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By G. F. Dillion, A. F. Armington

THE present method for the ultrapurification of boron involves the formation, distillation, and decomposition of boron tribromide.' However, the boron tribromide prepared contains several impurities in the ppm range, even after distillation. Some of these impurities, notably carbon, can be reduced after decomposition by zone refining. In this study, a comparison of the purity of boron tribromide at various formation temperatures is presented. The apparatus employed consisted of a bromine flask connected to a 22 mm ID horizontal quartz reaction tube packed with amorphous boron powder, which was in turn connected to a receiving flask cooled with an ice bath. Argon was used as a carrier gas. The approximate rate of passage of bromine to the reaction tube was 25 g per hr. The reaction was first investigated at several temperatures in order to determine the lowest temperature necessary to produce a colorless product which was assumed to be an indication of complete reaction of the bromine. The lowest temperature found in this study was 420oC. The amount of impurities found in the boron tribromide at various formation temperatures is shown in Table I. The data presented are emission spectroscopic results of boric oxide produced by the hydrolysis of 2 to 3 g of boron tribromide in 10 ml of distilled water. After hydrolysis, the samples were dried several hours on a hot plate. Assuming equilibrium conditions in the reactor, one can make approximate thermodynamic calculations estimatling the completeness of reaction of bromine with boron and its impurities at various temperatures. Data for these calculations were taken from Rossini,3 and must be taken as approximations since the T?S factor was not included in the calculations. The results of such calculations indicate that, with the exception of carbon bromina-tion, all impurities would react almost to completeness (> 99 pet) at all temperatures between 400" and 900oC. In the case of carbon, which cannot be accurately analyzed spectroscopically, it is estimated that only about one sixth as much carbon tetrabromide would be formed at 400" than at 900°C. Since some marked reductions in impurity content were observed at the lower reaction temperature which would not be predicted by thermo-

Jan 1, 1962

By A. Boltax

The effect of cold work on the electrical and magnetic properties of solution-treated and aged Cu-Fe alloys was studied. The electrical resistivity of solution-treated and of aged Cu-1.7 wt pct Fe samples increased by up to 25 and 140 pct, respectively, follozcing a 55 pct reduction of area. The principle contributions to the increase of resistivity of the solution-treated and aged samfiles are examined. Measurements of the .saturation induction, coercive force, and stacking fault Probability are also reported. 1 HIS paper is the second in a series which examine the behavior of the electrical and magnetic prop- erties of Cu-Fe alloys. The first paper1 was primarily concerned with the effects of thermal treatment whereas the present paper examines the effects of cold work on solution-treated and aged Cu-Fe alloys. The effects of cold work on the transformation of the coherent fcc iron precipitate to the ferromagnetic form2 and the coercive force and remanence3 have already been described, but the unusually large increases in resistivity (up to 220 pct) which occlir with cold work have not been reported previously. EXPERIMENTAL METHOD The methods used for alloy preparation, heat treatment, and electrical and magnetic measurements are described elsewhere.1 The specimens, initially 4-in. lengths of 0.0625-in. diam wire, were cold worked by swaging in hardened steel dies. Following each reduction, the samples were etched lightly in hydrochloric acid to remove surface con-

Jan 1, 1962

By M. L. Bowser

Pulse-forming circuitry is described for use in explosives research that requires precise synchronization and control of events in order to investigate detonation parameters. Included are pulse generators for oscilloscope sweep control, counterchronograph actuators, and a raster-type oscillographic method for the determination of velocities of detonation that are applicable to studies on solid, liquid, and gaseous detonations. INTRODUCTION Prom time to time, requests have been received for information on electronic circuitry used in explosives work at the Explosives Research Laboratory, Bruceton, Pa. The methods used are not entirely original;4 5 6 however, modifications of earlier techniques and some novel design aspects have resulted in time-tested methods that warrant a more detailed description.

Jan 1, 1962

By W. M. Dressel

A simple field test for detecting the presence of germanium in rocks, coals, and flue dust has been developed by the Bureau of Mines. The method consists of dissolving germanium from the samples by either acid or fusion treatment methods, adding a few drops of hematein or phenylfluorone dye, and extracting the resulting colored complex with carbon tetrachloride. INTRODUCTION Germanium is obtained commercially as a byproduct of zinc production, as a coproduct of base-metal refining from germanium-bearing mineral, and as a recovered product from the ash of some coals. The growing use of germanium in the electronics industry has increased demand for this semiconducting metal to the extent that an intensive search for new sources of supply is necessary.

Jan 1, 1962

The Bureau has published much data on sulfur (4, 15, 23)3, most of it dealing with national or international aspects of the sulfur industry. Little information, however, is available on sulfur marketing in specific States or areas, Therefore, the Bureau has conducted a survey of the resources, production, consumption, and economic future of the sulfur and sulfuric acid industry in States of the Central and Southern Rocky Mountain area - Wyoming, Colorado, Utah, Arizona, and New Mexico - and in the Northern Plains States - North Dakota, South Dakota, and Nebraska, even though these States do not represent an economic or marketing unit. The purpose of this survey is to review the demand for sulfur and primary sulfur compounds that draws upon the natural resources of the region, to discover opportunities for better use of these resources, and also to analyze and evaluate the patterns of consumption, sources of supply, and other factors that affect the demand for these mineral products. While this survey stresses the economic and marketing phases of the industry, a complementary report (32) emphasizes the resources of sulfur in Wyoming, Colorado, Utah, New Mexico, and Arizona.

Jan 1, 1962

By E. W. Davis

This paper deals with the role of the Maintenance Department in a milling operation; specifically, the Mines Development, Inc., processing plant at Edgement, South Dakota. The goal of very maintenance department is the smooth and uninterrupted operation of the plant it serves, To achieve this goal, maintenance men adapt various features and procedures into a program designed to fit the characteristics of their particular plant operation. A few of the basic elements of a sound maintenance program are: 1, A periodic preventive maintenance schedule. 2, A systematic inspection and lubrication procedure. 3. A training program for maintenance personnel. 4 A good equipment-history file system, 5. A carefully planned spare parts inventory.

Jan 1, 1962

By L. O. Bacon

This Bureau of Mines report summarizes the results of laboratory work in the design of instrumentation for obtaining the dynamic tensile strength of rock at minimum loading. Minimum loading is defined as the lowest tensile loading by pulse reflection to cause fracturing. The instrumentation for obtaining dynamic tensile strengths of rock cores evolved into the use of a compressed-air pellet gun to impact one end of a rock core, suspended by wires, at increasing increments of air pressure. Maximum strain was measured on most or all of the impacts, and the strain at fracture of the core was obtained by extrapolating the pellet velocity-strain curve to the pellet velocity at fracture. Stress at tensile fracture was obtained from the maximum s train, and the dynamic Young's modulus was calculated from the rod velocity by using simple rod theory.

Jan 1, 1962

By Elmars Ence, Harold Margolin

The titanium-aluminum system has been investigated in the composition region 0 to 34 pct Al in the temperature range 800" to 1450°C. The phases encountered in this region were: a,ß, TiAl3, The reactions observed are as follows: 13 ; L - 6T. A1, 0 (15 pct Al) + 6 (18 pct Al) - yTi Al (16.5 pct Al) at -1170°C andP (7 pctpct Al) + y (9.2 pet Al) - ah(9 pct Al) at - 1060°C. A eutectoid reaction: y — a +d belm 700°C is postulated. THE Ti-A1 system has been the sub.ect of a number of investigations. Several of these1-3 have indicated extensive solubility of A1 in both a and ß titanium. Ence and Margolin, as a result of work on the Ti-A1-0 system:'5 have shown that the a solubility ofalumi-num is considerably restricted, and found that a compound, Ti2A1 existed in the region formerly designated as Q a This structure was identified as hexagonal with c/a = 0.803. Pietrokowsky confirmed the existence of this phase7 and pointed out that the structure was isomorphous with Ti3Sn.8 Although the existence of Ti,A1 has been confirmed by others,9-12 there has been considerable disagreement regarding the composition and mode of formation. A detailed reinvestigation of the Ti-A1 system has been published by Sagel et al.13 The tentative diagram indicated two phases, a, and e, occurring in the former all a region. The a, phase has the same structure as Ti2A1 and was indicated as having a broad region of solubility. Epsilon, a tetragonal phase, was shown to form within the a, solubility region. AS a result of unpublished work,14 Ence and Mugy3 olin disagreed with the interpretation of Sage1 et al., although some common features existed. The present study was conducted in an attempt to clarify prevailing uncertainties. EXPERIMENTAL PROCEDURE Alloy Preparation—Alloys were prepared from iodide titanium (99.9 pct Ti with less than 0.01 pct Zr) or Bureau of Mines electrolytic titanium (BHN-73) and high purity aluminum (99.99 pct). Alloys were arc-melted in argon or helium atmosphere as 15-g buttons in the composition range up to 34 pct Al. Depending on need, alloys were made in increments varying from 0.25 to 2 pct Al. Up to five 15-g buttons of some compositions were made. Weight losses during melting did not exceed about 1 pct of the charge and chemical analysis revealed that both titanium and aluminum were evaporated. In general, nominal and analyzed compositions agreed within 0.5 pct and therefore nominal compositions were used in plotting the data. Unavoidably, some overlap of composition occurred, particularly where small increments of A1 were used. The small increments were primarily used to obtain alloys which would fall into the narrow a -, r region and this purpose was achieved. In general, the data obtained from Bureau of Mines base titanium and iodide titanium alloys were in agreement. Forging—Both as-cast and forged samples were employed. Samples were heated for hand forging by an oxygen-hydrogen torch to the region 1200" to 1300°C. A titanium anvil and cover plate were used to prevent any iron pick-up and consequent formation of a low melting point compound. Frequent reheating kept the temperature in the desired range. Under these conditions, alloys containing up to 15.5 pct could be successfully forged. To check on the depth of contamination, forged alloys were heated slightlybelow the ß transformation temperature. Metal was removed to a depth below the contaminated surface so revealed, and the subsequent results obtained from these samples agreed closely with those secured from as-cast material. Heat Treatment—Prior to heat treatment, all alloys were vacuum annealed to remove hydrogen. Samples

Jan 1, 1962

By J. W. Rutter, K. T. Aust

In previous studies of grain boundary migration in zone-refined lead, the authors used bicrystal specimens consisting of a striated crystal which was grown from the melt, and an adjacent striation-free crystal, introduced by artificial nucleation and growth.1 While this method permits the study of the motion of individual grain boundaries, it does not provide control of the relative orientations of the grains. The present note will describe a technique for controlling the orientations of the two crystals in this type of specimen. The technique consists essentially of placing a striated crystal and a striation-free crystal of controlled orientations end-to-end in a graphite trough, then melting a short zone at the junction of the two crystals and allowing it to freeze to form the desired grain boundary. The apparatus used to carry out this process is illustrated in Fig. 1. It consists of a trough milled from high-purity graphite,with grooves in the underside for the placement of thermocouples. The graphite piece fans out on one end at the level of the bottom of the trough; the sides of the trough are completed in this region by the attachment of a mating plate with a slot cut at any desired angle to permit reorientation of the crystal placed at this end of the assembly. The joint between the crystals is made at or near the point where the slotted plate joins the rest of the trough. The thermocouple slots are deepened in this region so that the thermocouples are separated from the melt by only 1/32 in. of graphite. An induction heater, with suitable temperature control, is used to obtain the molten zone. The two single crystals used are first chemically polished in a solution consisting of eight parts glacial acetic acid and two parts 30 pct hydrogen peroxide. They are then placed in the trough with the ends to be joined at the position of the thermocouples. Next, cooling is applied to the two crystals by means of air

Jan 1, 1962

By E. J. Ostrowski

The history of ironmaking dates back to 4000 BC when an open forge was used to produce a sponge iron from a heap of ore and charcoal. Even at this early date, man recognized the need for a fuel and a reducing agent. As time passed, man developed new methods of producing iron; however, these developments were centered on the mechanical aspects, and as a result, a furnace evolved which is now known as a blast furnace. During this period of evolution,' man struggled with the only fuel he knew - charcoal. Some 5600 years passed before any attempt was made to use coal as a fuel for the blast furnace. The use of coal had its beginning in 1619 when Dud Dudley of England first attempted its use in the blast furnace; as a-fuel and as a reducing agent. Coal charged to the top of the blast furnace was not satisfactory. The volatile matter of the coal choked the flues, and also the poor, strength qualities would not support the weight of the ore. Breaking up of the coal compacted the stock column to an impervious mass. One hundred and sixteen. years later in 1735, Abraham Darby of England introduced coke as the fuel and reducing agent in the blast furnace. The acceptance of coke as a fuel for the blast furnace was not spontaneous. As late as 1870, one-half of the pig iron product of the United States was made with anthracite coal, 30 per cent with raw bituminous coal and coke, and 20 per cent with charcoal. However, by 1910, 96.2 per cent of the blast furnace product was made with coke, 2.4 per cent with anthracite and coke admixture, and 1.4 per cent with charcoal. Coke became the standard fuel in the blast furnace. As the art of ironmaking progressed, more pig iron was produced and more coke was consumed. Coke oven capacity was progressively increased. In 1910, there existed approximately 4,000 coke ovens; in 1960 there was approximately 15,000 ovens. This increase in coke oven capacity was necessary to feed the mammoth appetite of modern blast furnaces.

Jan 1, 1962

By W. A. Backofen, F. de Kazinczy

FRACTURING under conditions of particular interest is identified with the junction of curves relating tensile yield and fracture stresses to test temperature; the intersection point gives the lowest stress, for brittle fracture (at the ductility transition temperature). An expression for is found in Cottrell's brittle-fracture analysis, Eq. [15],1 while measurements of this stress and temperature have been reported for a low-carbon steel heat treated to differ-

Jan 1, 1962

By R. S. Wagner, W. G. Pfann

METHODS that have been used to measure stress relaxation in metals and plastics have been reviewed recently by G. R. Gohn and A. FOX.' The ideal stress relaxation test comprises placing a sample under a constant strain (usually considered

Jan 1, 1962

By B. H. Kear

All the possible ways of forming simple two-dislocation boundaries in multiple slip orientations are deduced. It is shown that the principal differences in work hardening behavior of crystals plastically deformed in these orientations can he accounted for in terms of the likelihood of formation of diffuse boundaries, or deformation bands, consisting of the products of dislocation reactions of the Lomer type. Also, it is pointed out that the break-up of boundaries under the applied stress is more likely to yield interstitial jogs than vacancy jogs, whereas glide dislocations cutting throuqh dislocations trapped in particularly stable boundam'es can acquire both types of jogs. USING Frank's' grain boundary formula, Ball and Hirsch2 determined the parameters of all the possible boundaries that can be built from two sets of glide dislocations in the fee structure. This paper deduces the geometrical possibilities for the formation of these two-dislocation boundaries in the different multiple slip orientations, and discusses the role of boundaries in work hardening and in jog formation. Formation of Two-Dislocation Boundaries in Mutiple Slip Orientations. The parameters of the possible two-dislocation boundaries for any crystal orientation can be deduced most conveniently using the boundary formulae due to Amelinckx,3 in conjunction with the stereographic projection shown in Fig. 1. Suppose that slip occurs in a-BC and ß-CA. According to Amelinckx, when the two systems of glide dislocations are parallel, the rotation axis, u, of the boundary is parallel to (a x ß) and the unit normal, u, defining the boundary plane is parallel to (a x ß) x (BC x CA). On the other hand, when the glide dislocations form a crossed grid, u is parallel to (BC x CA) and u is parallel to (a x CA) x (ß x BC). In Fig. 1, (a x ß) is the pole of the great circle passing through a and ß, so that u is parallel to DC, i.e., parallel to [110]. Furthermore, (a x ß) x (BC x CA) is the pole of the great circle passing through DC and 6, so that u is parallel to [110]. Hence, when all the glide dislocations are parallel, the boundary is pure tilt with parameters u = [110], v = [ 110]. Similarly, it may be shown that the corresponding crossed grid of dislocations is a mixed boundary with u = [111], u = [111]. Consider the case of a crystal compressed in the [001] orientation. In this orientation, according to Fig. 1, there are eight available slip systems. In what follows, the different types of two-dislocation boundaries that are possible in this orientation will be examined by taking different combinations of two slip systems out of the available eight, with a-BC always one of the systems. Case (i)—Slip Systems a-BC and d-CB. The formation of a tilt boundary in (101), which consists of a crossed grid of edge dislocations with vectors BC andCB, is illustrated in Fig. 2(a). As the figure shows, slip is required in the system a-BC in one part of the crystal and in d-CB in the other part, with both sets of dislocations entering the boundary from opposite sides. The rotation axis of the boundary lies in (101), depending on the relative densities of the two sets of edge dislocations in the boundary. Case (ii)-Slip Systems a-BC and ß-CA. The two possible boundaries are shown in Figs. 2(b) and (c); boundary (b) is tilt with u = [110], u = [110], and

Jan 1, 1962

By Richard D. Graves

Pitch from low-temperature carbonization of bituminous coal was hydrogenated at cracking conditions in a continuous bench-scale unit to produce low-molecular-weight oils and tar acids. The pitch contained 15.6 pct benzene-insoluble material, 4.0 pct hexane-soluble oil, and 80.4 pct asphaltene by weight. At 475° C, 7,500 psig, and 1.5 hours residence time, hydrogenation products, based on the weight of pitch, were about 36 pct oil boiling below 325° C, 24 pct hexane-soluble heavy oil, 17 pct asphaltene, 1 pct benzene insolubles, and 12 pct hydrocarbon gases. The yield of tar acids boiling below 250° C was 4.3 pct, and the yields of C6 to C8 paraffins, naphthenes, and aromatics were each less than 1.0 pct. The yield of tar acids was within the range of yields obtained by hydrogenation or high-temperature carbonization of bituminous coal (2 to 5 wt pct). Yields of oil boiling below 325° C increased with increased residence time or temperature. There was little or no effect of residence time on yields of alkali- soluble material which contained tar acids. Yields of hydro-carbon gases increased markedly with an increase in temperature from 475° to 500° C. Lowering the hydrogen pressure to 4,500 psig resulted in yields similar to those obtained at 7,500 psig.

Jan 1, 1962

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By R. B. G. Yeo

Pronounced isothermal martensite formation at room temperature was measured dilatometrically in a steel containing 0.01 pct C, 24.9 pct Ni, 0.26 pctAl, 2.58 pct Ti and 0.25 pct Cb. It is shown that martensite will form isothermally if stabilization of the austenite-martensite transformation is eliminated by removal of carbon. The decarburization of two iron-nickel alloys allows isothermal transformation to martensite to occur at temperatures above their athermal Ms temperatures. In an Fe-22.4 pct Ni alloy, at the 0.008 pct C level, the Ms temperature during air cooling is 85°F higher than that during- water quenching-. At the 0.15 pct C level this difference is reduced to only 5°F. The introduction of carbon causes stabilization during air cooling which lowers the Ms temperature virtually to the same level as determined during mate?. quenching. Thus in the 0.15 pct C alloy, the Ms temperature is almost independent of cooling rate. It is suggested that rival theories of martensite formation should be reexamined in alloys of sufficiently low carbon and nitrogen content to eliminate the complication of stabilization. The Ms temperature of a steel containing 0.01 pct C, 24.9 pct Ni, 0.26 pct Al, 1.58 pct Ti and 0.15 pct Cb, solution treated at 1500°F and air cooled as 1/8-in. diam specimens, was found to be 57 °F. 1 However, when held for several hours at room temperature the steel hardened slightly and became appreciably ferromagnetic. Isothermal transformation to martensite was first revealed by Kurdjumov and Maksimova2 in an iron-base alloy containing 0.6 pct C, 6.0 pct Mn and 2 pct Cu. Most of the other studies of isothermal martensite have also been confined to highly alloyed steels which transform at subzero temperatures; for instance, DasGupta and Lement, 3 Cech and Hollomon, 4 Machlin and Cohen,5 Shih, Averbach, and Cohen.6 Averbach and cohen7 noted a rapidly decaying volume increase at room temperature in a steel containing 1 pct C, 1.5 pct Cr and 0.2 pct V. cina8 and Marshall, Perry, and Harpster9 have described the isothermal transformation to martensite at room and subzero temperature in stainless steels. Kurdjumov10 has recently reviewed the subject, noting that the isothermal formation of martensite can be observed only in the temperature range somewhat below Ms or below -50°C. The isothermal formation of martensite may be characterized as follows: 1) It occurs in steels of widely different compositions, the main prerequisite being a low transformation temperature. 2) The transformation occurs by the formation of new plates and not by the growth of old ones. 3) The isothermal transformation is suppresed by stabilization during slow cooling or holding at temperatures near room temperature. However, the factors governing this mode of transformation are still not fully understood. The formation of martensite isothermally suggests an activated process. The early theories of martensite formation did, in fact, utilize classical nucleation concepts. Kurdjumov 11 first proposed the presence of thermally activated nuclei of different sizes and compositions which would grow if they reached critical size during cooling. This treatment was enlarged and developed quantitatively by Fisher, Holloman, and Turnbull12,13 and was later reviewed by the latter two authors.14 Fisher15 associates Ms with a nucleation rate of one per cc per sec. At slightly higher temperatures the nucleation rate is so low that isothermal formation of martensite is not observed in reasonable times. At slightly lower temperatures the nucleation rate is so high that it could not be suppressed by rapid cooling. By judicious use of parameters Fisher 16 was able to obtain good agreement between classical nucleation theory and the incubation times of martensite formation.4 However the application of these principles to martensite formation in iron-nickel alloys15 predicts that an alloy containing about 30 pct (31 at. pet) Ni would not transform. The presence of an Ms temperature at -223° C in an alloy containing 34.1 pct (33 at. pct) Ni led Kaufman and cohen17 to reject the hypothesis of homogeneous nucleation in favor of the reaction path theory originally proposed by Cohen, Machlin and Paranjpe.18 This theory conveniently explains the formation of martensite athermally but becomes labored when dealing with isothermal formation. Kaufman and cohen19 did explain the isothermal activation of embryos by assuming it to be a result of the expansion of their boundary dislocation loops but this treatment predicts an upper temperature limit of isothermal martensite formation.

Jan 1, 1962

By D. J. Stoops

The object of the research described in this paper was to investigate the effect of metallurgical and surface treatments on the corrosion behavior of arc-melted reactor-grade zirconium in cupric or ferric chloride solutions. An apparatus was constructed and specimens of various metallurgical conditions and surface treatments were tested for 6 days at 35° C., with aeration. Some correlations were observed between corrosion rate and the metal's condition and treatment, Specifically, the unattacked or least attacked specimens were those that had been etched as a final treatment before testing. The most severely attacked specimens were those that had been vacuum-annealed as a final treatment before testing. The moderately attacked specimens were those neither vacuum-annealed nor etched, but having a final surface treatment which left a cold-worked surface. Attack by cupric and ferric chloride was by pit- ting with no preference for grain boundaries, The corrosion scale was cow posed predominately of very fine zirconim particles, Particles from the FeC1,-corroded specimens were more pyrophoric than those from CuCl2-corroded specimens, and appeared to have a higher surface area to volume ratio. Comparison of results to those of previous investigators showed that at certain salt concentrations the more pure, reactor-grade zirconium was quite resistant to attack while the less pure, graphite-melted zirconium was severely attacked.

Jan 1, 1962

By T. R. Cass, M. R. Achter

A technique for measuring the creep and rupture strength of nickel specimens bonded by sintered oxide layers has been developed for the investigation of the role of grain-boundary oxide in the oxidation strengthening of nickel during creep at 817 °C. Prom the inverse dependence of the rate of bonding on the thickness of the starting oxide, it is suggested that the rate of diffusion of Ni++ through NiO is the controlling process at the start of sintering. Cornparisons of the creep and rupture strength and of the microstructure of sintered couples with conventionul creep specimens suggest rupture in nickel is prevented by load-bearikzg, ikltergranular layers of oxide. A number of recent investigations have shown that at high temperature and low stress the creep-rupture strength of nickel and nickel-base alloys may be much greater in air than in an inert gas or vacuum.'-7 For example, at 817°C and 2500 psi, nickep failed in vacuum in 48 hr but not in air after 4000 hr, and a Ni-Cr-A1 alloy5 at 1038°C and 3000 psi failed in vacuum in 4 hr but not in air after 731 hr. Fig. 1 is a typical creep curve in air for materials experiencing this pronounced environmental strengthening. A common feature of these curves is the entry into a third stage of accelerating creep, concurrent with the for-

Jan 1, 1962

By M. Kaufman, A. E. Palty

The phase structure and aging characteristics of two nickel-base alloys, Inconel 718 and 702, were investigated. Wrought and cast Inconel 718 showed ArisCb as the major hardening phase, as well as ture was positively identified. Inconel 702 had Ni3Al as the major hardening phase, as well as Cr7C3-of the phase amounts with temperature was determined. 1 HE value of phase structure and aging rate information in the utilization of alloys has been well established. As part of a continuing program, the results obtained on two nickel-base alloys, hconel 718 and Inconel 702, are presented here. Inconel 718 is a relatively new alloy considered for application in both sheet and cast form. Its novelty lies in the use of high columbium tantalum levels in a Ni-Cr-Fe base. No previous work on this type of alloy has been reported in the literature. Inconel 702 is being used now as an oxidation-resistant sheet alloy. Occasional fabrication problems spurred work on its basic structural behavior. The composition of 702 is essentially nichrome plus aluminum and titanium for strengthening and added oxidation resistance. This puts it in the basic class of other nickel-base alloys which have already been studied. The two alloys will be treated separately. INCONEL 718 Phase Study Methods. The phases present after the various conditions investigated were determined by X-ray diffraction analysis of two different elec-trolytically extracted residues and microscopic examination. The extraction methods, using 10 pct HC1 in alcohol and 10 pct H3PO, in water and the X-ray technique have been described previously.' The effect of temperature on the phase behavior was studied on sheet material using the following heat treatments: 2250°F, 2 hr, ice brine quench 1300 100 hr, water quench 2250°F, 2 hr, ice brine quench 1400°, 100 hr, water quench 2250°F, 2 hr, ice brine quench 1500°F, 100 hr, water quench 2250o 2 hr, ice brine quench 1700°F, 48 hr, water quench 2250°F, 2 hr, ice brine quench 1850°, 24 hr, water quench 2250°, 2 hr, ice brine quench 2000°F, 6 hr, water quench The high solution temperature was an attempt to dissolve as many phases as possible without causing melting. Aging exposures were made longer than normal heat treating times in order to approach equilibrium conditions more closely. Cast material was examined only in the as-cast condition and with the normal heat treatment (1700°F, 1 hr, air cool 1325oF, 16 hr,air cool). Materials. The full phase study was performed on sheet specimens approximately 1/2 in. by 2 in. by 1/16 in. The cast pieces were cut from the gating system of a vacuum-cast test piece. An all weld-metal specimen was made by running many weld beads on the sheet using filler made from the sheared edges of the sheet. All external contamination was removed by belt-sanding followed by an electro-polishing treatment. The typical composition of wrought Inco 718 is as follows: The alloy is air-melted. Cast hco 718 may have higher molybdenum. Due to the expectation of finding a Ni-Cb phase (Ni, Cb) for which no X-ray diffraction pattern was available in the ASTM Index, a special 5 Ib heat to the stoichiometric composition of this intermetallic

Jan 1, 1962