Search Documents

By Robin O. Williams

The textures which are produced by simple shear in poly crystalline samples of copper, brass, aluminum, iron, and zirconium have been determined. For the fcc materials, there are two major textures, both of which are oriented for slip on the usual slip systems. It is shown that each grain will, in general, give rise to both orientations through the production of deformation bands. This is considered a clear demonstration that such bands aye produced by the heterogeneous deformation which takes place instead of the five-slip-system model considered by Taylor. The results on iron and zirconium are more limited but would appear to exhibit certain additional complexities. It is suspected, however, that the general consideration of deformation bands may apply here also. One finds some correlation between the textures produced by this single shear and the conventional textures although it would appear- that additional data and analysis are requived to produce a strong correlation. It is somewhat remarkable that of all the texture investigations only a very few have been concerned with the action of simple shear on polycrystalline aggregates. Of these limited investigations, all used torsional strains and only in Backofen's' and Backofen and Hundy's "ork was sampling carried out so as to derive a texture in terms of the shear direction. Some rather remarkable conclusions re- sulted from Backofens'1,2work: 1) the rate of texture formation in copper is high, being almost complete at a shear strain of unity; 2) the texture does not change if the sample is sheared back, although the surface grains return to their original shape; and 3) the texture is complex in that it has four components, three of which have [110] as a shear direction. These conclusions were based on both qualitative and quantitative data. Shear deformation is intermediate in complexity between simple shear of single crystals and the usual deformation of polycrystals; hence, one might expect to learn considerable from the extension of this work. CONVENTION Deformation in simple shear has the lowest possible symmetr3, less than the other simple modes of deformation (rolling, drawing, and compression); hence, one cannot necessarily expect the textures to have the same degree of symmetry. The geometry of the process is represented by Fig. 1 along with its sltereographic projection. One has the shear plane, the shear direction, the mirror plane normal to the shear plane and containing the shear direction, and a neutral plane normal to both the shear plane and mirror plane. These planes divide the projection into four quadrants. These quadrants are not, however, identical, since all directions within the upper left and lower right are being shortened by the shear process, and the other directions are being lengthened. The first kind are called compression quadrants and the direction of greatest contraction rate, at 45 deg, is labeled with a minus sign; the corresponding direction of greatest extension rate

Jan 1, 1962

By George R. Cowan

A number of studies hare been reported of the effects produced in metals subjected to deformation by shock waves with maximum pressures ranging from tens to hundreds of kilobars. On the basis of the equations for the flow of mass, momentum, and energy through a stationary shock front, the macroscopic stress-strain curve for the resulting shock deformation can be calculated within narrow limits from the experimentally determined Hugoniol curve. In relatively weak shocks which are preceded by an elastic wave, the stress rises above the clastic limit only as plastic deformation proceeds cold thus the shock has a long toe. In strong shocks that override the elastic wave a high stress is applied without prior plastic deformation. A more important effect of increasing the shock pressure is the generation of shear stresses, called supercrilical shear stresses, that exceed the strength of the perfect lattice. A change in the mechanism of deformation is expected to result from the onset of supercritical shear. The shock disordering of ordered Cu3Au in strong shocks appears to be an example of such a change. It is suggested that the formation of fine twins in copper and nickel and the formation of structures which enable visible twins to be formed in the rarefaction ware, observed in copper and presumably in disordered Cu3 Au, are related to the occurrence of supercritical shear in shock dcformation. In recent years several studies1,2 have been made of the changes in structural and mechanical properties of metals produced by the passage through the metals of strong shock-compression waves ranging from about 50 to 800 kbar pressure. Recent work involving dynamic measurements of the shock compression "Hugoniot" curves 3-8 of many metals has developed techniques and provided data required to obtain the shock pressure and the (transient! plastic deformation produced in the shock-conlpression experirnents.9 Shock deformation has been found to be much more effective than slow deformation in changing the mechanical properties of metals, when the two are compared on the basis of equal plasti strain, Holtzman and Cowan9 made quantitative estimates of the shearing stress occurring in a shock front in a metal by assuming that the shearing stress is similar to that occurring in a shock front in a viscous, heat-conducting fluid, with the addition of a yield stress. Taylor's solution9 for a weak shock was used to estimate pairs of values of shearing stress and thickness of the shock front obtained by assumed choices of the ratio of effective kinetic viscosity to thermal diffusivity. It was noted from these values that. unless the shock front is extremely thin. heat conduction has slight effect, and the shearing stress is nearly independent of the mechanism of deformation. This mechanism does, however, determine the thickness of the shock front and the rate of strain. Furthermore, since the maximum possible shearing stress occurring in shocks of moderate strength does not greatly exceed the shear stress occurring in conventional slow deformation, the mechanism of deformation is not expected to be qualitatively different. The greater effectiveness of shock deformation in changing the mechanical properties of metals can be attributed partly to the fact that dislocations, when driven by near-conventional stresses, cannot keep up with the shock front, thus necessitating a higher dislocation density than required for an equivalent slow strain. The fast uni-axial strain occurring in the thin shock front would also be expected to cause a larger number of dislocation intersections to occur. In the upper range of shock pressures that have been studied the estimated values of the shearing stress exceeded the estimated shear strength of a perfect crystal. Under these circumstances it is reasonable to expect that the mechanism of deformation might be considerably different from that involved in slow deformation. Except for the observation by smith1 of twins in shocked copper, the effects of shock waves on metals did not show any obvious or large changes in properties that would indicate the onset of a change in the mechanism of deformation. The recent investigation of the effect of shock waves on ordered and disordered specimens of Cu3Au by Beardmore, Holtzman, and ever" showed a spectacular decrease in the amount of long-range order retained by initially ordered Cu3Au when the shock pressure was raised from 290 to 370 kbar. Since Dr. Holtzman and I suspected that this behavior probably was due to the onset of a shearing stress in the shock front in Cu3Au which exceeded the limiting shear strength of the perfect crystal. it was considered appropriate to examine directly the shock-front equations for a solid. and to obtain a sound estimate of the shearing stress occurring in the front using equation of state data obtained from shock studies. In this paper an estimate is made of the

Jan 1, 1965

By P. C. Johnson, B. A. Stein

This paper describes a study of the effects of combined heat treatment and explosive loading on the mechanical properties of high-strength steels. nis program investigated two distinct areas: 1) the effect of shock waves, without gross irreversible defmmution, on a 3-Cr steel at various stages of heat treatment; and 2) the effect of rapid deformation (explosive forming) on H-11 and D6-AC steels in the metastable austenitic state. The mechanical properties of these steels were improved, in some cases markedly, as a result of these treatments. ,AUSFORMWG, which requires the plastic deformation of metastable austenite, is a process which can appreciably improve the properties of selected alloy stee1s.l,2 The Ausform process significantly increases the strength of these steels without decreasing their ductility. The properties at high temperatures are also improved through a change in the response of the steels to tempering. Although the mechanism by which ausforming alters the properties of these steels is not fully understood, it appears that the dislocation arrays produced by deformation of the metastable austenite influence the structure of the martensite on subsequent transformation. This, in turn, affects the strength, ductility, and tempering response of the martensite. This research used chemical explosives to deform steels at various stages in their heat treatment in order to improve the properties of these steels. The explosive energy is used in two ways; 1) high-pressure shock waves are propagated through the steel to produce extensive microscopic shear strain without causing a large irreversible change in shape, and 2) explosive energy is used to cause extensive macroscopic plastic strain in the metastable austenitic state (explosive forming). I) AUSFORMING WITH INTENSE SHOCK WAVES The steel used in this phase of the research was an alloy having a nominal composition 0.43 pct C, 3.0 pct Cr, 1.5 pct Ni, and 1.5 pct Si. The steel was subjected to intense shock waves in three conditions: 1) in the metastable austenitic state, 2) in the tempered mar tens itic state, and 3) in the tempered martensitic state after ausforming by conventional techniques. The specimens were in the form of disks 2.75 in. in diam and 5/16 in. thick. These were incorporated into a specimen assembly consisting of two disks pressed into a 5 by 5 by 1 in. block of stainless steel, Fig. 1. Spalling (or scabbing) is confined to the front disk. The specimen is protected from oxidation and decarburization by the surrounding metal. The temperature of the assembly is monitored by a thermocouple inserted into one side of the stainless steel block. The assembly is positioned over an oil reservoir which serves both as a means of catching the disks and as quenching medium for the disks shocked under ausforming conditions. Plane shock waves are introduced into the assembly by a metal driver plate impacting the top surface of the block. The driver plate is accelerated by a chemical explosive sheet supplied by E. I. du Pont de Nemours & Co. All the specimens were subjected to plane shock waves having a peak pressure of approximately 430 kbar. The pressure is that quoted by G. E. Dieter for the plane wave generator used in this work.' The driver plate used was 1/4 in. thick, so that the initial pulse was essentially a l/2-in.-wide square wave. The attenuation of the peak pressure during the subsequent 1/4 in. is estimated to be less than 5 pct. The shock front induces a temperature rise, a portion of which is irreversible. Rough estimates (+25 pct) of this temperature rise have been made for iron shocked at room temperature.4 For a 500-kbar shock wave, the temperature rise in the shock front is about 700°F, and is held for a time of the order of microseconds. The irreversible temperature rise, which remains after the shock wave passes, is about 450°F.4 The disks are quenched to room temperature within a few seconds of the shock treatment. It should be emphasized that the temperature rises given above are estimates for pure iron at room temperature, and are not necessarily true for the tests made in this work. The disks shocked at temperatures in the metastable austenitic range were austenitized in the stainless steel assembly in a furnace protected from the firing area. The assembly was removed from the furnace and placed over the recovery reservoir. The plane wave generator was then positioned and

Jan 1, 1963

By R. G. McQueen, E. G. Zukas

THE production of isotropic fine-grained ingot iron would be most useful since physical measurements associated with the elastic properties of iron are influenced by the size and orientation of the individual grains. This can be accomplished at present for small samples by established metallurgical procedures, but for large samples (in excess of 2 in. diam by 1 in. thick) it is virtually impossible to produce reasonably small uniform grains with random orientation. Such pieces can, however, be produced by impulsive loading followed by a suitable recrystallization treatment. The shock loading system employed is diagrammed in Fig. l. Here the 3/8-in. iron plate is accelerated by the plane-wave initiated high explosive charge through a 1 5/8-in. air space. Collision of this plate and the specimen of interest generates a shock wave in excess of 300 kbars which passes through the specimen. For this type of work it is not necessary to use machined parts: for example, the ingot iron pieces are saw cut from the billet so that they can be inserted in short sections of iron pipe. The recovered specimens are less distorted, however, if the air gap between the iron sample and pipe is filled with Woods metal. The dimensional changes resulting from this type of loading technique are minor, usually less than a 10 pct reduction in thickness. Compressive yield

Jan 1, 1962

By M. C. Smith, W. V. Green, D. M. Olsen

The creep-rupture behavior of commercial powder-metallurgy molybdenum rod is reported in the temperature range 1600" to 250O°C, at stresses up to 9000 psi and times up to 1 month. The effects of temperature, stress, and grain growth are discussed. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher-stress results reported by pugh.1 BECAUSE of its high melting point, molybdenum should retain useful strength to relatively high temperatures. Combined with its ready availability in the United States, this makes it attractive for many applications in missiles, rockets, and so forth—wherever its susceptibility to oxidation can be tolerated or overcome. The mechanical properties of molybdenum rod in the temperature range —200" to 1540°C have been reported by pugh,' Bechtold,' Parke,3 and Carriker and Guard.4 Madden and chen5 have measured the tensile properties of molybdenum single crystals in vacuum up to about 2500°C. As one further step in evaluating its mechanical usefulness, the constant-load creep-rupture properties of commercial powder-metallurgy molybdenum rod have been investigated in the range 1600" to 2500°C. MATERIAL TESTED Creep specimens were machined from 1/2-in. round commercial molybdenum rod, manufactured from powder by pressing, sintering, and swaging. Spectrochemical analysis of the rod showed "traces" (less than 0.01 pct) of silicon, aluminum, chromium, iron, and zirconium, and "faint traces" (less than 0.001 pct) of manganese, magnesium, cobalt, and nickel. Carbon content was 130 to 200 ppm, nitrogen was 110 to 180 ppm, and oxygen 30 to 35 ppm. A typical microstructure of the as-received rod is shown in Fig. 1. Room temperature tensile properties for five specimens strained at about 0.015 in. per in. per min are shown in Table I. CREEP SPECIMENS USED The specimens used for creep-rupture testing are illustrated in Fig. 2. The 1/4-in.-diam gage section was 3/4 in. long, and terminated at shoulders 5 mils high. These shoulders served as fiducial marks for optical strain measurements. Surface finish on the gage section was 16pin. r.m.s. One specimen, for a "long-time" test described below, was modified by dividing the 3/4-in. gage length into three 1/4-in. long sections with individual diameters of 0.250, 0.230, and 0.210 in., each terminating in a pair of fiducial shoulders. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.6 In it the specimen is held vertically on the axis of a cylindrical tantalum or tungsten heater tube by threaded molybdenum or tungsten grips. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. The bottom specimen grip is held at its lower end by a clevis pin. The testing load is applied to the specimen through the upper grip by means of hanging weights, a constant force-multiplication lever system, and a pull rod sealed to the chamber lid by a bellows. The incandescent specimen is viewed by an external optical system through slots in the heater-tube and radiation shielding, and an enlarged image of it is projected on a ground-glass screen. Gage-length measurements are made on this image with a pair of cathetometers. Thorium oxide coatings were applied to the threaded ends of most specimens, to prevent diffusion-welding of specimens to grips during testing. Without such a coating welding usually occurred, and grips were often broken by subsequent efforts to remove the tested specimens.

Jan 1, 1960

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The times at which the first detectable amount of a phase forms at temperatures between 900° and 1800°F were determined. Both X-ray diffraction and metallography were used to detect a in highly strained filings; metallography alone to detect it in annealed bulk samples of six different types of stainless steels. The a phase was found to form in accordance with the C-type reaction curve in both austenitic and ferritic alloys. In filings of types 304, 347, and 446, a formed in a few hours, and in types 316, 309, and 310, it formed in a matter of minutes at temperatures corresponding to the knee of the C-curve. Only in the bulk type 309 steel, after 500 hr, and in the bulk type 310 steel, after as short a time as 25 hr at temperature, was n detected; in both instances at approximately the same optimum temperature as in the filings. The annealing temperature affected a phase nucleation only for the filings of type 304 and 347 steels, and for the bulk samples of type 309 and 310 steels. KNOWLEDGE of both the rate of nucleation and the rate of growth of the new phase is required for a complete description of metallurgical rate phenomena. However, data on the time for nucleation alone may frequently be useful in evaluating the tendency of commercial stainlcss steels to form s under various conditions. Very little correlated information of this type is available in the literature. Shortsleeve and Nicholson' indicate that s forms in ferritic 24, 27 and 30 pet Cr steels according to a C-type of reaction curve, and Emmanuel's' data for austenitic type 310 steel also suggest this type of solid state reaction. In addition, significant, though fragmentary, information has been given by Binder, Dulis and Smith,4 Payson and Savage,.; Guarneri, Miller, and Vawter,8 rerichs and Clark,7 Wilder,5 Lismer, Pryce, and Andrews,' Smith, Dulis, and Link,10 Dulis, Smith, and Houston," and Henry, Cordovi, and Fischer." The bearing of these data on this work is covered in the discussion. The purpose of this paper is to present such correlated data on s formation in AISI type 304 (18 pct Cr-8 pet Ni), 347 (18 pet Cr-10 pet Ni-Cb), 316 (18 pet Cr-12 pet Ni-2 pet Mo), 309 (25 pet Cr-12 pet Ni), 310 (25 pet Cr-20 pet Ni), and 446 (27 pet Cr) stainless steels. Materials and Test Methods X-ray diffraction and metallographic methods were used to determine the first appearance of the s phase in cold worked filings and in annealed bulk samples of seven steels, under various combinations of time and temperature. The rate of growth of the s particles was not determined. Commercial heats of six AISI steels and a low carbon laboratory experimental heat containing about 28 pet Cr were studied. Analyses are given in Table I. Because cold work greatly accelerates the nucleation of s particles, the relative rates of s nucleation in mechanically strained samples, i.e., filings through 120 mesh, were determined for direct comparison with those in annealed bulk alloys of the same composition.

Jan 1, 1957

By K. P. Gupta

The Cb-rich boundary of the (Cb,Al) a phase field at 1250OC is near 41 pct Al. The Al atoms tend to occupy the C. N. 12 sites in this structure. A homologous (Ta,Al)a phase was identified. No a phase was found in the Mo-Al system at 1200°C. The first binary o-phase with a non-transition element as a major component was found1,2 in the Cb-Al system. The composition of this phase was reported2 as approximately 34 at. pct Al, based on X-ray diffraction patterns taken of alloys in the as-cast condition. Further study of the composition of this o-phase, therefore, appeared desirable. Since Si was previously found3,4 to occupy preferentially the lowest C.N. sites (I and IV) in the a phase, and preliminary resultsa indicated that Al may show similar ordering, one of the aims of the present work was to obtain more complete information on ordering in (Cb, Al) o. Among the binary systems of Al with Ti-, V-, and Cr-group elements, the Ti-Al, Zr-Al, V-Al, and Cr-Al systems are known to comprise no o-phase. In the present work a Ta-Al and a Mo-Al alloy were studied in an effort to find additional o phases with Al as a major component. EXPERIMENTAL PROCEDURES AND RESULTS An alloy with the intended composition of Ta + 40 at. pct Al was prepared by arc melting in He atmosphere. In both the as-cast condition and after annealing for 10 days at 1250°C and quenching in cold water this alloy consisted of two phases, as seen in the X-ray pattern and the microstructure. One of these phases was identified as the o-phase; the observed and calculated d-spacings are shown in Table I. The lattice parameters of this o-phase are a = 9.972 A, c = 5.214 A and c/a =0.5228, as determined from a Debye-Scherrer pattern using Fe K a radiation. The d-spacings for the unknown second phase are given in Table 11. The alloy contained approximately 25 pct of the unknown phase after annealing, as estimated on the basis of microscopic examination. A Mo-Al alloy was prepared by arc melting, with an intended Al-content of 35 at. pct. The alloy button was annealed for 7 days at 1200°C and water quenched. The X-ray pattern of the alloy in both the as-cast and the annealed state showed the reflections of Mo3Al (Cr30 type structure) and an unknown phase different from a. Six Cb-Al alloys were prepared in the composition range 30 to 50 pct Al. All alloys were arc melted in He atmosphere. After annealing for three days at 1175oC in evacuated silica capsules and quenching in water, the alloys with 30 to 40 pct Al contained three phases, namely the o-phase, Cb3Al (Cr3O-type structure) and an unknown phase. The alloys with more than 40 pct Al contained two phases, namely, what appeared metallographically, the o-phase and the same unknown phase. In the alloys containing less that 38 pct Al, the unknown phase was not present after annealing for 4 days at 1250°c,

Jan 1, 1962

By Joseph B. Darby, Paul A. Beck

IN isothermal sections of several ternary systems, the a-phase was found1 to extend in the form of a relatively narrow elongated field, connecting the U-phases that are present in the adjoining binary systems. This was interpreted in accordance with the conception that the U-phase is an electron compound and the ternary U-phase fields were shown in several systems' to extend approximately in the direction of constant average d-shell electron vacancy number per atom. ' However, in the various isothermal sections of the Fe-Cr-Mo system" the ternary a-phase field was

Jan 1, 1958

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7'8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

By W. C. Hagel, J. H. Westbrook

Usittg a sectioning technique with Agl10 as the tracer, the diffusion of silver in silver-excess (45.8 at. pct Mg), near-stoichiometric (49.8 at. pct Mg), and magnesium-excess (52.0 at. pct Mg) cylinders of CsCl-type AgMg was determined from 500" to 700°C. Diffusion coefficients conform to the expression D = Do exp (-q/RT) where the respective Do values are 1.53, 0.280, and 0.134 sq cm sec-I and the Q values are 41.3, 40.6, and 38.0 kcal g-atom-'. Lnttice-parameter and density measurements were performed on a more numerous assortment and wider range of compositions. Substitutional defects were found on both sides of stoichiometry. Activation energies for other rate processes in these alloys show related trends with changing composition, although silver may not be the rate-detemining species. KNOWLEDGE of diffusion coefficients is necessary for a quantitative understanding of the many rate processes (e.g., grain growth, precipitation, sintering, oxidation, or mechanical deformation) occurring in solids. Although these data are available for most metals and common alloys, they are quite limited for intermetallic compounds—a group of materials whose unique physical and mechanical properties are presently attracting great interest. From a fundamental viewpoint, diffusion in intermetallic compounds also offers several engaging aspects owing to: their ordering, the possibility of introducing large, stable concentrations of lattice defects, and the variety of bonding types and crystal structures which can be found. In the case of CsC1-type compounds, some previous work has been directed at examining the role of vacancy defects by changing their concentration compositionally. The diffusion of Co60 was measured in 0 NiAl1- and in P COA., Except for the results of Smoluchowski and Burgess, isothermal diffusion coefficients were found to pass through a minimum at the stoichiometric composi- they decreased sharply on what was reported by Bradley and co-wrkers' to be the vacancy-rich (aluminum excess) side of stoichiometry. This investigation of the diffusion of Agl110 in AgMg was undertaken both as an adjunct to a concurrent study of its deformation behavior and for the purpose of obtaining information on the influence of lattice defects and temperature on diffusion in another CsC1-type intermetallic compound. Bcc AgMg remains ordered up to and melts congruently at 820°C. Solubility limits at 300°C are about 41 at. pct Mg and 53 at. pct Mg. It is one of the Hume-Rothery electron compounds with a 3/2 electron-atom ratio. Previous investigations of its properties include hardress,' tenile,'-' electrical reistivity, and thermodyna-mic1',14 studies. Indications of a high bonding strength may be found in the large heat of mixing1' and in the 6-pct vol contraction on compound formaticp, as calculated using atomic radii of l.40 and l.55a for Ag and Mg. EXPERIMENTAL PROCEDURE Alloys were prepared by the induction melting of selected fine silver (99.95) and low-iron magnesium (99.95) in magnesia crucibles under 1 atm of A. Supplied by the Handy and Harmon and Dow Chemical Cos., respectivelv. Melts were poured under argon into graphite molds providing 1 1/8-in.-diarn. by 4-in.-long ingots. These were homogenized in evacuated and argon-filled fused-silica capsules by heating for 16 hr at 750'. Three 1 in.-diam. by 3/4-in.-long cylinders were machined from the mid-portion of each ingot for diffusion measurements. Three alloys, analyzing 45.8, 49.8, and 52.0 at. pct Mg were taken as representing the extremes of interest, with 49.8 at. pct Mg being very close to the stoichiometric composition of 50.0 at. pct Mg.

Jan 1, 1962

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß'. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß' which in turn form the Widmanstatten a in ß'. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.' There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence'..' in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"' ' report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

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 C. G. Dunn, P. K. Koh

TWO recent review papers have considered the origin of primary and secondary recrystalliza-tion textures from the point of view of oriented nucleation and oriented growth theories."' Both theories require nuclei for primary recrystallization but provide no unequivocal answer to the question of what nuclei are. The answer to the same question regarding secondary recrystallization, however, often is that nuclei are certain primary recrystallization grains or primaries. The two theories differ, however, in specifying what the certain primaries are. In support of the oriented growth theory Beck and Hua originally stated "It may be assumed that in a re-crystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as nuclei for the coarse grains, provided that conditions are favorable for their growth." In commenting on this statement one would say that there are two restricting conditions: namely, that 1) the certain primaries (nuclei) are large enough to grow, and 2) their boundaries have high mobility. More recently Beck2 has con-

Jan 1, 1958

By J. D. Lubahn

The influence of precipitation from solid solution on the subsequent deformation resistance of alloys is well known. However, the influence of precipitation or aging that occurs simultaneously with deformation may be entirely different and of considerable importance. It is thought1 that the presence or absence of a yield point jog in impure iron at room temperature and the presence or absence of discontinuous flow at higher temperatures may be directly related to aging phenomena, particularly since the yield point jog is absent when the carbon and nitrogen are sufficiently removed.2 As a preliminary attack on the problem of simultaneous aging and deformation, three kinds of tests—constant strain rate tensile tests, constant load creep tests, and variable strain rate tensile tests—were carried out on an age hardenahle aluminum alloy. Constant Strain Rate Tensile Tests Stress-strain curves at a strain rale of about 0.001 min-1 were obtained for specimens of 61S that had been quenched into liquid nitrogen after a one-hour solution treatment at 521°C, then aged at room temperature 10 min., 20 min., 4 hr, and 26.5 hr before testing. Strain-time curves were obtained on the same chart with the stress-strain curve by means of an auxiliary pen, driven parallel to the axis of the chart drum at constant speed by a synchronous motor and gear chain. The angle of rotation of the chart drum was proportional to strain. The strain rates reported are the measured slopes of the strain time curves. Constant strain rate was approximated (within a factor of 2) by manual adjustment of the oil inlet valve of the hydraulic testing machine in such a way that the course of the recorder pen was parallel to pre-drawn strain-time lines of the desired slope. The specimens were machined from 9/16 in. rod. The cylindrical portion was 0.357 in. in diam by 13/4 in. long and

Jan 1, 1950

By F. W. Glaser, W. Ivanick

A pressure-sintering method was used to produce binder-free and very dense TiC specimens. Some physical properties of these TIC bodies were determined and found to compare favorably with those of certain cemented Tic grades. It was also observed that the hot transverse rupture strength of TiC bodies remained substantially the same regardless of the amount or type of binder material used. STUDIES of the structure and physical properties of refractory materials have been intensified recently because of the urgent need for nonstrategic materials that retain their strength at high temperatures. Research aimed at determining and improving the physical properties of cemented carbides and borides has been accelerated with a view toward possible use of such materials in connection with turbine blades, rocket nozzles, and other high temperature applications. On the hypothesis that the strength requirements in connection with some of the above applications could be met only by proper choice of cementing agents for such refractory materials, the literature describing the physical properties of borides or carbides was reviewed. However, with a few exceptions,'-" references were found only to compositions containing at least one or more auxiliary binder metals. Cobalt and nickel are among the most frequently employed cementing agents. The melting point of Tic (approximately 3250°C) and therefore the sintering temperature, at which notable densification of a cold pressed Tic powder compact could be expected in the absence of a liquid binder phase, is relatively high. The present study makes use of a high temperature, pressure-sintering procedure, recently described by one of the authors in connection with the sintering of binder-free ZrB,," to produce dense bodies of sintered Tic—free of any cementing agent. During the course of this sintering study, some physical properties of dense Tic bodies produced by this method will be discussed. Materials, Preparation of Samples, Testing Methods The procedure for the forming of Tic powder consisted of mixing graphite and TiH, powders in stoi-chiometric proportions, and heating this mixture in a H, atmosphere and carbon crucible by high frequency, to temperatures ranging between 1900° and 2100°C (3452" and 3812°F). The powdered carbide was then comminuted and screened to the desired particle size. Table I shows the chemical analysis of the two grades that were employed for the production of samples during this work. Bodies of Tic, approximately 2.5xlx0.5 cm were produced in graphite molds that were heated by direct conduction. Sintering was carried out at temperatures for time intervals ranging from approximately 0 to 30 sec under a constant pressure of about 1.3 tons per sq in. An alternate method for the production of samples consisted in cold pressing the individual Tic grades at pressures ranging from 4 to 10 tons per sq in. and sintering in a hydrogen atmosphere in graphite crucibles heated by high frequency induction. Sintering temperatures ranged from 2600° to 2900°C (4715° to 5255°F). Electrical testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp at room temperature. Cross-sectional areas as well as densi-

Jan 1, 1953

By J. H. Brophy

Experimental evidence in recent years shows that nickel coated hydrogen reduced tungsten powder can be sintered to 98 pct of theoretical density at 1100°C. New data indicate that the sintering rate is the same for nickel contents ranging from 0.125 wt pct (mon-atomic layer) to 5.0 wt pct Ni coated on 0.561. tungsten powder. Nickel tungsten made by coreduction from oxides sinters in a kinetically similar way, but the rate tends to increase with higher nickel contents. The activation of sintering can be accomplished with a minimum amount of nickel if coated powder is used. Transverse rmpture strength was found to increase in specimens containing 0.25 pct Ni as density increased during the initial stage of the carrier-phase sintering process. Upon the onset of grain growth in the final stage, strength was found to decrease. With increasing nickel contents up to 4 pct, strength increased. Maximum strengths in three-point loading were observed at 73,000 psi for 0.25 pct Ni and 93,000 psi for 5 pct Ni. These were comparable to that of massive tungsten recrystal-lized in the presence of nickel and tested in the same way. The results were sensitive to the mode of powder treatment and ductility was negligible in all cases. The study and application of sintered bodies of nickel and tungsten is not new; however, the analysis of the mechanism by which small additions of nickel increase the sintering rate of tungsten promises to Contribute new information regarding sintering theory in general. Initial experimental evidence was presented by the authors showing that nickel-coated hydrogen-reduced tungsten powder may be sintered to 98 pct of theoretical density at 1100°C in 16 hr.' Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the 'solution-precipitationo step postulated when the carrier phase is liquid3 although in the nickel tungsten case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in mi-crostructures at the temperatures under consideration. In the present work, new data for nickel-coated tungsten powder are offered in support of the proposed mechanism, and a more explicit study of the second stage of densification is presented. Concurrently, the sintering kinetics of these coated powders are compared to Ni-W powder made by coreduction of oxides. In this way the present work can be compared to earlier results in nickel activated sintering of tungsten in which the coreduction process was emplyed. The ultimate utility of such an activated sintering process will be determined to some extent by the mechanical and physical properties of the final prod-

Jan 1, 1962

By E. J. Westerman

Prealloyed powders of nickel-base superalloys were sintered to almost theoretical density in short sinterilzg times. It was ascertained that the rapid densification was caused by a small amount of liquid phase at the grain boundaries, which apparently ovriginated by incipient melting at temperatures considerably below those at which macroscopic melting of the compacts occurred. An increase in the quantity of liquid phase present during sintering-, caused by an increase in the sintering temperature, increased the densification rate, but resulted in a decrease in the room temperature tensile propevties. NICKEL-base superalloys, which presently comprise an important group of high temperature alloys, are difficult to fabricate by the forging, casting, and machining operations presently used. As it was felt that fabrication by powder metallurgical techniques might offer advantages in the production of super-alloy parts, a basic investigation of the most important process in the sequence of powder metallurgical operations, the sintering process, was undertaken on Rene 41, Udirnet 500, and Nimonic 90 and 100 powders. These alloys age harden by the precipitation of the ? Ni, rA1,Ti) phase. Nickel-base superalloys of the Nimonic type have been fabricated by powder metallurgical methods, and their mechanical properties reported in detail.' Other alloys for high temperature service which have been fabricated by powder metallurgical methods include a Co-base alloy of the Vitallium type;2,3 alloys with a Co-Ni-Fe-Cr base;4 stainless steels;5'6 Cr-W-Co alloys;" and a Co-base alloy, X-40.8 METAL POWDERS The superalloy powders investigated were: a) a prealloyed at.omized Rene 41 powder; b) a prealloyed atomized Udirnet 500 powder; c) a prealloyed atom-

Jan 1, 1962

By W. L. Finlay

Size effects in quenching steel are particularly prominent and well recognized because of the existence of a critical cooling rate separating nuclea-tion and growth transformations, as exemplified by the formation of pearl-ite, from the shear type of transformation characterizing the martensite reaction. The absence of a similar, sharply demarcating cooling rate is characteristic of precipitation hardening systems and size effects in these are correspondingly less prominent. This paper is concerned with a size effect in high-purity, precipitation-hardenable alloys which appears not to have been recognized previously. This effect is believed to result from the thermal fluctuations which inevitably occur in quenching a specimen of finite size into a cooling liquid rather than from the existence of a critical cooling rate. QUENCHING "ANOMALIES" The precipitation hardening literature contains many references to so-called anomalous quenching and aging results. By "anomalous", investigators usually meant that their alloys did not consistently harden on aging after quenching according to some anticipated pnttern: not infrequently virtually no age hardening occurred with compositions known to be precipitation-hardenable. Perhaps the most prominent series of anomalies was reported over a 15-year period by Gayler and coworkers on aluminum-copper.l,2,3,4 Working with silver-rich copper alloy, Cohen5 secured some very interesting Rockwell F hardness changes of from 1-5 Rockwell points between the first peak and valley. Fink and Smith borrowed one of Cohen's specimens and, following his heat treatment and quenching practice to the letter, secured6 very different results in which only one peak was obtained and in which the hardness level at the aging lime of Cohen's first peak was 20 Rockwell F points higher. Fink and Van Horn7 encountered serious deviations in age-hardening high purity aluminum-zinc alloys. They stated that "the discrepancies were larger than might be expected from possible experimental errors in the Brinell readings." Geisler, Barrett and Mehl8 likewise encountered anomalous hardening results in aluminum-silver alloys, securing quite different age-hardening curves from two identical specimens. They stated that "the treatments of these samples had been the same, so that the different behaviors could be attributed only to accidental variations in the quenching practice."

Jan 1, 1950