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By Richard S. McCaffery, Morrison B. Yung

While assaying some copper carbonate ore from the Frazer claims, Similakameen, B. C., I noticed that on parting the gold button a deep orange solution was formed. The button gave off pink bands in the nitric acid, which became deep orange at a short distance from it; and as it traveled over the surface of the porcelain dish, it left a deep orange track behind. As the button brightened in the cupel, it appeared to have a bronze color; but I have since found that when amarillium is in large excess of the gold, the button is a very dark gray. The button parted easily. To the orange solution I added a salt (NaCl) solution, shook in a silver testbottle, and filtered. With H2S I obtained a precipitate, which I supposed due to platinum. However, on further tests, it did

Jan 1, 1903

By S. R. Goodman, Hsun Hu

A study has hem made of the formation of annealing textures in an 18-8 austenitic stainless steel (Type 304L) from various deformation textures obtained by rolling at different temperatures. When the deformation texture is a mixture of the ferritic type and the brass type owing to the pres -ence of both martensitic ferrite and retained aus-tenite in the specimen, recrystallization takes place by the growth of the existing austenite phase. In a previous report,' it was shown that the rolling texture of austenitic stainless steel (Type 304L) changed gradually from the brass type to the copper type with increasing temperature of deformation above 200°C. These changes are similar to those in high-purity silver2,3 and electrolytic copper;4 a brass-type texture is favored at low rolling temperatures, whereas a copper-type texture is favored During the course of rolling -texture transition from the brass type to the copper type, the subsequent recrystallization textures change accordingly. The orientation relationship between the annealing textures and the various rolling textures, being consistent with previous observations on various fcc metals, can be described as [Ill] rotations of approximately 25 to 40 deg. Carhide precipitation may influence the annealing textures. at high rolling temperatures. Furthermore, the annealing textures in high-purity silver5 and electrolytic copper4 were found to depend entirely on the prior deformation texture. From a copper-type rolling texture a strong cube texture will form upon recrystallization, whereas from a brass-type rolling texture the annealing texture will be quite different from the cube orientation. In an earlier comm~nication,6 the formation of a strong cube texture in 18-8 austenite stainless steels (Types 304 and 304L) was reported briefly by the authors. The present paper constitutes the results of a complete study of the annealing textures obtained from a

Jan 1, 1965

"In the spring of 1927, six members of the American Institute of Mining and Metallurgical Engineers met for dinner at the Chemists' Club in New York to discuss the possibility of setting up a committee within the Institute to further the current interest in the science of steelmaking. Attention' to this subject had been crystallized by a symposium held by the Faraday Society in 1925. ' After a prolonged discussion, ranging from thermodynamics to slag conditioning, it was decided to approach the Institute with the request that a standing committee on "The Physical Chemistry of Steel Making" be set up. This committee proposed to promote scientific and practical papers on the subject, and was designed to cooperate with the Open Hearth Committee of the Institute in bringing scientific developments to the attention of open-hearth operators throughout the country... . "As the life of the [Physical Chemistry of Steelmaking] Committee lengthened and general interest in the technical phases of steelmaking grew, it became evident that there was a distinct need for a book that might serve the open-hearth interests to better advantage than standard texts whose scope is necessarily wide and whose detailed exposition of the open-hearth process is, therefore, somewhat limited. With this thought in mind, the Committee, after some years of consideration and debate, embarked on the venture of writing a manuscript on `Basic Open Hearth Steelmaking'." The foregoing paragraphs, taken from the introduction by C. H. Herty, Jr. to the first edition, well describe the circumstances which led to the publication of "Basic Open Hearth Steelmaking" in the spring of 1944. The book consisted of nineteen chapters contributed by twenty-three authors and edited by the staff of Alloys of Iron Research and T. S. Washburn, B. M. Larsen, and J. S. Marsh with Frank T. Sisco as consulting editor. The Engineering Foundation and the Open Hearth Steel Committee of the Iron and Steel Division, AIME, made financial grants; steel companies and other organizations supported the publication by contributing time and expenses of staff members in their capacity as authors or editors. The volume was sponsored by the Seeley W. Mudd Memorial Fund and appeared under the

Jan 1, 1951

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.'-4 Samsonov et al.' reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami's Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965

By P. T. Carter, A. B. Murad, H. B. Bell

N. A. Gokcen (Michigan College of Mining and Technology, Houghton, Mich.)—The activities of silica, represented in Fig. 5 for the systems MnO-SiO2 and CaO-SiO2, are in disagreement with the established binary phase diagrams. At Ns102 = 0.50 in MnO-SiO2, and at Ns102, = 0.65 in CaO-SiO2, each binary system is saturated with respect to silica at 1550°C, and therefore as102, is unity in each case. The curves for as102 (FeO-SiO2) and as102, (MnO-SiO,) should nearly co-

Jan 1, 1953

By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By G. J. W. Kor, F. D. Richardson

The sulfide capacities a1 1500°C of slags in the systern CaO + CaF, +Al2O3 have been measured by bringing samples into equilibrium with gas mixtures made from CO + CO2 + SO, + N2. The capacities are negligzble both JOY CaF, and CaF, + Al2O3 melts but when lime is present even at 20 wt pct capacilies as high as 30 x lom3 can be obtained. The results have yielded information concerning the liquidus at 1500°C and fluoride-oxide melts in general. The slags used in electroslag refining contain substantial amounts of calcium fluoride. Robinson and Grainger' report that good results can be obtained by using slags of the approximate composition 70 wt pct CaF2 + 30 pct Al2O3. It has also been reported2 that a mixture of 50 pct CaF2 + 30 pct A12O3 + 20 pct CaO makes a good slag for general use. In view of the fact that very low sulfur contents are claimed for ingots produced by the electroslag process. studies have been made of the sulfide capacities [c, = wt pct S (PO2/Ps2)1/2 at 1500°C. of slags consisting of pure calcium fluoride, and of its mixtures with lime and/or alumina. These studies have also provided information on the phase diagrams. The slags were brought into equilibrium with gas mixtures prepared from NZ + CO + CO2 + SO2. Because CaFz is volatile and also easily hydrolyzed. measurements were made of its loss in weight in various flowing gas mixtures. EXPERIMENTAL Procedure. The apparatus and procedure were the same as described previously. Both platinum and iridium crucibles were used (height and inner diameter about 1 cm), but those made from iridium were stronger and able to withstand a greater number of experiments. In each experiment two crucibles were set in an alumina support and 1 g of slag mixture was divided between them. The materials from each crucible were analyzed separately after being brought to equilibrium with the gas, and then quenched in the water-cooled end of the reaction tube. Materials. Alumina and lime were prepared as de-scribed previously.4 Calcium fluoride was obtained by igniting Analar calcium fluoride in a platinum boat at about 800°C in a stream of pure dry nitrogen: the product was cooled in a desiccator. The slags were produced from mixtures of the powdered constituents, these being melted together in the course of each equilibrium experiment. The sulfur analyses and the X-ray diffraction meas- urements on the solidified slags were made as described previously.4 From the latter it appears that the CaF2 contained less than 0.5 mol pct CaO. RESULTS Values of (ps2/po2) for the Gas Mixtures. The re-sults have been represented in terms of (ps, /Po,)"? for the various gas mixtures used. The va1;es of this function at 1500°C are listed in Table I: they were calculated from the data cited previously for calculations at 1350°C 4 Weight Losses with CaF, and CaF, + CaO. The re-sults of the weight loss measurements* at 1500°C for

Jan 1, 1970

By H. C. Fiedler

Heats of high purity iron containing 3.1 pct Si and be -tween 0.0003 and 0.0295 pct N were prepared by vacuum melting ad then pouring while in a nitrogen atmosphere with the pressure between 0 and 90 psi. Strip from a heat with 0.0184 pct N underwent complete secondary recrystallization during the final anneal. Heats with less nitrogen had too few Si3N4 particles to restrain normal grain growth, and the heat with higher nitrogen had too many particles to allow complete secondary recrystallization. In the hot-rolled structure, Si3N4 precipitates only at the grain boundaries, with the consequence that annealing after hot-rolling diminishes the ability to subsequently undergo secondary recrystallization. In contrast to this behavior, ALNprecipitates uniformly in the hot-rolled structure. Under 1 atm of nitrogen, Si3N, in 3.1 pct Si-Fe dissociates between 900" and 950°C; the solubility of nitrogen increases from 0.0010 pct at 900" to 0.0030 pct at 1200°C. The solubility of nitrogen in Si-Fe has been the subject of many investigations. Corney and Turkdogan1 heated a 2.83 pct Si alloy in nitrogen and found the solubility, under 1 atrn of nitrogen, to be 0.0019 pct at 900°C. They claimed that Si3N4 did not form in the alloy above 705°C in 1 atrn of nitrogen. Fryxell et al.2 heated samples of 3.25 pct Si-Fe containing 0.0025 pct N over a range of temperatures and then analyzed for total nitrogen by vacuum fusion and for nitrogen in solution by a modified Kjeldahl technique. At 900°C, they reported the solubility of nitrogen in equilibrium with Si3N4 to be 0.0011 pct. pearce9 found the solubility of nitrogen at 900°C under 0.95 atrn of nitrogen to be 0.0017 pct in a 3.06 pct Si alloy. He reported that Si3N4 does not form above 770°C in 1 atrn of nitrogen. Although internal friction measurements have given somewhat higher values for the solubility,4-6 if the solubility of nitrogen is as low as has been reported by most investigators, and if Si3N4 is stable up to at least 945°C at 1 atrn pressure of nitrogen as reported by Seybolt,7 a small amount of nitrogen in properly processed Si-Fe should be effective in promoting secondary recrystallization. The requirement is that in the final heat treatment there be enough small, well-dispersed particles of Si3N4 to restrain normal grain growth. Fast8 has obtained secondary recrystallization by nitriding high-purity 3 pct Si-Fe after hot-rolling to a thickness of 0.118 in., followed by processing to 0.012 in., and annealing. A large amount of nitrogen, 0.076 pct. was introduced during the nitriding heat treatment, but he has since reported9 that "a few hundredths of a percent" is sufficient. Small amounts of aluminum10 or vanadium" nitride are capable of promoting secondary recrystallization. Heats containing as little as 0.010 pct A1 or 0.042 pct V and from 0.006 to 0.009 pct N underwent complete secondary recrystallization at final gage, whereas heats with lesser amounts of aluminum or vanadium did not.l2 To be reported is the behavior of nitrogen in high-purity 3.1 pct Si-Fe, and the relation of this behavior to the ability to undergo secondary recrystallization. PROCEDURE Ingots weighing 1 lb were made by vacuum melting high-purity electrolytic iron (A104, Glidden Co.) and high-purity silicon (Monsanto Co.). The latter was used in preference to ferrosilicon to insure a low aluminum content. The design of the melting furnace permitted pouring with the furnace atmosphere either below or above atmospheric pressure. Accordingly, at the completion of melting, nitrogen was admitted to the desired pressure and the heat then immediately poured. The ingots were sound, with no indication of porosity. In Table I are listed the heats investigated, the nitrogen pressure at pour, and the nitrogen and oxygen contents as determined by vacuum fusion with a platinum bath at 1850°C, a procedure which insures measurement of the total nitrogen.13 In addition, all heats contained 3.1 pct Si and not more than 0.002 pct C, 0.003 pct S or 0.005 pct Al. It was subsequently found that the quantity of nitrogen contained in the heats in Table I does not necessarily represent that obtained under equilibrium conditions. For example, the ingot poured immediately after 1 atrn of nitrogen was admitted to the chamber contained 0.0093 pct N, whereas an ingot poured 3 min after the nitrogen was admitted contained 0.021 pct N and another poured after a 6-min delay contained 0.029 pct N. While some bleeding of the hot top occurred in the latter instance, the ingot when examined in cross section appeared sound. The ingots were heated to 1325°C in hydrogen and rapidly rolled to 0.080 in. in 3 passes. The roll speed of the final pass was reduced so as to increase the quenching effect of the rolls. The hot-rolled pieces were processed both as-hot-rolled and after heating for 3 min at 900°C in hydrogen. After cold-rolling to 0.026 in., the strips were heated for 2 min at 900°C in hydrogen, then cold-rolled to the final gage of 0.012 in. The loss of nitrogen in going from the ingot to cold-rolled strip was no more than 10 pct. The final heat treatment, which was for the purpose of develop-

Jan 1, 1970

By A. D. Schwope, L. R. Jackson, A. M. Hall

IN the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of recrystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. MATERIALS USED IN THE INVESTIGATION Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table 1. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871°C in air and hot rolled to 3/8 in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hrs. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pct reduction) in 6 passes and annealing at 427°C for 4 hrs. This annealed wire was then drawn to 0.081 in. wire, (37.1 pct reduction) in 2 passes. Square rod was made by hot rolling wire bars to 9/16 in, rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 3 1/2 hrs at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°C for 3 1/2 hrs. Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 X 0.268 in. square, annealing for 332 hrs at 538°C and cold rolling to 0.257 X 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hrs in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from 0.015-0.025 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. EFFECT OF COLD DRAWING AND TENSILE STRAIN ON STRENGTH OF COPPER Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are

Jan 1, 1947

By N. J. Grant, C. Stein

A more complete determination of the chromium-rich portion of the Cr-Ni phase diagram was made, based in part on resistivity measurements. The existence of a eutectoid reaction at 1215°C,made,based in addition to the previously reported eutectic reaction at 1343°C, was confirmed. Metallographic studies, lineal analysis, and diffusion-couple evidence were utilized to support Metallographicand extend the findings of the resistivity measurements. Delineation of the a chromium solvus line shows that the maximum solubility of nickel in a chromium decreases rapidly from 25 wt pct Ni at the eutectoid temperature to 16 wt pct. Ni at 950°C. IN recent years alloys of high chromium and nickel content have become of more interest as better performance of metals at higher temperatures is sought. It has become increasingly important, therefore, that the Cr-Ni binary diagram, which is composed of two of the elements commonly found in many high temperature alloys, be known more accurately. In particular, the chromium-rich portion of this diagram has for a long time remained incompletely determined and has been reported in the literature with a great deal of conflicting evidence. In general, electrolytic chromium of nominal purity was used by most of the earlier workers, who, except for Jenkins et al., made no further attempt to purify the metal. In the present redetermination of the chromium-rich portion of the Cr-Ni phase diagram, every effort was made to use the purest component metals available and to retain this purity throughout the preparation of the alloys and their subsequent handling. Early work by Voss, Bain," and Phebus and Blake4 indicated that the Ni-Cr binary diagram was a simple eutectic system with rather extensive terminal solid solutions. Later, Nishigori and Hamasumi," Tasaki, Weaver and Jellinghaus,' Matsunaga, and Jette, Nordstrom, Queneau, and Foote attempted to determine the limits of the phase fields. Except for Jette and coworkers, the other investigators agreed that the temperature of the eutectic reaction occurred between 1320" and 1340°C and at a composition of 50 or 51 pct Cr. There was, however, considerable disagreement as to the melting point of the chromium-rich alloys and the limits of the solid-solution fields. As a result of the studies of Jenkins et al., the liquidus and solidus curves up to 80 and 90 pct Cr, respectively, were outlined. In addition, the solid-solution phase fields at higher temperatures had been investigated and showed only two phases. The boundary of the chromium-rich a phase was not determined precisely according to these authors, but indications were that it tended to confirm the earlier work of Nishigori and Hamasumi. A more recent investigation by Taylor and Floyd,'" using X-ray methods, essentially corroborated the diagrams proposed by Jenkins et al., and by Wise and Eash (see Fig. 1). Again, no indication of a third phase in the chromium-rich portion of the diagram appeared. The earlier observations, however, are not substantiated by the modifications to the Ni-Cr binary diagram proposed by Bloom and Grant." In the investigation carried out by Bloom and Grant, X-ray methods showed that an eutectoid reaction existed at approximately 1180°C, in addition to the eutectic reaction at 1343°C (see Fig. 1). Their determination of the melting point of pure chromium was 1930°C (later revised to 1903"C)." Experimental Procedure and Results The chromium used for this study was electrolytic chromium, made available by the United States

Jan 1, 1956

By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki's phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki's data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962

By Walter Renton Ingalls

Metallurgical literature has no record of any ore beneficiated for cadmium alone, and the cadmium of commerce is derived from zinc ore, with which cadmium is generally associated. Zinc ores free from cadmium—e.g., the ores of the Franklin and Stirling mines, New Jersey, and of Broken Hill in Rhodesia—are rare. Blende concentrates of 50 to 60 per cent grade have contained (in production of important tonnage) as much as I per cent Cd, which is unusually high. The concentrates from the Tri-State district average from 0.3 to 0.4 per cent Cd, which is high. The concentrates from mines west of the Rocky Mountains seldom are higher than 0.2 per cent. In the periodic system of the elements, cadmium is in the same group with zinc. Its properties and compounds are similar. Its metallurgy is also similar. Cadmium has a melting point of 320°C. and a boiling point of 778"C., while the melting point of zinc is 415'C. and the boiling point gos°C. These conditions, together with the lower reduction temperature of cadmium oxide, indicate means for. separating cadmium from zinc. Cadmium in spelter is viewed, if not as an impurity, at least as an alloying element that may be objectionable, its special effect being hardening. However, for some purposes, a little cadmium in spelter is desired, and 0.4 per cent may be permissible, even in spelter for rolling. Cadmium in spelter for brassmaking is completely volatilized at the temperature of that process, and in bygone days an immense quantity of cadmium must have been lost in the fumes from these furnaces. Pyrometalltjrgy—Early Cadmium compounds, sulphide and oxide, being more volatile than the corresponding compounds of zinc, loss of cadmium begins to occur from the first furnace operation. In normal roasting, even with Tri-State ore, this loss may not be very high. Raw ore, assaying 0.4 per cent Cd, may be expected to give a roasted product of the same assay, which would imply a cadmium loss of about 15 per cent. Roasted ore, assaying 0.4 per cent Cd when distilled at ordinary furnace temperature, yielded spelter containing about half of that in the ore charged. The first draw of spelter under these conditions may assay 0.8 per cent Cd (accounting for 22 per cent of the cadmium recovery) and after the several draws of spelter have been equalized the cadmium content may average 0.35 per cent. If, therefore, 2000 lb. of blende averaging 0.35 to 0.4 per cent Cd is roasted and distilled, there may be obtained 1000 lb. of spelter, assaying 0.35 per cent Cd or 3.5 lb. content, which entering into Prime Western spelter will be sold at the spelter price. It will be observed from the outline hereinbefore (summarizing conditions prior to the introduction of sintering) that the main loss of cadmium occurred in the distillation process and by failure to condense, which could be ameliorated by attaching a prolong to the condenser, thus collecting

Jan 1, 1944

Single orders 2.5 c. Pamphlets 10. c. each in lots of three or more. Pamphlets 5 c. each in lots of fifty or more. These prices prevail for orders for pamphlet, of the same or different titles. The pamphlets listed on the following sheets are advance copies printed to facilitate discussion at the meetings of the Institute. They are offered for sale at the reduced prices given above as long as the supply, lasts. This list is published in the Bulletin in order that members may have the first opportunity to secure pamphlets, which sometimes are in such great demand that the supply is exhausted before the wants of members can be supplied. The following list includes only a fraction of the pamphlets that have been published by the Institute. Any other paper published by the Institute may be obtained for the price of $1, except those published in Volume XXXI, which are rare.

Jan 5, 1917

By H. D. Kessler, F. A. Crossley, J. J. Rausch

The titanium-rich corner of the system Ti-AI-V has been studied to determine the phase relationships in the temperature interval 600° to 1200°C. Metallographic examination of long time isothermally annealed specimens was the principal method of investigation. TWENTY-SIX alloys in the region 1 to 22 pct A1 and 2 to 11 pct V, and the temperature range 600° to 1200°C, were studied as part of a program on phase relationships and transformation processes of titanium alloy systems. Experimental Procedure Preparation of Alloys—Materials used in the preparation of alloys were high purity Bureau of Mines sponge titanium (103 Bhn), 99.7 pct pure V chips obtained from the Electro Metallurgical Div., union Carbide and Carbon carp., and 99.71 pet pure A1 in the form of granulated shot from Aluminum cO. Of The alloy ingots, weighing l5 g, were melted in a nonconsumable tungsten electrode arc furnace un-

Jan 1, 1957

Albin, B. R Billings, Mont. '28 Amster, Nathan L . , 25 Broad St, New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave, Chicago, Ill. '28 Baum, Frank G Hobart Bldg., San Francisco, Cal. '28 Bayless, Ron. William S Russ Bldg , San Francisco, Cal. ' 28 Bean, Louts H., V.P., Dwight P. Robinson & Co, Inc 125 E. 46th St, New York, N Y. '23 Beatty, Ross J 1105 First National Bank Bldg., Chicago, Ill. '28 Benwell, Oswald F 205 Colorado National Bank, Denver, Colo. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Bingham, Charles W 1542 Hanna Bldg, Cleveland, Ohio. '28 Blumenthal, Hugo 44 Pine St, New York, N. Y. '28 Boettcher, Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H Iola, Kans. '28 Bragg, E. B Carmel, Cal. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1923

By S. Skowronski

PURPOSE OF INVESTIGATION Since cuprous chloride melts at 418° C., boils at 954° C. to 1033° C.,1 and is known to be volatile at a much lower temperature, the presence of chlorine in any form in or on copper to be melted has always been looked upon by copper refiners as a possible source of-serious copper loss. Although this fact has been known for some time, the copper literature contains little or no information regarding it and the field seems .never to have been properly investigated from a metallurgical standpoint. According to Greenawalt,2 cupric chloride, CuCl2, when ignited gives cuprous chloride; therefore cuprous chloride is always formed when copper enters into reaction with chlorine at a high temperature. Cuprous chloride melts somewhat below a dull red heat, and does not volatilize in closed vessels, even if strongly heated, but if heated in the air it goes off as a white vapor. Hofman3 gives the melting point of cuprous chloride

Jan 2, 1919

By E. O. Wagner, V. F. Parry, J. B. Goodman

C. P. HEINER*—If you take out 35 pct of the total weight of the coal in the form of moisture, would that be about what it was in the case of North Dakota lignites ? V. F. PARRY (authors' reply)—That is about it. C. P. HEINER—That will be about a 35 pct loss and the final product will be about 11,000 Btu? V. F. PARRY—That is right. The heating value of the dried lignite is 10,000 to 11,000 Btu. C. P. HEINER—And the thought is not, then, to produce a commercial coal with that heavy loss, but to make other products—that is, synthetic fuel base, is that it? V. F. PARRY—The principal thought is to upgrade the coal, making it a more favorable raw material for industrial purposes, both for shipment and direct use. You see, the trouble in these lignites is that their moisture penalizes their

Jan 1, 1950

By P. R. Kalischer

IN the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more components that tend to form very stable oxides Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken If, however, it s required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible Since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets All of the pertinent properties of the magnets could be accurately and delicately measured by density measurements and magnetic tests of sufficient scope to give a complete demagnetization curve From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties NATURE AND REMOVAL OF SURFACE BARRIERS The early work of the present investigation was based upon published processes In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 per cent Fe, 50 per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200ºC or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics However, this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen Both the iron and nickel powders sintered

Jan 1, 1941

By John Fulton

Early in the year 1875, some difficulty was experienced in the " Old blast-furnaces " of the Cambria Iron Company, at Johnstown, Pennsylvania, arising from the increased use of native coke, prepared in Belgian ovens near the furnaces, in mixture with Connellsville coke, in the production of Bessemer pig-iron. This was the more surprising at that time, because a very caulplete coal-crushing and washing apparatus, after the Bradford plan, had just been put into successful operation, affording a pure coal for coke-making. It was confidently expected that this thorough cleansing of the coal would improve the quality of the coke and fit it for the increasing manufacture of Bessemer pig-iron. But the trouble with the native coke continued. Experiments in fuel charges-increasing and reducing them—failed to correct the irregular working of these furnaces. Increasing the charge of native coke produced abnormal heat at the top of the furnace, reducing it cooled the furnace below. At this stage of affairs, the Hon. Daniel J. Morrell, general manager of the Cambria Iron Company, requested the writer to make the requisite investigation to determine the nature of this coke-difficulty, and to ascertain why the Johnstown coke could not be used in blastfurnace work as well as Connellsville. This task at first did not appear to present any special difficulties, but subsequently it expanded into proportions that caused no little anxiety. The first effort was directed to procuring average samples of Johnstown and Connellsville coke. At this period of the investigation, it was assumed that the whole matter could be intelligently solved by comparing the chemical analyses of the two cokes: Johnstown Coke. Connellsville Coke. Moisture,.......... 0.30 Volatile matter,......... 0.46 Fixed carbon,.90.48 89.57 Ash,.8.96 9.11 Sulphur,.0.56 0.82 Phosphorus,..... 0.014 100.00 100.274 Analysts, T. T. Morrell. A. S. McCreath.

Jan 1, 1884