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By P. H. Brace, N. A. Ziegler

THE study of the relations between gases and metals is one of perennial interest to all who are connected with the production of high-grade metallurgical products. The data reported here are the outcome of work of which the object is to determine the effects of dissolved gases upon the properties of metals and to gain a more detailed knowledge of the reactions between gases and molten metals, particularly iron, under definitely controlled conditions. We have attempted to reduce our margin of error by dealing with relatively large quantities of metal, from 4 to 13 lb. (2 to 6 kg.), and keeping the ratio of refractories to metal as small as practicable. The ingots produced are large enough to provide adequate material for making determinations of magnetic and other physical properties. In choosing the bell-jar type of furnace we were influenced by the results of considerable experimentation along the same general line which indicated that, for the scale on which we were to work, it was important to have the furnace structure independent of the vacuum enclosure. The use of a bell-jar surrounding the entire furnace accomplishes this and also gives great freedom of observation during operation and ready accessibility for the replacements which are necessary after each run. Our choice of analytical method was made in the light of the results secured by H. M. Ryder, who used a method similar in principle for the analysis of very small quantities of gas extracted from strips of metal heated electrically in high vacuum. We have presented some selected preliminary experimental data as being illustrative of the quantity and nature of the gases which occur in iron of different origins, but do not urge any hypothesis at this time. THE FURNACE Our furnace may be described as "a high-frequency induction furnace of the bell-jar type." It is similar in a general way to that described by Cain and Peterson' though we have introduced certain refinements of

Jan 1, 1928

By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.' Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.' For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By H. M. Faust

THERE are a number of different types of power plants. Some use coal to generate steam, others use oil or gas either in the form of steam or internal combustion equipment, while still others avail themselves of water power as a source of energy. A general comparison of the relative power production with different sources of energy in the United States, for several different years is set up in Table 1. This table shows that coal was used to generate 85.6 per cent of the total heat power requirements of 1909, and only 59.2 per cent of the 1930 requirements. The increasing proportion of modern heat energy generated by the use of fuel other than coal is apparent. If coal is to maintain its importance as a source of heat energy, the necessity for its improved perform-ance, in which preparation plays an -important part, cannot be stressed too strongly.

Jan 1, 1933

By H. LeChatelier, B. Bogitch

Page Introduction........................... 134 Methods of Investigation....................... 135 The Tridymite Network...................... 137 Independent Variables....................... 146 Manufacturing Operations..................... 153 Introduction Silica brick are indispensable in the manufacture of steel because they alone are able to withstand the high temperature of regenerative furnaces. All attempts to replace silica brick by other refractory materials for this purpose have failed, but the reason for this failure has remained obscure; we shall give an explanation later in this paper. Before the war, silica brick employed in France came principally from abroad, for which reason, since the beginning of hostilities, certain French steel works have been seriously handicapped. Our attention was first directed to the question by M. Bied, Engineer of the Teil Works. With him, we began certain investigations, at first using our laboratory and the furnaces of neighboring steel works. The larger part of our experiments, however, have been made in the laboratory of the Faculty of Sciences at the Sorbonne. For the heating of our samples, we are deeply obliged to MM. Charpy, Yeatmann and Guerineau. In undertaking these studies, our first aim has been to render assistance to French industry, by indicating, as precisely as possible, the necessary conditions for the manufacture of high-grade brick; but at the same time me have

Jan 1, 1919

By E. R. Parker, D. L. Martin

In a previous paper one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a. strengthening, so that a longer life at a given stress and .temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver.2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. Experimental Procedure Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1944

By D. L. Martin, E. R. Parker

In a previous paper one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a. strengthening, so that a longer life at a given stress and .temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver.2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. Experimental Procedure Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1944

By R. H. B. Jones

This paper reviews pertinent geology of the Biwabik iron formation, Mesabi Range, Minnesota. This iron formation is divisible into four members. Each member is distinctive and contains marker horizons, which are recog nizable throughout all phases of alteration from lean, fresh rock to high-grade iron ore. Some beds have a larger magnetite content than others. During the process of ore genesis, which is essentially an oxidation process, the magnetite content is lowered. Alteration from iron formation to ore includes both oxidation of iron minerals and silica removal by leaching and these distinct processes progress at variable rates for different locations and structures. Magnetic intensities, of each horizon of the iron formation are dependent chiefly upon its preoxidation magnetite content, upon the subsequent degree of oxidation, upon the character of the enclosing rocks, and on the extent of fracturing, folding, or faulting. The results of a number of magnetic surveys are described and are correlated with results of drill-hole and mine exploration and developmerit. The magnetic anomalies obtained are discussed in relation to phases of formation of ore within the iron formation. General Information One hundred years ago a party of surveyors, applying the principles of geophysical prospecting, discovered iron ore in the state of Michigan in the Lake Superior district. This event was officially reported as follows:' On Sept. 19 (1844) while running the east line of Town 47 North, Range 27 West, they observed by means of the solar compass remarkable variations in the direction of the needle, amounting to 87" from the normal. Ascribing this phenomenon to iron ore, they sought and found it in ledges or outcrops at several points. The solar compass referred to was invented by William A. Burt, deputy surveyor in charge of this party.2 It is used for determining the true meridian by an observation on the sun. Eight years later, on July 7, 1852, the first iron 're, consisting of 6 bbl. of Ore, was shipped from Marquette, Michigan. It was another 40 years before the first or> shipment left the Mesabi Range in Minnesota, in October 1892. It totaled 4245 tons. Fifty years later, 90 years after the original shipment, during 1942 the Lake Superior district shipped 93,495,392 gross tons of iron ore. Production came from Minnesota, Michigan, Wisconsin, and Ontario, Canada. Throughout the 90-Year period it was known that magnetic properties of most of the ore bodies, and of the iron formations in which they occur, affected the compass. This phenomenon, later to be made use of to outline areas of ground favorable for exploration, was at first a

Jan 1, 1949

By R. H. B. Jones

This paper reviews pertinent geology of the Biwabik iron formation, Mesabi Range, Minnesota. This iron formation is divisible into four members. Each member is distinctive and contains marker horizons, which are recog nizable throughout all phases of alteration from lean, fresh rock to high-grade iron ore. Some beds have a larger magnetite content than others. During the process of ore genesis, which is essentially an oxidation process, the magnetite content is lowered. Alteration from iron formation to ore includes both oxidation of iron minerals and silica removal by leaching and these distinct processes progress at variable rates for different locations and structures. Magnetic intensities, of each horizon of the iron formation are dependent chiefly upon its preoxidation magnetite content, upon the subsequent degree of oxidation, upon the character of the enclosing rocks, and on the extent of fracturing, folding, or faulting. The results of a number of magnetic surveys are described and are correlated with results of drill-hole and mine exploration and developmerit. The magnetic anomalies obtained are discussed in relation to phases of formation of ore within the iron formation. General Information One hundred years ago a party of surveyors, applying the principles of geophysical prospecting, discovered iron ore in the state of Michigan in the Lake Superior district. This event was officially reported as follows:' On Sept. 19 (1844) while running the east line of Town 47 North, Range 27 West, they observed by means of the solar compass remarkable variations in the direction of the needle, amounting to 87" from the normal. Ascribing this phenomenon to iron ore, they sought and found it in ledges or outcrops at several points. The solar compass referred to was invented by William A. Burt, deputy surveyor in charge of this party.2 It is used for determining the true meridian by an observation on the sun. Eight years later, on July 7, 1852, the first iron 're, consisting of 6 bbl. of Ore, was shipped from Marquette, Michigan. It was another 40 years before the first or> shipment left the Mesabi Range in Minnesota, in October 1892. It totaled 4245 tons. Fifty years later, 90 years after the original shipment, during 1942 the Lake Superior district shipped 93,495,392 gross tons of iron ore. Production came from Minnesota, Michigan, Wisconsin, and Ontario, Canada. Throughout the 90-Year period it was known that magnetic properties of most of the ore bodies, and of the iron formations in which they occur, affected the compass. This phenomenon, later to be made use of to outline areas of ground favorable for exploration, was at first a

Jan 1, 1949

By Harmel A. Dawson, Robert A. Wilson

First the basic steps to determine the values present and the minerals involved which are the basis for the metallurgical testing are presented in this paper. Next, choosing the process or processes indicated for treating an ore are discussed. This is followed by the test procedures used, the results of which will indicate amenability to treatment. These test procedures have been developed, used and proven effective in laboratory evaluations relative to plant processing. Special, uncommon processing is beyond the scope of the paper. Evalutation of test results and incorporation into the preliminary and final flow sheet for plant design are discussed. The value of a flow sheet, with material and water balances, to plant design is shown.

Jan 1, 1978

By C. M. Wayman, J. F. Breedis

The crystallography of the martensitic transformation in the Fe-30 Ni alloy was reinvestigated. The scatter in the habit Plane as determined from measurements on the mid-rib plane was smaller than reported previously, and the orientation relationship was determined from a martensite plate having known direction cosines. From agreement with crystallographic theory and from observations of the morphnlogy of the martensite plates, it is suggested that the mid-rib plane represents the starting region of the transformation. THE crystallography of the martensitic transformation in the iron-nickel system has been the subject of many investigations.&apos;-7 However, for iron alloys containing approximately 30 wt pct Ni, a wide scatter in the reported habit planes exists. In only one instance has a Laue determination of the orientation relationship been made, but the habit plane of the martensite plate studied was not determined experimentally. Because the most successful thermodynamic and kinetic analyses8 of the martensite transformation have been based on Fe-30 Ni alloys, it was considered desirable to reinvestigate the crystallographic features of the transformation in this alloy. Lieberman9 suggested that the most significant information for use in a theoretical treatment involves the determination of all the crystallographic observables from a single plate of the product phase. This was first done in essence by Greninger and Troiano10 for Fe-22 wt pct Ni-0.8 wt pct C, and is the method followed in this investigation. Some theoretical approaches11-13 in describing the martensitic transformation consider the overall transformation distortion to be comprised of a Bain distortion, or lattice deformation (PI, which produces the structure change, and a lattice invariant deformation (G), such as twinning, which together leave the interface or habit plane un-distorted. The incorporation of a rigid body rotation (R) results in a transformation distortion (E) such that the interface plane is left both undistorted and unrotated. In matrix notation, E = RPG where the lattice invariant deformation has "taken place" in the austenite. Bowles and Mackenzie14-16 in formulating a theoretical approach proposed an adjustable scaler quantity, denoted as 6, which represents a uniform dilation in the interface plane. This dilation acts to adjust the lattice spacings of the parent and product structures at the plane of contact. Using the dilation parameter as a variable, these authors were able to account for a continuous variation of habit planes in steels along a curve in the stereogram between {225}A and {259}A. she invariant line strain14 of the transformation is 6 RP, and the corresponding transformation distortion is E/6.) With the dilation parameter known, the invariant line is computed as the triple coincidence of the habit plane, the shear plane of the lattice invariant deformation, and the initial Bain cone.14 The contraction axis for the Bain distortion can be taken9&apos;17 as [010]A, and the correct permutation of the habit plane indices used. Kelly and Nutting 18 have established the shear plane (of twinning) in the tetragonal martensite of Fe-22 Ni-0.8C to be {112)M by means of transmission electron microscopy. The reasonable shear system is then {112}M which is equivalent to {011}A <01l>A. The as-

Jan 1, 1962

By David J. Mack, Dennis R. O’Boyle

The mechanical properties of three polycrystalline intermediale Phases that have the y bvass structure were measured in compression between 400° and 900°K. At the lower testing temperatures— termed Region I— no plaslic deformalion occurred prior to brittle fracture. A1 higher temperatuves— lermed Region III—the three phases deformted plaslically for all strain rules from 1.5 to 36.0 x 10-4 sec-1. The homologous temperature for the inilialion of plaslic flow increased in the same order as tile atomic size difference between atoms in each plmse (0.50Tmp for y AgZn, 0.62Tmp for y CuZn, and 0.76 Tmp for y CuCd). The increased flow resistance oj. y CuCd above 0.50Tmp is explaitzed in terms of the more random arrangement of copper and cadmiwn atoms on the laltice sites of&apos; the y bvass slrilctlire. Plaslic deformation of the three intevmiediate phases in the smooth plaslic flow region appears to be controlled by oacancy-induced dislocation climb. RESULTS are reported in this paper on the mechanical properties of three binary intermediate phases having the complex cubic y brass structure (D82, 143m) containing fifty-two atoms in the unit cell. The structure of the prototype y brass phase, y CuZn, was first analyzed by Bradley and Thewlis&apos; based on the X-ray work of Westgren and Phragmen.2 The y brass structure can be visualized as an arrangement of twenty-seven body centered cubes (3 by 3 by 3) into a unit cell containing fifty-four atoms. From this cell the center atom and the four corner atoms are removed and the remaining fifty-two atoms are slightly displaced, resulting in the y brass structure. Approximately thirty-five binary intermediate phases that have an electron to atom ratio of 21:13 have been reported to form the y brass structure. The three y brass intermediate phases selected for this study are formed from elements in groups IB and IIB of the first and second long period. Each compound exists over a composition range that includes the stoi-chiometric composition A5BB (Cu5Zn8, Ag5Zn8, Cu5Cd8). y CuZn (a0 = 9.944A) has solubility limits extending from 57 to 67 at. pct Zn at 500°C apd melts peritecti-cally at 834°C; y AgZn (a0 = 9.326A) has a solubility range from 58 to 63 at. pct Za and melts peritectically at 661°C. y CuCd (a, = 9.596A) melts congruently at 563°C and has a maximum range of solubility extending from 58 to 64 at. pct Cd. In order to minimize coring and microporosity during solidification, the composi- tion of the compounds that form peritectically (y CuZn and y AgZn) was chosen so that the temperature difference between the liquidus and the solidus is only a few degrees centigrade. In selecting y brass compounds for this study, phases were avoided that contained a transition element or that had an electron to atom ratio greater than 1.70. Hume-Rothery et a1.3 has observed that, when the electron to atom ratio of y brass intermediate phases exceeds 1.70, atoms begin to drop out of the unit cell to maintain a constant electron to unit cell ratio. EXPERIMENTAL PROCEDURE Each of the three intermediate phases was prepared from elements having a purity >99.999 pct. Only trace quantities of impurities (<0.0001 pct) were detected by spectrographic analysis of the four elements. A master alloy of each compound weighing approximately 130 g was prepared by melting the elements in evacuated sealed quartz tubes heated in an electric furnace. Specimens having the desired diameter for the mechanical property measurements were obtained by remelting the master alloy in a Vycor tube under argon and drawing specimens from the melt into 4-mm-diam quartz tubes. To obtain a smooth surface on specimens drawn from the melt, the inside of the quartz tube was coated with a thin layer of graphite formed by thermally decompositing acetone. All specimens were imbedded in sealing wax and cut to the proper length with a diamond-impregnated cut-off wheel. The individual specimens (4 mm diam by 8 mm long) were then sealed in evacuated Pyrex tubes and homogenized at 500°C for 72 hr. Chemical composition, variations over the length of the rod (10 cm long) were generally less than 0.2 pct and the analyzed composition differed from the desired composition by less than 0.5 pct.4 Metallographic evaluation of the specimens after homogenization showed no evidence of a second phase in any of the compounds. The average grain size of the specimens after homogenization was 1 to 2 mm. All mechanical property measurements were carried out in an argon atmosphere using a compression apparatus described previously.5 Prior to applying the load to the specimen, the test apparatus was evacuated, back-filled with argon, and heated to the test temperature for 20 min to establish thermal equilibrium. EXPERIMENTAL RESULTS Mechanical properties measured as a function of temperature and strain rate for each of the three y brass phases were similar. From room temperature to the ductile-to-brittle transition temperature, only elastic deformation was observed prior to fracture.

Jan 1, 1968

By J. L. Wyatt

The electrical resistance of titanium as a function of purity and temperature was measured from —325" to 2800°F. Two points of inflection in the data plots were found, and an increase in resistance with increase in temperature above the transformation was observed. IN 1948 Greiner and Ellis&apos; reported on the thermal and electrical properties of titanium, including a study of the effect of temperature on the electrical resistance. The materials used in the research were obtained from the United States Bureau of Mines, where powder metallurgy techniques were being employed for consolidation purposes. These authors found a decreasing resistance with increasing temperature above 1625°F, and concluded that the latter temperature represented the point of transformation from hexagonal close-packed to body-centered cubic structure on heating. They reported a specific resistivity value of 55x10-6 ohm-cm, and showed that dp/dt was positive, decreasing with increasing temperature above ambient. In one of his early texts Hume-Rothery2 mentioned that certain metals, including titanium, exhibited minima in plots of resistance vs temperature. He indicated that this occurred at 212°F. Reporting many years ago on the effect of temperature on the electrical resistance of zirconium, de Boer and Fast³ showed that phase transformation in this sister metal occurred over a range of temperatures, the extent varying with its purity. Graphs of resistance vs temperature, showing transformation effects over a range of several hundred degrees, were presented for relatively impure metal. In the latter case the resistance decreased with increasing temperature throughout the region of partial phase transformation, thereafter increasing as predicted for normal metals by modern theories of the solid state. Since the quality of metal used in previous studies was substandard compared with iodide-type titanium, and in view of the fact that there seemed to be some rather unusual observations in the reported literature, it was decided to undertake a more extensive study of the thermal effects using high purity titanium, and to include temperature ranges beyond those which had been studied in order to ascertain whether or not the characteristics of zirconium would be duplicated. Experimental Materials Materials used in this investigation included commercial quality titanium (Ti-75A produced by the Titanium Metals Corp. of America) in the form of ¼ in. diam rods, and high purity iodide titanium (produced by the Foote Mineral Co.) in the form of crystal bar of irregular size. The latter was cold-swaged into rod form and machined to the desired size. Lead wires to all specimens consisted of 18 gage Ti-75A. Chemical analyses of the stock materials are given in Table I. Experimental Procedures Specimens 2½ to 3 in. in length were prepared with diameters nominally 0.15 to 0.20 in. Two holes,

Jan 1, 1954

By E. C. Nelson

An equation is derived for calculating approximately the solubility of nitrogen in an alloy steel over a temperature range from 1200" to 1900°C using data on the effects of alloys on the activity coefficient of nitrogen in iron at 1600°C. Calculated values are compared with experimental data. STUDIES involving the solubility of nitrogen in complex iron alloys have been aided by a system devised by Lanenberg for calculating the solubility of nitrogen in ternary and higher alloys of iron at 1600C using available data on the activity coefficient of nitrogen in binary alloys. Calculated nitrogen solubilities agree well with experimental determinations on complex alloys,&apos; and the calculation procedure is useful when experimental data on specific alloys are not required. A method for extending calculations of nitrogen solubilities in alloy steels to temperatures other than 1600°C would be useful because of the paucity of experimental data in this area. Assumptions which must be made to permit this calculation introduce an element of approximation; however, the calculation is useful in cases where a large number of alloys and temperatures are under consideration, and the precision of experimental measurements is not required. The activity coefficient can be freed from the isothermal restriction of Langenberg&apos;s calculation if it is assumed that the solution is "regular". This is a reasonably good assumption for solutions of nitrogen in iron alloys, because usually they are dilute and the heat of solution is relatively small. The presence of large amounts of certain alloying elements would make this assumption less tenable.3 One of the properties of a regular solution is: when "f" is the activity coefficient of a solute and "T" is the temperature in OK. If the activity coefficients at temperatures T and T2 are denoted by subscripts 1 and 2 respectively: The activity coefficient of nitrogen in a complex alloy then can be calculated at any temperature from the sum of the effects of the other solutes on the activity coefficient of nitrogen at 1600°C. It will be convenient to incorporate this expression into an equation which will give directly the logarithm of the solubility of nitrogen at any temperature in the presence of alloys. Two constants, the solubility of nitrogen in pure iron at 1600 "C and the partial molar heat of solution of nitrogen in iron are required. The heat of solution value of 1400 cal at 1600 °C quoted by Kubaschewski and vans will be used. The accuracy of the calculation will suffer if the heat of solution should change materially with temperature. In the absence of experimental data on the temperature dependence of this quantity, it will be expedient to restrict the application of the calcula-

Jan 1, 1963

By W. R. Ingalls

THE present administration has made sincere and effective efforts to reduce the expense of the Federal Government, but it has reached a point beyond which it seems impossible, or anyway extraordi-narily difficult, to go. This is ascribable to the large part of the budget that is represented as war expense. There is no doubt that this spells high taxation for many years to come. Nevertheless, although a large part of the taxation will be attributable to the war, the paying out of the proceeds of that taxation by the government will not be war expense, except in minor part, as will be hereinafter made clear. It will be useful to explain the economic meaning of this situation, for it has bear-ings upon several open questions, such as a bonus to the ex-soldiers, the foreign debt accounts, etc. The expense of the war on the part of the American people was in the main paid concurrently with its prose-cution. This was necessary. Warfare is not conducted with money, but with materials and labor. Except for such previous production as was represented by stocks of goods, the requirements had to be supplied by coincident production. With the end of 1918 our war expense ceased, save for such production, e.g., of ships, that was allowed to run on unchecked, and the indemnities that had to be paid for cancelled contracts. When those matters have been settled we shall be done, barring one important thing. Of course, our war expense began to contract right after the armistice and shrunk rapidly with the demobilization of the troops in 1919. If we had not been able to obtain all needful material from our own sources and had been constrained to borrow it from foreign countries, incurring a foreign debt, we should have been in the quite different posi-tion of having to repay that material, or its equivalent, during subsequent years. The European countries had to come to us for such supplies. This outlines the fundamental difference between their present situations and ours. We were therefore compelled not only to furnish materials and man-power for our own warfare but also much for the Allies.

Jan 3, 1923

By D. Kramer

HASEN1 has published a phase diagram for the zirconium-nickel system. This phase diagram has been redetermined by Hayes, Roberson, and paasche2 in the range 0 to 50 at. pct Ni. Recently, Smith and Guard3 have published a tentative diagram for the

Jan 1, 1960

By Richard Miller

WORK was undertaken two years ago at the Hammond Laboratory for the purpose of determining the magnitude of the elastic range in single crystals of pure metals by means of creep tests, the assumption being made that if a true elastic range exists, the elastic limit represents the maximum stress for no creep. A sensitive extensometer was constructed, and creep tests were made on zinc single crystals at a variety of loads and temperatures1. It was soon discovered that there is tip measurable elastic limit in ductile zinc single crystals at, or above, room temperature. The inference that pure metallic single crystals may not possess a definite elastic range was not justified, however, since zinc had been tested in creep only above its recrystallization temperature, and several investiga-tors2,3,4 had already shown that above the recrystallization temperature polycrystalline metals will flow under very small stresses, while below that temperature stresses of a much larger magnitude are required. For that reason, it was decided to extend the study of the elastic limit to other metals having a higher recrystallization temperature than zinc. Aluminum and silver were selected, because of the ease of obtaining pure materials and of preparing large single crystals, and because the crystallo-graphic glide system of these metals is well known. Owing to the limited time available, the elastic range was investigated by slow tensile tests rather than by creep tests.

Jan 1, 1937

By Charles S. Barrett

Metallurgists are making use of the stereographic projection to a steadily increasing extent. In the last five years no less than 20 papers in American metallurgical journals alone have employed the stereographic projection; recent books on physical metallurgy, plastic deformation, X-rays and their applications, and crystal structure use it. Mineralogists have used the stereographic projection for many years in the description of symmetry classes and crystal planes, for it presents an accurate, easily understood plot of any angular relations in crystals with all unessential features eliminated (such as the accidentally determined size and shape of crystal faces). In metallography and physical metallurgy the projection is much used for the analysis of markings appearing on polished grains: slip lines, twins, cracks, structures formed by precipitation, magnetic-powder patterns, etch pits, etc. Data from certain types of X-ray photograms are most conveniently analyzed by its use, particularly those for determining the orientation of single crystals or the preferred orientation of grains in an aggregate. Calculations of how to tilt or cut a crystal parallel to a certain crystallographic plane or to reflect X-rays from a certain plane are rapidly carried out. It has been adopted almost universally to the exclusion of other methods by those studying the deformation of metallic crystals, save where the accuracy required is greater than a few tenths of a degree. Any directional property in a crystal or polycrystalline material can be shown on a stereographic projection; for example, the modulus of elasticity, yield point, etc. It has been repeatedly called to our attention that there is need of an elementary explanation of the principles and methods of stereographic projection, covering all the common applications in the field of metallography and physical metallurgy. The following contribution is an attempt to fill this need. The description of each method is supplemented with references to publications in which the method has been used. For convenience to the reader, these illustrative references are chiefly in American journals, particularly the publications of the American Institute of Mining and

Jan 1, 1937

By R. E. Ogilvie, J. I. Goldstein, R. E. Hanneman

The interdiffusion coefficients for the Fe-Ni system were determined as a function of composition in both the a and y phases at 1 atm pressure. The inter diffusion coefficients were also determined in the y phase at 40 kbar pressure. The concentration gradients were measured with an electron probe, and the diffusion coefficients were calculated by the Matano analysis. At 1 atm, Ey increases with nickel content up to 65 at. pct Ni. The relationship of Dy with temperature and nickel concentration, up to 50 at. pct Ni, is given by the equation DY-l atm = exp(.0519 CN~ +1.15) MANY of the transformations that occur in the solid state are diffusion-controlled, especially those involving precipitate growth in most metallurgical systems. Multicomponent diffusion is usually expressed in terms of a chemical or an inter diffusion The activation energy Q at 1 atm decreases from pure iron to 60 to 70 at. pct Ni and decreases from pztre nickel to 60 to 70 at. pct Ni. The Kirkendall marker movement indicates that DFe is greater than DNi zcp to about 60 at. pct Ni. Above 60 at. pct Ni, however, DNi becomes peater than DFe The inter diffusion coefficients were also compared with those calculated from self-diffusion data. A comparison between calculated and measured coefficients shows only rough agreement. The effect of 40 kbar pressure is to decrease DyPl atm by an order of magnitude. The activation volumes for high-pressure diffusion are in favorable agreement with theoretical models developed for self-diffusion. coefficient which determines the rate at which material is transferred from the matrix phase to the precipitate and hence determines the growth rate of the precipitate. Since the numerical values of the diffusion coefficients differ widely as a function of the metallic system, temperature, and pressure, the diffusion coefficients must be determined for each particular environmental condition. Of long-standing interest is the growth of the classic Widmanstatten pattern in metallic (Fe-Ni) meteorites. The growth rate of the pattern is controlled by the diffusion coefficients in the Fe-Ni system. Since these coefficients are essential to calculating the growth rate of the pattern, we found it necessary to determine the diffusion coefficients

Jan 1, 1965

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757&apos; and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick &apos;needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,&apos; are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed&apos; by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke&apos;s law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967