Daniel Martínez, Janaina Accordi Junkes, Dachamir Hotza, Tatiana Pineda

"The rice husk combustion in a bubbling and atmospheric fluidized bed reactor was investigated. The results showed the technical viability of producing both heat and amorphous silica from a renewable energy source. This paper presents the characterization of rice husk ash (RHA) obtained under varying fluidization velocities (0.13-0.15 m/s) and rice husk feed (4.5-7.2 kg/h). Characterization techniques include X-ray fluorescence, X-ray diffraction, particle size distribution and scanning electron microscopy. For the employed range of fluidization velocities of rice husk feed no noticeable influence on the chemical composition of produced RHA was observed. After combustion, RHA containing ~93% amorphous silica and <3% unburned char was obtained. RHA primary particles presented sizes from 90 to 100 µm and a tendency for agglomeration in aqueous media. Thus, the potential of this type of reactors with respect to speed, continuity and self-sufficiency energy of the process was shown.IntroductionDue to the increase of the agroindustrial production, the concern with processing by-products, such as rice husk (RH), is growing. For a better material and energy use, allowing a cleaner production and a more maintainable development, RH can be used as renewable fuel in the production plant, for instance, in steam generators. The adequate combustion of RH generates hot gases with low levels of pollutants, as carbon monoxide and particulate material.RH is the protecting coating formed during the growth of the rice grain, composed by four structural layers.1 The main components of the husk are cellulose and hemicelulose (50%) besides lignine (26%) and organic components (4%), as oils and proteins. The remaining amount includes inorganic materials (SiO2, Al2O3, K2O, Na2O, MgO, CaO, Fe2O3, MnO, P2O5).1The rice husk ash (RHA) is the product of the termochemical transformation of RH. The conditions of the different conversion processes (pyrolysis, gasification and/or combustion) determine the physical-chemical characteristics of the final product. RHA corresponds to 14 to 25% RH, depending on the variety of the rice, climate and soil of the producing area.2-4 The main component of RHA, which is generated at moderate combustion temperatures, is amorphous silica (SiO2) in the range from 80 to 97%.4,5"

Jan 1, 2008

By G. Sachs, L. J. Ebert, W. F. Brown

IT is a generally recognized fact that a steel quenched from the austenitic range and tempered to yield a structure composed of tempered martensite becomes increasingly more ductile with increasing tempering temperature. However, the conventional tensile test fails to yield any value that is sensitive to differences in behavior on tempering among the various low-alloy steels or among different heats of a particular steel. The notched impact bending test, on the other hand, has been recognized for a considerable length of time as capable of revealing differences in impact properties among various steels tempered to the same strength level (i.e., the same tensile strength in a conventional tensile test), However, this test is very complex and its significance has not been clarified up to the present time. Of its three characteristic features-the high speed, the notch, and the bending-the notch has been found by Davidenkov2 to be the most potent embrittling factor. Recent investigations on low-alloy steels3,4,7,8 have shown static notch-bar tensile tests to be more lucid and to evaluate the metal properties in much the same manner as impact tests, In an attempt to analyze the fundamental nature of this test,8 it was found possible to separate the effects of the two basic characteristics of the stress pattern introduced by the presence of a circumferential notch, the stress state and the high initial stress concentration at the notch bottom, The major conclusions drawn from these previous investigations were as follows: I. The magnitude of the triaxiality at fracture depends primarily on the initial notch depth. Its effect is a great reduction in the average ductility (contraction in area at fracture in the notched section) as compared with that observed in uniaxial tension, This triaxial stress state occurs at a point in the interior of the notch specimen, It determines the notch ductility if the notch is mild and/or the metal possesses a considerable ductility. On the contrary, brittle specimens probably fracture on the metal surface (at the notch bottom) at which point biaxial stress state is present, This biaxiality also considerably reduces the ductility of the metal. For small notch ductilities the notch strength and the notch ductility become very sensitive to embrittling factors, This is contrary to the behavior of the ductility values derived from a conventional tensile test, which are comparatively insensitive.

Jan 1, 1946

By J. Etcheverry, E. Seguel, R. Díaz, F. Parada, R. Parra, E. Balladares

A thermodynamic and kinetic model is proposed to explain the formation of bornite, chalcopyrite and magnetite during partial roasting of enargite-containing copper concentrates. The proposed mechanism involves solid-solid-gas and solid-gas reactions between chalcocite, pyrrhotite, gaseous sulfur and oxygen. The formation of bornite could be explained by a two-step reaction: the first one involving the formation of chalcopyrite by a reaction between Cu2S, FeS and gaseous sulfur, followed by a second step in which the newly formed chalcopyrite reacts with additional chalcocite to form bornite. Although thermodynamically the direct formation of bornite is more favorable than that of chalcopyrite, the lower diffusion kinetics of bornite formation could explain the preferential formation of chalcopyrite. If the reaction occurs with stoichiometric chalcocite and pyrrhotite in the presence of gaseous sulfur to form chalcopyrite, no bornite is formed, while for the stoichiometric reaction between chalcopyrite and chalcocite in the absence of sulfur, only bornite is formed. For the formation of magnetite and chalcopyrite the mechanism could involve the partial reaction of chalcocite and pyrrhotite in the presence of oxygen. The proposed model is thermodynamically consistent with the experimental results obtained in laboratory and pilot plant. INTRODUCTION The processing of high-arsenic copper concentrates with over 0.7 wt.-% arsenic by conventional smelting-converting normally require an additional arsenic removal step to reduce arsenic content to levels below 0.2–0.3%. One of these high-arsenic copper concentrates is the one produced by the Ministro Hales Division (DMH) of CODELCO, which has the typical chemical composition shown in Table 1. Enargite (Cu3AsS4), chalcocite (Cu2S) and pyrite (FeS2) are the main mineralogical species present in these concentrates, with over 75 wt.-%, as shown in Table 2. Partial or “neutral” roasting of these concentrates under controlled temperature and partial oxygen pressure conditions at 923–993K (650–720ºC) can remove up to 95% of the arsenic as As2S3 (As4S6), which has a high vapor pressure under these conditions, leaving a calcine with low residual arsenic. In copper concentrates, arsenic is present generally as enargite and arsenopyrite. This compounds as well as others such as pyrite and covelite, decompose readily above 770 K (500ºC), releasing, in addition to gaseous arsenic trisulfide, gaseous sulfur which by oxidizing to SO2 generates most of the heat required by the process.

Jan 1, 2019

By D. G. Macintyre

Thick westward prograding clastic wedges were deposited along the margin of ancestral North America from Mid-Proterozoic to Mid-Paleozoic time. Periodic rifting and tectonic subsidence resulted in the formation of starved sub-basins along this otherwise passive continental margin. These sub-basins host important sedimentary exhalative barite-zinc-lead-silver deposits. In northeastern British Columbia, a thick succession of Paleozoic basinal facies clastic rocks is preserved within the northwest-trending Kechika Trough. Within the trough, sedimentary exhalative barite and barite-sulfide deposits occur in starved basin sediments of Middle Ordovician, Early Silurian, and Late Devonian age. The last are the most economically sigrrificant and are hosted by carbonaceous cherty argillites and siliceous shales of the Middle to Late Devonian Gunsteel Formation of the Lower Earn Group. The largest deposit, Cirque, has reserves in excess of 35 million tonnes averaging 100J0 (Pb +Zn) and 47 g/t Ag. Other potentially significant deposits include Driftpile Creek, Bear, Mt. Alcock, Fluke, Pie and Elf. Stratiform barite deposits are also common, particularly near the basin-to-shelf transition zone. The Late Devonian barite-sulfide deposits typically are zoned: interlarninated barite-sphalerite-galena-pyrite occurring near suspected vent areas grades outward into bedded barite. Laminated beds of pyrite typically occur in hangingwall siliceous shales, particularly above the inferred vent zone. The apparent absence of epigenetic stringer sulfide zones and footwall alteration implies that the deposits were formed from ponded brines at relatively low temperature. Away from the main deposits, the favourable stratigraphic interval is marked by the presence of thin beds of nodular and laminated barite and thin laminae of pyrite. Thin tuff beds also occur locally in this stratigraphic interval and are evidence for a Late Devonian volcanic event. A paleogeographic reconstruction of the Kechika Trough in Late Devonian to Mississippian time suggests that the barite-sulfide deposits formed in third-order starved basins between uplifted, northwest-trending horst blocks that were capped by shallow-water carbonate banks. The presence of intraformational breccias suggests that fault movement accompanied barite-sulfide precipitation. This tectonic activity may have allowed the escape of heated, overpressured metalliferous brines from permeable reservoirs within the sedimentary pile. Sedimentary exhalative deposits formed where these brines were exhaled as buoyant plumes onto the seafloor, cooled, and ponded in anoxic seafloor depressions.

Jan 1, 1992

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube&apos;s and the author&apos;s observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,&apos; whose conception of the phenomenon

Jan 1, 1929

By J. H. Slater

There is nothing particularly new about the use of sinter in a blast-furnace burden. For many years flue dust has been sintered at the various blast-furnace plants to put it in a form that could be recharged to the furnace with some assurance that it would stay in the second time. This paper is not a compilation of scientific data but only an attempt to give our experience with sinter. There are some unexplained discrepancies in the tests given here, such as the flue dust produced and iron tonnages, but the results given are the results that were obtained. Sinter is not the cure-all for blast-furnace problems. A good coke is still the most important factor in good furnace operation. However, good sinter is a big help. As flue dust is produced under varying operating conditions and fluctuates greatly in carbon content, it is difficult to produce from flue dust alone a uniform sinter, which will give satisfactory blast-furnace results. Sinter made from flue dust alone will change in character with every carbon variation. Almost invariably flue dust contains carbon in excess of the amount necessary to make good sinter, and this excess must be burned out. This, of course, necessitates reduction of the speed of the sintering machine and thus a decrease in tonnage. An alternative is to dilute with a carbon-free material to use up the excess carbon. High-carbon material when sintered results in a very dense, undesirable product, since the excess heat melts the charge into a hard, nonporous mass, and tends to form refractory silicates. At the Republic Steel plant in Cleveland, there had existed since 1924 a continuous-type sintering machine having 224 sq. in. of grate-bar area, capable of producing 9 to 11 tons of sinter per hour from flue dust. Under a former management, it was the practice to sinter only the flue dust from the blast furnaces, no attempt being made to recover the gas-washer sludge. As the dust was limited, the plant operated only part time. In other words, there was a sintering plant representing considerable investment, with good facilities for screening and preparation of raw materials, and flue dust available for only part-time operation. The sinter produced was costly and not a very desirable product. The first step was to install equipment for the recovery of the gas-washer sludge. This was done in the form of two large thickeners and a filter, which have proved very satisfactory. It was then decided to screen out the minus 3/8-in. fines from the Mesabi ores, mix them with flue dust and coke breeze when necessary, and operate the plant at full capacity. The tonnage increased to 18 tons per hour and the product was much improved. Sintering costs fell and the product was a preferred blast-furnace material, which on an iron unit cost compared very favorably with good Mesabi ores. On the average, 40 per cent flue dust and 60 per cent fine ore was being used. The oversize from the ore screening also became a preferred product for the

Jan 1, 1941

Time as a Factor in the Making and Treating of Steel. By John Johnston. (Howe Lecture) (T.P. 1478) Influence of Chromium and Molybdenum on Structure, Hardness and Decarburization of 0.35 Per Cent Carbon Steel. By R. F. Miller and R. F. Campbell. (T.P. 1345) Mechanical Properties of Iron-manganese Alloys. By F, M. Walters, Jr., I. R. Kramer and B. M. Loring. (T.P. 1369) The Instability of Low-expansion Iron-nickel-cobalt Alloys. By I. R. Kramer and F. M. Walters, Jr. (T.P. 1370) The S-curve of a Chromium-nickel Steel. By B. M. Loring. (T.P. 1383) A Magnetic Determination of the A3 Transformation Point in Iron. By B. A. Rogers and K. 0. Stamm. (T.P. 1388) Rapid Tension Tests Using Two-load Method. By A. V. de Forest, C. W. MacGregor and A. R. Anderson. (T.P. 1393) Effects of Scrap in the Blast-furnace Burden. By C. L. T. Edwards. (T.P. 1270) Temperature Gradients through Composite Carbon Columns and their Application to Blastfurnace Linings. By F. J. Vosburgh and M. R. HatFIeld. (T.P. 1363) Correlations of Some Coke Properties with Blast-furnace Operation. By H. W. Johnson. (T.P. 1402) The Technical Cohesive Strength and Yield Strength of Metals. By D. J. McAdam, Jr. (T.P. 1414) Effects of Eight Complex Deoxidizers on Some 0.40 Per Cent Carbon Forging Steels. By George F. Comstock. (T.P. 1417) Significance of the Bessemer End Point. By H. T. Bowman. (T.P. 1428) Structural Diagrams of Nickel Irons and Steels. By J. T. EasE and N. B. Pilling. (T.P. 1432) Carbides in Low-chromium Steel. By Walter Crafts and C. M. OFFenhauer. (T.P. 1436) Hardenability Calculated from Chemical Composition. By M. A. Grossmann. (T.P. 1437) Recrystallization of Silicon Ferrite in Terms of Rate of Nucleation and Rate of Growth. By J. K. Stanley and R. F. Mehl. (T.P. 1438) The Solubility of Carbon as Graphite in Gamma Iron. By R. W. Gurry. (T.P. 1440) An Evaluation of the Factors Affecting Iron Oxide in the Open-hearth Bath. By J. E. Gould and H. J. Hand. (T.P. 1442) Precision in Creep Testing. By J. A. Fellows, Earnshaw Cook and Howard S. Avery. (T.P. 1443) Lattice Relationships in the Decomposition of Austenite to Pearlite, Bainite and Martensite. By G. V. Smith and R. F. Mehl. (T.P. 1459) Rate of Nucleation and Rate of Growth of Pearlite. By F. C. Hull, R. A. Colton and R. F. Mehl. (T.P. 1460) Weight Change as a Criterion of Extent of Decarburization or Carburization. By R. W. Gurry. (T.P. 1470) Observations in the Making and Use of Sulphite-treated Steels. By E. L, Ramsey and L. G. Graper. (T.P. 1476) Diffusion in Metal Accompanied by Phase Change. By L. S. Darken. (T.P. 1479) Engineering Properties of Heat-resistant Alloys. By Howard S. Avery, Earnshaw Cook and J. A. Fellows. (T.P. 1480) Distribution of Manganese and of Sulphur between Slag and Metal in the Open-hearth Furnace. By L. S. Darken and B. M. Larsen. (T.P. 1481)

Jan 1, 1942

By E. Rudy, St. Windisch

The only complete phase diagram investigation of the Ti-W system is by Maykuth and coworkers,&apos; Fig. 1. Although previous work by Gonser2 indicated complete miscibility, later investigations3°5 essentially confirmed the diagram depicted in Fig. 1. The present study was undertaken because preliminary results on metal-rich ternary Ti-W-C alloys indicated complete solid solubility between 0 titanium and tungsten at temperatures above 1300°C—in contradiction to the presently accepted diagram. The powdered elements, as well as crystal bar titanium and tungsten sheet, were used in the preparation of the experimental alloys. The iodide titanium, obtained from Foote Mineral Co., Exton, Pa., had a total impurity content of less than 410 ppm, of which 150 ppm were interstitials (H, O, N, C). The overall purity of the titanium powder (Var-Lac-Oid Chemical Co., New York) was better than 99.7 pct. Major contaminants, in ppm, included: 0, 800; N, 10; H, 1500; Fe + Co + Ni + Cu + Zn, 50; C1, 200. The measured lattice parameters of the titanium were a = 2.94A and c = 4.68,A. The tungsten sheet and the tungsten powder (Wah Chang Corp., Albany, Ore.) contained the following impurities (in ppm, values in parentheses refer to the sheet tungsten): Mo, 50 (70); 0, 140 (110); Fe, 20 (60); Ni, 20 (not determined); N, 110 (not determined); sum of other impurities, <60 (<100). Samples from the iodide titanium bar stock and from tungsten sheet were prepared by repeated melting of the chipped materials in a nonconsumable electrode arc furnace under high-purity helium. The melted alloys were heavily cored, and homogeneity of the alloys could only be achieved after prolonged heat treatments at subsolidus temperatures. The majority of the alloys were therefore prepared by cold compacting the well-mixed powders in steel dies and pre-homogenizing the compacts for 6 hr at 1300°C in a tungsten-element furnace. The vacuum was better than 10"6 Torr, but for additional protection the sample container was wrapped in zirconium foil. Both preparation methods led to identical results. The measurements of the solidus temperatures were carried oat in the Pirani-type furnace described in a previous paper.6 Incipient melting in alloys containing between 20 and 90 at. pct W was rather difficult to detect visually, and therefore a photoelectric transducer system7 was employed to indicate the phase change. For the investigation of the solid-state equilibria, the specimens were first homogenized for 2 hr at slightly subsolidus temperatures in the Pirani fur- nace and then reequilibrated at, and rapidly cooled (-100°C per sec) from, the selected equilibrium temperatures. After the runs, the alloys were analyzed microscopically and by X-ray diffraction. With the exception of spot checks for oxygen and nitrogen in processed alloys, no other chemical analyses were performed. However, as the weight changes of the alloys during processing were within 0.05 pct and the lattice parameters of indeqendently prepared alloy series agreed within 0.0015A, it is reasonable to assume that no significant concentration shifts with respect to the nominal compositions had occurred. The measured solidus temperatures, shown together with literature data in Fig. 2, ascend smoothly from

Jan 1, 1969

By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.&apos; However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By C. S. Smith, K. K. Ikeuye

In an earlier paper1 one of the authors called attention to the significance of the relative free energies of grain boundaries and interphase boundaries in alloys in determining the shape and distribution of micro-constituents. The ratio of the interphase and inter-crystalline boundary energies (that is, —?12, where ?12 is the energy of the interface between a crystal of phase 1 and a crystal of phase 2, and ?11 is the energy of the boundary between two crystals of phase 1) will be denoted by F. It is this ratio that determines, by the simple triangle of forces relation, the dihedral angle, ?, of phase 2 where it adjoins a boundary between two grains of phase 1. On a metallographic sample various angles are actually obtained because of the random orientation of the plane of observation, but the statistically most frequent angle is the true one. These basic principles were discussed in detail in the earlier paper. The experiments described below show the effect of both composition and temperature on ? and T for some alloys containing a liquid phase, and provide data on the rate of approach to the equilibrium angles in both solid and liquid phases. All the alloys were melted in a graphite crucible and cast into ingots 3/4 by 11/8 in. cross-section. Some of the aluminum alloys consisted of two immiscible liquids from which uniform castings could not be obtained. The amount of liquid phase varied locally to a considerable extent and the analyses were meaningless. Nevertheless, the composition of the liquid would not differ from that in an alloy of the intended gross composition, and the synthetic composition of the alloys was therefore used in considering the surface energy results. The ingots were given initial deformation by cold-rolling to 50 pct reduction, annealed, and given a second 50 pct reduction prior to cutting into small samples for heat treatment at the times and temperatures subsequently reported. The resulting micro-samples were carefully prepared metallographically and examined at magnifications of 650, 1280, or 2500. The objectives used were 21X, 0.40 NA (dry); 41X, 0.65 NA (dry); and 80X, 1.40 NA (oil emulsion). The appropriate angles were measured by rotation of the stage of a Bausch and Lomb metallograph to align the appropriate boundaries successively with a cross-hair in a micrometer eyepiece. About 250 angles were measured on each phase. Though the angles were read to 1°, the accuracy is probably not above 3°, because of uncertainty in setting the cross-hair tangent to the sometimes curved boundary. The corners of very small particles, particularly in early stages of adjustment after cold-rolling, were difficult to measure and the results were slightly dependent on the magnification used (compare Fig 1-C and 1-D). With particles of larger size and more nearly equilibrium shape, magnification made no difference (vide Fig 1-F and 1-G). The measured angles were grouped in 10° intervals (5° if ? was less than 20°) and plotted in bar

Jan 1, 1950

By J. C. Uy, A. A. Burr

IN the primary solid solutions of zirconium-base alloys, there is a striking regularity of the effect of solute valence on the stabilization of the allotropic phases.1 The valences derived by pauling2 are for elements as they are bonded in the solid metallic state. Effects of variations in isotopes, alloying elements, and allotropes on their valences are difficult to determine and such data are presently unavailable. Pauling&apos;s values are somewhat empirical and approximate, but if some definite correlations can be found between those values and experimental observations, this will lend support to the tacit assumption that the possible variations in valence mentioned above are small. Pauling has amassed a large amount of evidence of such correlations. It is the purpose of this technical note to show another application of the Pauling valences and to offer a possible explanation for this observation. The relationship between the Pauling metallic valence of the solute and the stabilization of allotropic phases in zirconium is shown in Table I, which has been compiled from available data in the literature3 plus the results of work done at Rens-selaer Polvtechnic Institute.&apos; The chemical valences are included for comparison. It can be seen that a solute whose metallic valence is lower than that of the solvent tends to stabilize the a phase while one whose metallic valence is higher than that of the solvent tends to stabilize the 0 phase. It should be noted that, inasmuch as the Pauling valences are periodic with atomic number, this is tantamount to saying that the elements in groups I-A, 11-A, III-A, III-B, IV-B, V-B, and VI-B are a stabilizers while those in groups IV-A, V-A, VI-A, VII-A, VIII-A, I-B, and 11-B are ß stabilizers. The chemical valences do not show such consistency. Although the zirconium-rich end of the Zr-Au diagram is not available, it call be expected that gold, having a metallic valence of 5.56, would stabilize the ß phase. At absolute zero, the Fermi energy level is the criterion of equilibrium, i.e., the structure having the lower Fermi level will be more stable. Conse- quently, allotropic transformation occurs in a metal when thermal excitation raises the Fermi level to a point at which the atoms can be better accomodated by a different structure which yields a lower Fermi level.4-6 Thus in allotropic transformation, a change in structure occurs as a result of the change in the energies of the bonding electrons. Since the Pauling valence is the number of bonding electrons per atom, and these are the only electrons whose energies are affected by thermal excitation,* it can be inferred that the introduction of a solute which has a higher Pauling valence than that of the solvent raises the initial Fermi level; consequently, the transformation temperature is lowered. The converse is also true. The fact that at the transformation temperatures this statement is still fairly valid implies that the contribution due to the difference in specific heat terms of the two allotropes is comparatively small.

Jan 1, 1962

By P. Niessen, S. J. Bercovici

RECENTLY Aust et al.&apos; proposed a model of non-equilibrium grain boundary segregation based on a vacancy gradient induced uphill diffusion process of solute to grain boundaries. According to their proposal, solute atoms which are attracted to vacancies would, during the cooling of a sample, migrate with vacancies toward grain boundaries (vacancy sinks) and thereby enhance the solute concentration in boundary regions. For solute atoms which are not attracted to vacancies no such boundary solute enrichment would be expected. These concepts were given experimental support by boundary and bulk mi-crohardness measurements of various thermally treated dilute zinc and lead alloys and also doped aluminum oxide. The underlying assumption in their work was that solute enrichment in boundary regions is indicated by higher microhardness values. From thermodynamic considerations1&apos;2 it appears that the solid-liquid solute distribution coefficient (K), defined as the concentration of solute in the solid to the concentration of solute in the liquid at equilibrium, indicates whether attractive or repulsive forces exist between vacancies and solute atoms. K < 1 indicates a solute-vacancy attractions, K > 1 indicates no, or a repulsive, vacancy-solute interaction. This note is to report on observations of different grain boundary etching phenomena in high purity zinc alloys. These phenomena appear to depend on whether a K < 1 or K > 1 solute is present. In experiments designed to measure directly the solute enrichment in grain boundary regions, samples of zone refined zinc with 0.1 at. pct solute additions were cooled from 380°C at a rate of 3°C per min. A surface layer of approximately 50 was then removed from the samples by chemical polishing. The samples&apos; surfaces were then protected by a chromating treatment such that in a subsequent etch only grain boundary regions were dissolved. The dissolved regions were approximately semicircular troughs, 10 µ in width. The grain boundaries were usually in the middle, i.e., at the bottom, of this trough. For zinc containing the K < 1 solutes cadmium and aluminum, the grain boundary was always indicated by a ridge as shown in Fig. 1. For pure zinc, and zinc containing the K > 1 solutes copper and gold, a groove at the bottom of the trough indicated the boundary position, Fig. 2., To test if these different grain boundary etching behaviors were possibly connected with the segregation process discussed above, the Zn-Cd alloy was again heated to 380°C and quenched into brine. After surface protection and etching it was found that this specimen no longer exhibited the grain boundary ridges but rather grain boundary grooves as shown in Fig. 2. It would appear, therefore, that the boundary ridge is a consequence of a process occurring during the slow cooling of the samples. From absorption spectrophotometric analysis it was found that for slowly cooled samples containing K < 1 solutes, the solute/zinc ratios of the material from the boundary trough were consistently considerably higher than the solute/zinc ratios of the bulk alloys. This boundary region solute enrichment was not observed in quenched samples. It is concluded therefore, that the boundary ridge shown in Fig. 1 is directly or indirectly connected with nonequilibrium solute segregation.

Jan 1, 1970

By Walter Bonsack

THE CHAIRMAN.-This is the third and last session of the Institute of Metals Division&apos;s Symposium on Secondary Metals, and certainly the best of those that I have attended in the last few years. I would say that the increase in interest in secondary metals is quite noticeable by the steadily increasing attendance at these meetings. We have heard about the necessity of utilizing salvaged materials, but we still speak about them as low-grade, or down-graded materials. We still have the wrong perspective. We must willingly admit that these materials are valuable; we cannot go on using the choicest primary metals as morsels for our economic diet in a war of such unbelievable dimensions. This brings up the question-why are we so selective. The answer certainly is not that we know nothing else will do, but rather that we do not know what else will do. To be honest, we should admit our lack of knowledge concerning our complex alloys. Compared to the organic chemists, we metallurgists are very conservative, and the sooner we realize this and start to overcome it the better, because if we do not eliminate this difference, many customers of the metals business will go over to the plastics. If we take for example the development of aluminum alloys, you will see what I mean. From the binary aluminum alloys of 1920, we have progressed to ternary and quarternary alloys in the 1930&apos;s. We are only now beginning to use more complex alloys as we are forced to learn more about the effect of various elements on existing alloys. The effects of these elements should be studied now. They can be studied by two methods of approach. The usual method is to start from the base alloy and add various elements one by one in increasing amounts and study the resultant changes in properties. This is a tedious, long way. The other method which the smelters frequently use is to take the off-grade heats and study their characteristics. While the producer of primary alloys often has difficulties in alloying certain elements with the alloy under investigation, the smelter often finds them well alloyed in his raw materials and has no difficulties at all. Elements such as lead are difficult to alloy with aluminum and they tend to segregate severely. However, the amount which will remain alloyed in the metal is usually found in some "secondary" aluminum alloys. If one considers such concentration as the saturation, then by dilution with the same type of alloy, but free of such element, one can produce numerous intermediary alloys for investigation. In this fashion one is fairly certain to get uniformly spaced concentrations of the element under investigation. Similar cases probably exist with other metals. Nevertheless, the amount of work necessary to study all possible combinations is still tremendous. Necessity forces us now to utilize alloys which contain more elements than we are accustomed to. It is, therefore, necessary to study carefully the more complicated alloys. In secondary aluminum we are working and using the alloys which contain as many as 6 to 10 elements and we have learned over a period of several decades to balance

Jan 1, 1943

By R. A. Swalin, B. W. Roberts

ONSIDERABLE controversy has centered about the existence of an order-disorder transformation in alloys in the composition vicinity of 75 atomic pct Ni and 25 atomic pct Cr. All the evidence to date for such a transformation is of a rather indirect nature, since direct X-ray confirmation is difficult to obtain as a result of the small difference in X-ray scattering factors between nickel and chromium. As a result, superlattice lines would be very faint if present. Several investigators1-5 have observed anomalies in the electrical resistivity vs temperature curves of alloys in the vicinity of 25 atomic pct Cr. The observed change is characterized by a rather broad resistivity peak at about 540°C. A discontinuous drop in resistivity is normally associated with ordering. However, Taylor and Hin-ton4 have rationalized that the discrepancy could conceivably be caused by changes in the Brillouin zones upon ordering. The same investigators measured the specific heat as a function of temperature and have also observed anomalies in the vicinity of 540°C. Nordheim and Grant5 have proposed, because of the absence of superlattice lines and the absence of a discontinuity in the resistivity vs temperature curve, that long-range order is improbable and that the results could be better explained by short-range ordering. To date, however, the question has not been resolved satisfactorily. Neutron diffraction techniques provide a method for partially resolving the question since nickel and chromium have considerably different atomic scattering factors in the case of neutrons and, therefore, superlattice peaks, if ordering occurs, should be readily discernable. The results of a neutron diffraction investigation* coupled with a dilatometric in- vestigation are reported here. An alloy containing 28.0 atomic pct Cr was prepared from carbonyl nickel and electrolytic chromium in the form of a 1-in. diam x 10-in. ingot. Melting was done in an alumina crucible and casting in a graphite mold. The ingot was homogenized at 1250°C for seven days, after which a 5-in. long piece was cut into shavings in order to obtain a suitable neutron diffraction sample. Hardness samples and samples suitable for dilatometric analysis (% in. diam x 2 in.) were prepared from the remainlng piece. The neutron diffraction sample, along with a hardness sample, was annealed at 501°C for seven days, at which time the temperature was lowered to 479°C and held at this temperature for twenty-four more days. The hardness was observed to increase from 133 to 147 Vhn during the course of the annealing treatment, in qualitative agreement with Nordheim and Grant." Neutron diffraction traces taken at room temperature and at 42 °K are shown in Fig. 1. The insert shows the trace taken at room temperature with short counting times and thus only fair statistical accuracy. No evidence for superstructure reflections of Cu3Au-type ordering is observed. The statistical accuracy of the 4.2°K trace was improved by using longer counting periods. Several weak intensities are observed at small angles, including an aluminum reflection from the cryostat assembly and a very

Jan 1, 1958

By Anand Kumar, Pradeep kumar Jha, Suman Kant, Pradeep Kumar

"It has been a major challenge to reduce the intermixed grade formation during ladle change-over operation in continuous casting process of tundish steelmaking. The F-curve generated by step input of the tracer (new grade steel) tells about the intermixed grade amount for different grade specifications. Use of flow modifiers is beneficial in reducing the intermixed grade because of the change in slope (in different time zones) and position of the F-curve due to their placement at tundish bottom. Present study aims at investigating the role of dam placed before the outlet in a multi-strand tundish with reference to the slope behavior of F-curve in different time zones during the teeming operation plays an important role in determining the intermixed amount.Introduction In Continuous casting process, the old grade steel remaining in the tundish (reservoir between ladle and mould) from the old ladle gets mixed with new grade steel from new ladle and leads to intermixed grade which is considered to be of inferior quality. Although formation of intermixed grade is inevitable with the sequential method of casting, its amount can be controlled by changing the flow behavior of steel inside the steel. Intermixing in a slab caster tundish was simulated using 3-D numerical model based on k-å turbulence equation and compared their result with that of water model experiment Yeh and Hwang [1]. Huang and Thomas [2] reported that quantity of residual fluid in tundish affects the composition distribution in the transitional slab and thus the intermixed length. Huang and Thomas [3] developed three sub models to predict mixing in tundish, liquid core of strand and solidification. Thomas [4] developed a one dimensional model to simulate the final composition distributions in slab caster of continuous casting and investigated the effect of process variables on the intermixing. Alizadeh mehdi et al., [5] simulated of the intermixing phenomenon for slab casting for three different sub models. Goldschmidt et al. [6] developed a numerical model that predicted the location of the intermixed steel in a four line round caster. Lan and Khodadadi [7] studied for the transient fluid flow of liquid steel, heat transfer and solidification during the flying tundish change process. Cho and Kim [8] developed a mixing model to predict the outlet concentration of the tundish during grade transition. Most of the work reported in the literature has dealt with intermixing in slab caster tundish. Billet caster units are more often being used by steel industries due to growing demand of billets. The multiple outlets lead to varying degree of intermixing with time owing to their different distance (location) from the inlet. Use of flow modifier to minimize the intermixed amount, however has also not been discussed in detail so far. Further no work has been reported regarding effect of slope of F-curves obtained through different outlets on intermixing. Hence keeping these objectives in mind attempt has been made by authors to analyze the slope of Fcurves after dividing them into three different time zones and the effect of these time zones on intermixing."

Jan 1, 2012

By Carl H. Eckert, James P. Berson

INTRODUCTION The demand for specialty metals in industrial applications is in it&apos;s healthiest state since the late 1970&apos;8, and several specific markets are recording record sales. Such metals as gold, silver, zirconim., titanium, beryllium, gallium, germanium, the platinum group, and the lanthanides accounted for sales in excess of $2 billion in 1985 among the end uses covered in this report. Although specialty metals as a group have suffered the effects of recessionary pressures in the past, these metals have proved more resiliant than such large volume metals as copper and nickel. This is due to the unique physical properties they possess which makes the threat of substitution or replacement through technological development uneconomic. The outlook for these specialty metals is optimistic in electronics, catalysts, ceramics, and alloys, and their specialty status results .in a combined average annual growth in demand of 7% through 1990. WHAT MAKES THESE METALS SPECIAL? Such characteristics as electrical conductivity, corrosion resistance, catalytic activity, thermal stability, and optical properties allow the term specialty to be applied to these metals. More importantly, all of these metals possess more than one of these qualities, as shown in Table 1. [ ] These five major functions are important in the end uses for these metals, although the specific applications vary somewhat. Conductivity in term of low or high electrical resistance is of obvious importance to electronics manufacturers. Producers of circuit boards or semiconductors require such metals as gold, palladium, platinum, and gallium due to their low electrical resistivity. However, these producers also require such metals as beryllium in the oxide form for insulation components because of the compound&apos;s low electrical conductivity. Although the lanthanides&apos; conductive characteristics are not particularly attractive in electronics, they are of great importance to alloy manufacturers producing permanent magnets for automotive and computer applications. Corrosion and wear resistant properties are extremely attractive to a number of end-use industries, particularly in view of the estimate by the United States Bureau of Mines that $10 to $50 billion in losses are experienced by U.S. industry due to equipment corrosion and $100 billion due to equipment wear. The strength of high purity titanium and zirconium make these metals the obvious choice for corrosion and wear resistance particularly in the chemical processing industry, where the ability to maintain integrity in corrosive environments is a must. Heat exchangers, nuclear control rods, and a number of parts in jet engines have benefited greatly from the use of these metals. However, such other specialty metals as beryllium, and the lanthanides also improve the wear or corrosion resistance in various products. For example, a beryllium-copper alloy contact maintains it&apos;s spring like character, and does not loose this character after repeated use, which could result in the loss of an electrical contact. Lanthanide, in the form of cerium oxide, is commonly employed in alloys used to produce catalytic converter casings for the purpose of reducing damage by corrosive road salt. In some instances, the catalytic activity of several of the specialty metals assists in the economic production of other materials. However, the importance of specialty metals in catalysts is most apparent in catalytic converters for emission control. Platinum, palladium, and rhodium are

Jan 1, 1986