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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 AS a result of unpublished work,14 Ence and Mugy3 olin disagreed with the interpretation of Sage1 et al., although some common features existed.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. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated' single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-' atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By S. Y. Ogawa

The effects of sulfur (up to 0.1 pet) on the deformation and fracture characteristics of iron, in cast form, were studied at strain rates up to 100 pct pcr sec and at temperatures of 1600o to -3300 oF. The effects of oxygen and manganese additions on the behavior of Fe-S alloys were studied under comparable test conditions. Brittle fracture characteristics, evident at all strain rates, resulted from the presence of the liquid iron sulfide phase at grain boundaries. Ductility could be restored in three ways: solution of the sulfide in solid y iron at higher temperatures, spheroid-zzation of the liquid sulfide, and increase. in the melting point ot the sulfide. THE literature shows that most previous studies of deformation and fracture at hot working temperatures have been based on measurements of energy absorption, reduction of height in forging upset tests, torsion tests of bar or wire samples, and so forth,' but that relatively few tension tests have been used at high temperatures and strain rates. The present work was initiated to study the ef- fects of temperature, strain rate, composition, and structure on the deformation and fracture characteristics of iron, utilizing cast specimens tested in tension. As in a previous study,' strain rates up to 100 pct per sec were chosen for the temperature range 1600° to 2400° to provide data which might be useful in the interpretation of the deformation and fracture behavior of steels under hot working conditions. The previous work was with Fe-P solid solution al10ys;2 this work is concerned with Fe-S alloys, and with the effects of oxygen and manganese additions. MATERIALS AND PROCEDURE Cast tes! specimens were employed throughout, since most of the difficulty during hot working occurs in the initial breakdown of the ingot. Alloy Systems. Ten 25 lb. heats containing sulphur were prepared. Of these, three had manganese additions, and two had oxygen additions. The sulfur content varied from 0.023 to 0.10 pct. Manganese contents were intended to be ten to twenty times the sulfur content of the particular alloy. Oxygen, being more difficult to control in small melts, was varied by the amount of solid deoxidizer added, but poor control of the oxygen content was experienced in most instances. Table I shows the chemical analyses of the heats. Melting and Casting. Electrolytic-iron chips were melted by high frequency induction in a prefired, clay-graphite crucible lined with rammed magnesite.

Jan 1, 1962

By M. E. Nicholson

The effect of boron on the austenitic transformation rate of iron is smaller than on low carbon steels. The influence of austenitizing temperature on B-Fe is the reverse of its influence on steels. THERE have been many studies made of the influence of boron on the hardenability of steel, but apparently none has been made of its influence on the y-a transformation of pure iron. There are several facts suggesting that boron should have a pronounced effect on the transformation rate of iron. First, Simcoe et a1.l indicated that boron reduces the nucleation rate of ferrite and bainite. Second, they showed, along with others,', " that the lower the carbon content of steel the greater the influence of boron on hardenability. If this trend extends to pure iron, the influence on rate of ferrite formation should be considerably greater for iron than for medium carbon steels. According to Rahrer and Armstrong," the multiplying factor for boron in pure iron should be about 2.40, compared with 1.50 in a 0.35 pet C steel. According to an extrapolation made by Grange and Mitchell,' the effect should be even greater, and the multiplying factor should be about 3.5 in iron. Many investigations of the boron influence'.7, 2, 5 indicated that boron is effective only when in solid solution. On the other hand, Chandler and Bredig" suggested that boron increases hardenability by combining with nitrogen, thereby preventing formation of AlN, which catalyzes the decomposition of austenite. If their hypothesis is valid, boron should have no effect on an alloy free from nitrogen. Digges et al." showed that so far as low nitrogen high purity Fe-C alloys are concerned this is not the case. No experiments, however, have been made on low nitrogen iron. To determine whether or not boron has an effect on low nitrogen iron and, if an effect exists, to determine whether it is as large as predicted from the investigations of boron treated steels, the following work was performed. Because of the rapidity with which iron transforms from austenite to ferrite at even a moderate degree of supercooling, it was decided to study the influence of boron on the transformation rate of iron by determining the effect of quenching rate on the temperature of the beginning of transformation. The technique, essentially that used by Greninger' and Duwez,H consisted of heating small specimens, 0.1 in. sq and 0.010 in. thick, in an atmosphere of purified helium with a resistance heater coil, and then quenching the sample in a jet of helium gas. At the time the jet was applied, the heating coil was removed from around the sample. The sample was suspended in the furnace on 30 gage chrome1 and alumel wires, one welded to each side of the specimen, which also served as a thermocouple for measuring the specimen temperature. Specimens were prepared from vacuum-melted iron obtained from the National Research Corp. which was rolled to a thickness of 0.060 in. and then decarburized in wet hydrogen for 51/2 hr at 700°C. This treatment also removed any boron present in the iron. The resulting iron contained 0.001 pet C. 0.0002 pet N, and 0.005 pet 0. One half of the piece was then boronized by surrounding it with 325 mesh boron powder and heating it for about 2 hr at 900°C in H,. The boronized iron was then homogenized at 1100°C for 24 hr. The iron boride case formed by boronizing was removed by grinding 0.010 in. from each side of the plate, and the piece was finally rolled to a thickness of 0.010 in. The resulting alloy contained

Jan 1, 1957

By H. Bernstein

Grain coarsening tests were carried out on AI-4.5 pct Cu and AI-4.5 pct Si alloys. The effects of three variables, melt composition, pour temperature, and mold temperature, were determined. It was found that the macrostructure generally coarsened with increased pour and mold temperatures. Coarsening was extreme in the unrefined alloys but was retarded by the active grain refiners like titanium and columbium. The effect of boron was spectacular in suppressing coarsening tendencies. The results of the investigation support the carbide theory of nucleation as opposed to the peritectic theory. A REVIEW of prior work on the subject of grain refinement in the light metals indicated that, for the most part, it had been concerned with the positive effects of addition agents upon structure. This work produced various theories of refinement. Prominent among them were the peritectic theory and the transition element carbide theory. Certain inadequacies in the former theory appeared to be explained satisfactorily by the transition element carbide theory. In order to appraise these theories further, a study was undertaken of the permanence of grain refinement effects when subjected to thermal or chemical variations. It was considered that a study of this kind would be of practical value, since the light metals are exposed to thermal and chemical variations in the normal course of foundry operations. Accordingly, two alloys of commercial importance were selected for this investigation, the A1-Cu and A1-Si alloys. Experimental Procedure and Results Raw Materials: The base alloys, A1-Cu and A1-Si, were prepared from virgin aluminum and hardeners, induction melted, and pigged for remelting. The grain refiners, including titanium, columbium, zirconium, and boron, were added as master alloys. Analyses of the raw materials and base alloys are listed in Table I. Melting and Casting Practice: The metals were melted in clay-graphite crucibles in a Hevi-Duty pit-type resistance furnace, equipped with a Leeds and Northrup Micromax Recorder and Controller. After melt down of the base alloys, the additions were made. For each casting, approximately 80 grams of metal were poured into a preheated graphite mold held in a transite flask. The mold (Fig. 1) weighed 320 grams. To determine the effect of superheat upon structure, a set of melts was heated successively to four temperature levels, 705°, 775°, 845°, and 915°C, and test specimens were cast at each level. Prior to each pour, the furnace temperature was held constant for 20 min. Next, a set of melts was put through a superheat cycle and test specimens were cast at melt temperatures of 705" and 915°C successively. The crucibles then were cooled in air to 705°C as deter-mined by immersion thermocouple and additional test specimens were poured. The cooling interval was approximately 1 min. Another set of melts was furnace cooled with the cover slightly ajar and test specimens cast as before. The interval in this case was 15 to 20 min, varying with the superheat temperature. The mold temperature for all these tests was 400°C. To determine the effect of cooling rate without superheat upon structure, a set of melts was heated to 705°C, and castings were poured at mold temperatures of 205", 400°, and 540°C. An interval of 15 min elapsed between each pour. Mold temperatures were measured by a direct reading millivolt-meter, using a chromel-alumel thermocouple located at midwall thickness of the mold. To demonstrate the phenomenon of chemical coarsening, agents such as chromium and beryllium, which had acted as coarseners in a previous investigation,' were added to the A1-Cu alloy. Test speci-

Jan 1, 1955

By G. R. Speich, S. A. Kulin

The isothermal formation of martensite at subzero temperatures has been studied in an austenitic stainless steel. The amount of martensite formed isothermally in a given time was found to follow a C-curve behavior with decreasing temperature. Since isothermal rnartensitic transformation occurs at temperatures above the true M. temperature of the olloy, the observed M. temperature is dependent on the cooling rate. It is believed that a general martensite theory must include the basic concepts of the strain embryo theory, and also the important role of thermal fluctuations. UNTIL recently the isothermal component of the martensitic transformation had been considered as a trivial effect in theoretical considerations of this type of transformation. One of the postulates used in defining a martensitic transformation was that the reaction was temperature dependent but not time dependent. Cohen and his associates1'2 were the first to report the isothermal formation of mar-tensite. They obsel-ved the time dependency of the martensite reaction at room temperature in plain carbon steels and certain tool steels. They found that a small amount of additional transformation occurred after the specimen reached the quenching temperature and that the rate of this isothermal transformation decreased rapidly with time. These authors considered this phenomenon to be a "tailing-off" of the main athermal reaction. Kurdjumov and MaksimovaL 5 studied the isothermal formation of martensite at subatmospheric temperatures in steels containing 0.6 pct C-6 pct Mn, 1.6 pct C, and in an iron-base alloy containing 23 pct Ni and 3.4 pct Mn. In each case it was found that both the initial rate and the total amount of isothermal transformation exhibited sharp maxima with decreasing temperature. They stated that it was possible to completely suppress the martensitic transformation in the 0.6 pct C-6 pct Mn steel by drastic quenching in liquid nitrogen. They interpreted their results in terms of a thermally activated process. The maximum in the rate of nucleation vs. temperature curve was assumed to be a result of the temperature dependence of the rate of growth of the martensite plates. It has been demonstrated," however, that martensite plates can form with great rapidity even at temperatures approaching absolute zero. In addition," attempts to confirm the reported suppression of the martensitic transformation by rapid cooling of a 0.6 pct C-6 pct Mn steel have proved unsuccessful. On this basis, and on other theoretical grounds, the validity of some of Kurd-jumov's results and conclusions is open to serious question. Cohen, Machlin, and Paranjpe' have proposed a theory of martensite formation based on the nucleation of strain embryos and a growth mechanism involving cooperative atomic displacements. According to this theory thermal fluctuations can make a strain embryo supercritical and thereby produce martensite isothermally. Das Gupta and Lement' have investigated the isothermal formation of martensite in a 17 pct Cr-0.7 pct C steel at temperatures below the ambient. They found that partial suppression of the martensitic reaction occurred on quenching into liquid nitrogen. That part of the reaction which can be suppressed is taken to correspond to the isothermal rather than the athermal part of the rnartensitic transformation. The initial rate of isothermal transformation for this steel was found to go through a maximum with decreasing temperature. This is in conformity with the findings of Kurdjumov and Maksimova for the steels used in their investigation. Das Gupta and Lement conclude that isothermal martensite formation occurs by the nucleation of new plates and is always preceded by some athermal transformation. An iron-base alloy containing 14 pct Cr-9 pct Ni was used in this investigation to study further the kinetics of the austenite to martensite transforma-

Jan 1, 1953

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By O. Chanute

In discussion of Mr. Macdonald's paper, I can say little more thau to add t~ the general acknowledgments of iguorae, and like several of the gentlemen who have preceded me, make one of those confessions which are thought to be good for the soul. Having had some experience in the erection of bridges during past years, I am aware that We yet need much information in order to proportion them to the best advantage. I would more especially like to emphasize three of the points mentioned by Mr. Macdonald, as among those upon which we lack knowledge; these are: first, the behavior of steel; second, the proportions of compression members; and, third, the influence of the size of a bar upon its strength per square inch. First, as to steel. While we all acknowledge this as the material of the future, our position map be said to be still one of expectaucy. Feu? engineers are bold enough to employ it largely in bridges, and those who do, find such serious difficulties in obtaining uniform grades of it, are so puzzled by apparent anomalies and unexpected phenomena, that it requires considerable faith and courage to apply it in large structural masses. A series of systematic experiments,

Jan 1, 1882

By K. Mukherjee

Instantaneous resistance change during martensitic transformation in Fe-30 at. pct Ni alloy has been studied using a low-noise electronic system. The smallest signals recorded in this investigation were of the order of 10 pv. These small signals did not show the initial increase reported by earlier investigators to support a double shear mechanism.&apos; A variety of pulse shapes and sizes was observed during "burst" transformations, and these signals were neither a linear function of the size of martensite plates nor of the volume fraction transformed. Even the smallest signals, presumably from single plates, showed complications resulting from elastic and/or plastic deformation, shock wave propagation, and so forth, which are inherent in the growth process of a martensite plate. The time of formation and interface velocity determined froni this experiment agree very well with the pioneering work of Bunshalz and Mehl.&apos; AN Fe-30 at. pct Ni (c0.005 pct C) alloy was used to study the time of formation of martensite plates. Martensitic transformations, unlike the nucleation and growth processes, are usually characterized by an extremely fast reaction rate. During the transformation, the crystal structure changes and this change is propagated through a finite volume of the parent crystal lattice within a very short time interval. The interface between the two phases probably consists of moving dislocations, and the time of formation of the plate depends on how fast this dislocation interface can move. Knapp and Dehlin~er or Cottrell and Bilby mechanisms, or similar dislocation models, can be used to calculate the time of formation of a martensite plate of a given size. In the past, conventional photographic technique475 as well as electrical resistivity techniques"~-" have been used to measure the time of formation of a martensite plate. The specific resistance of the martensitic phase in Fe-30 at. pct Ni alloy is lower than that of the austenite phase. Therefore if a current is passed through a small austenite sample in series with a large external resistance, then one would observe a voltage change across the sample as martensite is formed. Such dc measurements are shown in Fig. 1. The initial large voltage drop in Fig. 1, at the M, temperature, is due to a "burst" transformation where a large number of plates are formed in a cataclysmic manner within a very short interval of time. Even during the later stages of transformation as shown in Fig. 1, one can observe discontinuous voltage changes due to small bursts. In order to resolve the time scale of such discontinuous stages, the voltage signals are amplified and fed into a highspeed oscilloscope. In this investigation a low-noise amplifier was used for the first stage of amplification. The signal to noise ratio was further improved by the design of a pulse transformer. This transformer was capable of amplifying the signal by a factor of six. Voltage signals were studied over a wide time scale ranging from 2 sec to 0.1 psec. I) EXPERIMENTAL PROCEDURE A) Specimen Preparation. Specimens were cut from induction-melted Fe-30 at. pct Ni (<0.005C) alloy and cold-rolled to 0.2 by 1 mm cross section and an average length of 5 cm. During mechanical shaping, the specimens were strain-annealed at 950°C for 24 hr in vacuum. Finally the finished samples were vacuum-annealed at 1000°C for 6 hr and water-quenched to room temperature. The average grain diameter was 0.02 cm. B) Cooling System. The M, temperature of the alloy was -55°C. Fig. 2 shows the arrangement which was used to cool the specimen at a slow rate. The specimens were mounted inside a i -in.-diam hole in the 2-in.-long section of the copper specimen holder. This cavity was filled with silica gel. A dummy specimen was used under identical conditions for

Jan 1, 1969

By M. L. Hammond, G. M. Bowers

Silicon dioxide films have been prepared on silicon wafers by the oxidation of SiH, near 400°C. Results previously reported by Goldsmith and Kern7 have been qualitatively corrobovated using a system of different geometry, and significantly greater deposition rates have been achieved. The deposition rate is independent of thickness and nearly independent of the O2/SiH, ratio over a wide range; however, the rate is strongly temperature-dependent. The structure of the deposit depends upon the cleanliness of the substrate, and the electrical field strength of the deposited oxide depends upon the nature of the electrodes. MULTILEVEL interconnects in integrated circuits using aluminum metallization require an insulator that can be deposited at low temperature. Because the A1-Si eutectic is only 577°C, the maximum deposition temperature must be below about 500°C to prevent reaction of the aluminum with the silicon and with other materials in the integrated circuit. Many methods of depositing insulating films of SiO, and other dielectrics have been reported&apos;-6 but the technique described by Goldsmith and Kern7 offers the simplest method of preparing SiO, films. The technique involves the reaction of SiH, and 0, to form SiO, films in the 300" to 500°C temperature range. Previous work using this gas system has been reported8 and the initial development work at Philco Microelectronics was done at the East Coast R&D Laboratories. 9 This paper corroborates some of the results of Goldsmith and Kern,7 shows that much higher deposition rates can be obtained than previously reported, and presents some observations on the structure of deposited SiO, films. EXPERIMENTAL CONDITIONS Fig. 1 is a schematic drawing of the apparatus used in this study. It differs from that of Goldsmith and Kern in that 1) the gases are mixed before they enter the reaction chamber, 2) there is no fritted glass diffuser, and 3) the wafers are stationary during deposition. The control thermocouple was in a well located 0.06-in. from the substrate, and three gas supplies were used: 1 pct SiH4 in N 2, O 2, and N 2. Water vapor must be excluded from the plumbing to prevent the formation of colloidal SiO, and the SiH4 must be diluted with an inert gas because SiH4-0, mixtures are extremely flammable above about 4 pct SiH The wafer temperature was determined by attaching a thermocouple to a test wafer and the temperature was maintained to +5 C. The conditions used in this investigation are listed in Table I. The temperature range was chosen for compatibility with the A1-Si system. The volume ratio of 0, to SiH4 is the actual volume of 0, delivered to that of SiH4, taking into account the initial dilution of the SiH4. This ratio, which was used by Goldsmith and Kern,7 is a useful indicator of the experimental conditions. The active/inactive ratio is the ratio of the volume of active gases, SiH4 and O2, delivered to the volume of dilution gas. The active/inactive ratio is an important parameter to specify for deposition rate determinations since it determines the amounts of reactants that arrive at the sample per unit time. Fairly high dilution ratios were necessary to achieve uniform deposits of SiO,. Most of the process characterizations were performed on the polished (111) face of 3 to 5 ohm-cm, n-type silicon wafers which were 0.009 in. thick; but the data approximately apply to deposition of SiO, on thin films of aluminum. It is difficult to obtain accurate deposition rate data over aluminum films because of coarsening the aluminum surface during exposure to 300" to 400°C. The deposited SiO, film fol-

Jan 1, 1969

By D. Harker, W. E. Seymour

CERTAIN alloys of iron and nickel, when rolled and annealed, possess a preferred crystal orientation: (001) in the rolling plane and [loo] in the rolling direction, when recrystallized at 850" to 1050°C after approximately 98 pct cold reduction. Since the preferred orientation makes a direction of easiest magnetization coincide with the rolling direction, these alloys, especially a 50 pct iron in nickel alloy, have found wide application in the electrical industry&apos; for choke coils and special types of transformers. The rate of the recrystallization reaction was studied at temperatures ranging from 500° to 600°C. The heat of activation for the reaction was calculated from the observed rates, and crystal orientation determinations were made before and after re-crystallization. A vacuum melted iron-nickel alloy* analyzing 49.6 pct nickel, 0.018 pct carbon, and 0.30 pct manganese was used for the experiments. The alloy was cold-rolled 98 pct into strips 1/2 in. wide by 0.002 in. thick. Specimens 1 in. long were sealed under a vacuum (approximately 10-8 mm Hg) in 1/2 in. ID pyrex glass tubes. For heat treatment these tubes were fastened to Nicrohm wires and submerged in a molten salt bath controlled to ±2°C. (The maximum measurement error was within 3°C.) The time at temperature was varied logarithmically from one sample to another, and runs were made at 500°, 525", 550" and 575°C. A molten lead bath was used for a run at 600°C which was controlled to the same accuracy. To determine the extent of recrystallization after a particular time at a given temperature, a method was used suggested by the work of Decker, Asp, and Harker.3,4 This method employs an X-ray spectrometer whereby X rays are diffracted from crystallites whose diffracting atom planes are parallel to the rolling plane of the specimen. The intensities of the diffracted rays are measured by a Geiger counter. The counter can be rotated through a range of angle, and can be motor driven through this range at a speed of 2" per min. The measured intensities are plotted vs. angle by a potentiometer recorder. In a 50 pct iron-nickel alloy it was found that only (200) reflections were obtained from the rolling plane with recrystallized material, and that only (220) reflections were obtained from the rolling plane with unrecrystallized material. No other reflections were obtained under these conditions over a range of Bragg angle of 0 to 45" using either type of specimen. As a consequence, the intensity of the (200) reflections from the rolling plane was taken to indicate the amount of recrystallized ma-terial present in a specimen, and the corresponding intensity of the (220) reflections was taken to indicate the amount of unrecrystallized material present. To insure flatness and proper alignment of the reflecting specimen in the spectrometer, the sample was laid in a slot 1/2 in. wide x 0.001 in. deep which was machined in a 3/4x2x1/2 in. steel carrier. The specimen then was taped down with cellophane tape. This steel cradle was mounted vertically in the specimen holder of the spectrometer so that the bottom edge of the carrier rested against a horizontal shoulder. Intensity data used in plotting the percent of recrystallized material vs. time at temperature were obtained by directly counting the diffracted beam of nickel filtered copper Ka radiation used throughout the work. The X-ray spectrometer was employed also in obtaining pole figure data to be used for orientation determinations. At the beginning of this investigation a transmission pole figure holder was used." As a thickness of 0.002 in. of this alloy was found to be opaque to the copper Ka radiation, it was necessary to reduce the thickness of the pole figure specimen. A cold-worked sample was etched in a 50 pct HCl solution for 5 min and was found to transmit a

Jan 1, 1951

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram for the gadolinium-cobalt system has been determined. Seven intermetallic compounds have been found at compositions corresponding to the follwing gadolinium-cobalt ratios: 3:1, 1:1, 2:3, 1:2, 1:3, 1:4, 1:5. The GdCor compound has a congruent melting point above 1600°C. whereas the remaining compounds melt incongruently. Eutectics exist at 16 wt pct Co and 84 wt pct Co, with melting points of 620° and 1260°C, respectively. PREVIOUS papers&apos;" have recorded constitutional data for systems of gadolinium with iron and nickel. This paper presents data obtained on alloys of gadolinium with the remaining 3d transition element-cobalt. voge13 found that cerium forms, with cobalt, the intermetallic compounds; Ce3Co, CeCo, CeCo2, CeCo3, CeCo4, and CeCo5 Other workers4-&apos; found the 1:2 compound in this series to exist in a C-15 (face-centered cubic) structure and the 1:5 compound to exist in a hexagonal crystal system. Comparison of earlier data with that now reported will be made subsequently. EXPERIMENTAL Methods of alloy preparation, annealing procedures, and experimental techniques have been previously reported.&apos; The cobalt content of alloy specimens was determined volumetrically. RESULTS Microstructure—The alloy containing 10.5 wt pct Co corresponds closely to the composition of the first intermetallic compound Gd3CO. In Fig. 1 the microstructure is essentially single phase composed of Gd3Co which formed peritectically. The globular areas are remnants of the peritectic reaction which did not quite go to completion. A eutectic occurs between Gd3Co and the next higher compound GdCO, which is followed by a series of peritectic compounds. Fig. 2, an arc-cast alloy containing 20.2 wt pct Co, shows large primary crystals of GdCo etching either white or black (depending on crystallographic orientation), embedded in the eutectic. Similarly, in Fig. 3 at 31.2 wt pct Co, a compound, probably GdCo3, has separated from the melt. Subsequent peritectic reactions were almost completely by-passed as the alloy cooled, the residual liquid freezing as a fine eutectic. In the 47.5 wt pct Co alloy, Fig. 4, the high melting point compound, GdCO4, has solidified as massive, white-etching grains, which reacted with the liquid to form GdCo3 as the second phase. The microstructure of an arc-melted alloy containing 60.5 pct Co is complex, Fig. 5, and presents some difficulty in interpretation. The grey etching matrix is probably primary GdCO4. The dappled phase represents grains of GdCO5 which have separated from the melt on cooling. The discrete spots in this phase are eutectic liquid. Small light etching crystallites are probably GdCO5 formed by the incomplete high-temperature peritectic reaction. GdCO4 is retained in arc-melted specimens containing 70.5 wt pct Co, Fig. 6. White areas of this compound are held in a matrix of GdCO5 the appearance of which is mottled slightly by inclusions of the second eutectic in this system. The development of the spheroidized eutectic at high cobalt contents is depicted in Fig. 7 (80.3 wt pct Co) in which the white massive crystals are GdCO5 compound. Further development of this eutectic is seen in Fig. 8, the primary white phase here being pure cobalt. Thermal Studies—Differential thermal analyses and melting point determinations have yielded the data shown in Fig. 10. The high gadolinium eutectic, indicated by microscopy, was confirmed at about 16 wt pct Co, melting at 620°C . A eutectic also occurs at about 84 wt pct Co melting at about 1260°C. The thermal arrests at 8803 960°, 1060; and 1210°C,

Jan 1, 1962

By R. Grierson, R. N. Parkins

The m.echanica1 properties, at high lzomologous temperatures, of the intermetallic compounds InzBi and Mg17A112 were measured as a .function of temperature, applied strain rate, previous thermal and mechanical history, and composition. Mgl,Al12 was investigated ilz compression, whereas Zn,Bi was investigated in tension. A decrease inflow stress with increasing strain was observed jor both alloys. The results obtained are discussed in terms of the dislocation-multiplication processes in these materials. MANY intermetallic compounds are reported to undergo a brittle-ductile transition at high homologous temperatures.&apos; There is evidence in the literature that some of these compounds exhibit a large yield drop when plastically deformed.&apos;j3 Both of these forms of behavior are shown by the covalent elements germanium and silicon4,5 and also by certain ionic compounds.8 The present work is a study of the deformation, at high homologous temperatures (>2/3 Tm), of two intermetallic compounds, In2Bi and Mg17Al12. InzBi has a disordered hexagonal structure7 (c/a = 0.598) and a solubility range of 32.3 — 33.2 at. pct Bi.8 It has a melting range from 72° to 89°C. Mg17Al12 has an ordered bcc (A12 type)7 structure and exists over the range 50 to 60 at. pct Mg8 with a melting range from 437° to 462°C. We have been unable to find any reference to previous investigations of the mechanical properties of BiIn,. Novikovg has reported that cast samples of Mg17A112 show ductility, when bend-tested, at temperatures above 380°C. EXPERIMENTAL Ingots of In2Bi and Mg17Al12 were melted under an argon atmosphere and cast, in situ, in a graphite crucible. The materials used were of 99.99 pct purity. The alloys prepared contained 66.9 at. pct In in the case of In2Bi and 58.4 at. pct Mg in the case of m17A112. The ingots were homogenized and then extruded. Two-in.-diam Mg17Al12 ingots were extruded at 375°C to give 3/8-in.-diam rod. The rate of formation of this rod was 0.25 in. per min. One-in.-diam InzBi ingots were extruded at 20°C, using a rate of 1 in. per min, to give 1/8-in.-diam rod. In both cases the extruded rod had a recrystal- lized, fine-grain, structure. (For Mg17Al12, d = 11.2 µ; for BiIn2, d = 22 µ.) Mechanical-property determinations were made in a hard-beam machine, in tension in the case of In2Bi and in compression with Mgl7Al12. The tensile tests were on specimens having a gage length of 1.1/2 in. and a diameter of 1/8 in. The compression tests on Ml7A112 were on specimens of 3/8 in. diam by 3/8 in. high and the ends were coated with poly-tetrafluorethylene to minimize friction. RESULTS In2Bi. Fig. 1 shows, particularly at the higher applied strain rates, that In2Bi exhibits a marked yield drop as the deformation increases to about 2 pct, after which the material shows neither hardening nor softening up to 15 pct strain. The magnitude of the yield drop, the stress in the region of flow under constant stress (the stress plateau), and the 0.5 pct proof stress were all dependent upon the applied strain rate according to an expression of the form

Jan 1, 1965

By R. F. Sheldon

Largest uranium deposit in the Northwest is Dawn Mining Co.&apos;s Midnite mine on the Spokane Indian Reservation. The orebodies lie along the contact of granite and metamorphosed sedimentary rock and are controlled by faults and shear zones near the granite contact. In the oxidized zone the deposits consist mainly of the secondary uranium mineral meta-autunite; sooty uraninite and primary uranium minerals are known to occur at greater depths. Elevations in the mine area range from 2500 to 3500 ft. The rolling hills and low, rounded mountains are covered with grass and evergreen trees. HISTORY AND DEVELOPMENT Original showings were discovered with a geiger counter in the spring of 1954 by prospectors Jim and John LeBret. High radioactivity in several schist outcrops was found due to scaly coatings of a greenish-yellow, fluorescent mineral, later identified as meta-autunite. Prior to this time autunite was not known to occur in the state of Washington, and no significant uranium deposits had been found in the Pacific Northwest. Outcrops in the area were few, and most of the ground was mantled with 2 to 10 ft of overburden, but three other radioactive zones were discovered by prospecting the ridge southward along the strike of the schist near its contact with granite for three quarters of a mile. Midnite Mines Inc. was formed

Jan 1, 1960

By Jean Howard, E. V. Walker

ManY papers have been published during the last few years on the formation of cube texture in 3 1/4 pct Si-Fe, e.g., those of Assmus, Detert, Dunn, and Walter.1,5 All are concerned with the formation of the texture by a process involving secondary re-crystallization and the relative surface energies of (100) and other planes under certain conditions of annealing. The authors have found that cube texture can also be produced by heavily cold rolling strip in which the cube-on-edge texture has first been formed. Cube texture develops on annealing, but in this case it is not accompanied by secondary recrystallization. The starting material is a sintered compact, the preparation of which has been described elsewhere. Using a conventional processing schedule employed for producing commercial silicon-iron with the cube-on-edge texture, the sintered compact is cold rolled to such a thickness that, after annealing in pure hydrogen for 24 hr at 1350&apos;~ to produce the cube-on-edge texture, the final thickness required can be obtained by giving a further cold reduction of 85 pct. Cube texture is developed by annealing at -900~~ in pure hydrogen: it has been produced in strip up to 0.024 in. thick. The microstructure of the strip consists of a mass of small primary grains within the boundaries of the much larger secondary grains which ex- hibited cube-on-edge texture before the final cold roll. If the strip is annealed at -1000 after the 85pct reduction, secondary recrystallization begins to take place, provided a strong cube texture is present. On raising the temperature more secondaries grow, complete secondary recrystallization being obtained on annealing at -1150&apos;. From this it is concluded that the secondary crystals are produced by the texture inhibition mechanism: they show (110) and (111) planes in the surface of the strip, the former being the more numerous. It has been observed that the more perfect is the (110) [001] texture prior to cold rolling by 85 pct, the further from the ideal is the (100) [oo].] texture. A similar treatment applied to high quality commercial grain-oriented silicon-iron strip failed to produce cube texture. The tilt and rotation of the [loo] from the rolling direction was less than 10deg, but (to within a few degrees) the planes (130), (450) and (210) lay in the surface of the strip. Acknowledgment is made to the Engineer-in-Chief of the British Post Office for permission to use the information contained in this note.

Jan 1, 1962

OFFICERS AND DIRECTORS President and Director AUGUSTUS B KINZEL, &apos;60, New York City Past President and Director GROVER J HOLT, &apos;59, Ishpeming, Michigan President-elect and Director HOWARD C PYLE, &apos;61, Los Angeles, Calif

Jan 1, 1958

OFFICERS AND DIRECTORS President and Director HOWARD C PYLE, &apos;61, Los Angeles, Calif Past President and Director AUGUSTUS B KINZEL, &apos;60, New York City President-elect and Director JOSEPH L GILLSON, &apos;62, Wilmington, Del

Jan 1, 1959

By George Rice

SOME form of longwall mining is generally used in Continental Europe; also in Great Britain where the coal is weak and friable, or the coal bed provides material for pack walls and filling, or where the bottom is soft and squeezes up easily, or the roof is pliable, or the bed is thin and brushing provides building material, or the thick multiple seams are mined in layers, such as the 24-ft. seam at Weymss, Scotland or the 10-yd. pitching bed near Coventry, England. Pillar methods have been retained in British fields where the coal beds are from 5 to 9 ft. (1.5 to 2.7 m.) thick, and free from thick partings or binders or without draw slate, which would provide waste rock for pack walls, or where the roof is hard and requires shooting to bring down and also the bottom or floor is comparatively hard. The room-and-pillar system, by which probably 95 per cent., of the coal of the United States is produced, is now found in only a few mines in Wales, where it is known as the pillar. and .(single) stall method. The American room-and-pillar system is not equivalent to the bord-and-pillar or stoop-and-room system. The essential difference between the bord-and-pillar and the average American room-and-pillar system is probably due to natural conditions. The majority of the coal mines in the United States have a depth of less than 700 ft. (213.m.). The bulk of the coal mined in Europe comes from a depth of more than 1200, ft., while the deepest mines in Great Britain, Belgium, and France reach 3500 to 4000 ft. In deep workings wide spans are impracticable, even with the use of abundant timber; accordingly, as the mines in the United States become deeper the rooms will become narrower and the pillars thicker, and the bulk of the coal will be extracted on the retreat. It is generally conceded, without reference to the cost of production, that the larger the pillars left on the first mining, the more thoroughly can the, coal be extracted. In Europe complete extraction is generally compelled either by the lessors or by the governments; whereas in this

Jan 2, 1921

By O. N. Carlson, H. A. Wilhelm, H. E. Lunt, J. M. Dickinson

On the basis of data obtained from microscopic examination, melting observations, cooling curves, X-ray analyses, and resistance measurements, phase diagrams have been proposed for the Th-Cb and Th-Ti alloy systems. Both are simple eutectic systems and have no terminal solid solubility or intermediate phases. The eutectic between thorium and columbium occurs at a composition of about 8 wt pct Cb and a temperature of 1435°C. The Th-Ti eutectic occurs at 1190°C at the composition 12 wt pct Ti. No change was observed in the transformation temperature of thorium in either system or in the titanium transformation. RECENT study of thorium and its alloys has been promoted because of the possibility of employing this metal in nuclear reactors. Their corrosion resistant properties, nuclear characteristics, and high melting points put columbium and titanium among the many metals being employed in the study of thorium alloys. Since a knowledge of the phase relationships would be important in the application of such an alloy, investigations were undertaken to propose phase diagrams for the Th-Cb and Th-Ti systems. Experimental Procedures Thorium metal sponge was specially prepared for use in this investigation. Carbon in a quantity less than 0.04 wt pct was the principal impurity. There was also less than 0.01 pct each of iron, calcium, zinc, aluminum, and nitrogen in the thorium. Columbium, both as a powder and sheet metal, was obtained from the Fansteel Metallurgical Corp. The manufacturer&apos;s specifications indicated that the metal contains less than 1 wt pct total impurities. An analysis of the metal showed approximately 0.18 pct C in the powder and less than 0.05 pct C in the sheet. The titanium used was commercial sponge, reported to be 99.5 pct Ti. An analysis showed that this metal contained 0.2 pct Fe. Preparation of Alloys—Since the metals used in this investigation are reactive and might become contaminated on melting in a refractory crucible, the alloys were prepared by arc melting. The titanium sponge was employed in the form of small lumps while the columbium additions were made either as pressed pellets of powder or as clippings from sheet. The alloying material and the thorium sponge were melted together under argon in conventional arc melting equipment employing a tungsten electrode and a water cooled copper crucible.

Jan 1, 1957

By A. U. Seybolt

Since the time this topic was originally treated in 1954, more recent French3,1 work has been published making it advisable to repeat the earlier oxygen solubility experiments, but using iron of a higher purity. Upon repeating oxygen saturation experiments with zone-refined iron, it was found that the oxygen solid solubility was at least an order of magnitude less than previously observed. SINCE the publication of an earlier paper1 (1954) on this subject by the present author, several contributions on this topic have appeared. Meijering2 in 1955 attempted to reconcile recent conflicting solubility data, without reaching any definite conclusion. sifferlen3 (1955) found that iron of high purity appeared to absorb a quantity of oxygen (0.005 to 0.025 pct) approximately proportional to the structural imperfections present, such as polygonization and grain boundary area. However, he also indicated that purity itself was a significant factor. He concluded that very pure iron nearly free of lattice imperfections would have essentially zero oxygen solubility. His second paper4 (1957) supported this contention since a zone-melted iron containing initially 0.0007 pct O analyzed only 0.0006 pct 0 after prolonged soaking at 850°C with an FeO layer on the surface. Because of the discrepancy between the results of Ref. 1 and those of Sifferlen, it seemed desirable to attempt to resolve this disagreement. EXPERIMENTAL PROCEDURE AND MATERIALS The experimental method used by sifferlen3,1 was essentially the same as that of Ref. 1. In this technique thin iron strip with a surface layer of FeO is soaked for prolonged periods at an elevated temperature in order to saturate the iron with oxygen. After two days at temperatures near 800° to 900° C, one would expect that the iron would be in equilibrium with the surface FeO. In the work reported in Ref. 1 there was evidence that two days holding at 8000to 900°C was more than sufficiently long for saturation. Sifferlen used 48 hr at 850°C. Because of the evidence presented by Sifferlen that the apparent oxygen solubility is a function of iron purity, three grades of iron were used as indicated in Table 1. The Bureau of Standards wire was used only for resistivity tests, while the other two irons were used for saturation-analysis tests of the type described above.

Jan 1, 1960