Search Documents

By P. G. Sprang, S. Rosen

The Y-Al- C ternary phase diagram for the com -position range from 55 to 100 at. pct Y and for a temperature of 950°C has been constructed from metallographic and X-ray diffraction data. The significant features of the isothermal section which is presented are the small solubility of aluminum in the binary Y3C phase and the presence of a ternary carbide phase with a small homogeneity range around the composition Y3AlC. The similarity in structure and composition between these two carbide phases is discussed in the light of the misci-bility gap which exists between room temperature and 1300°C, which was the temperature range studied. THE occurrence and stability criteria of ternary T3BC, carbide phases having the L'12 structure and the general formula T3BCx have been discussed in detail by stadelmaier1 and more recently by the present authors., Stadelmaier found many representatives of these phases formed between the T metals Mn, Fe, Co, and Ni and the B metals Mg, Al, Zn, Ca, Ge, Cd, In, Sn, Hg, T1, and Pb. The present authors reported on a new series of iso-structural carbide phases formed between the T metals of the Sc group and the B metal, aluminum. These new phases are unique in that many of the Sc group elements form stable binary carbide phases which occur about the composition T3C and which crystallize with a structure similar to that of the T9BCx ternary carbide phases. Furthermore, these binary and ternary phases are found to coexist in equilibrium with each other. The similarity in structure and composition between, for example, Y3C and Y3AlC in the light of the mis-cibility gap which had been found to exist between these two phases indicated a need for a more thorough knowledge of the phase relations which occur in alloys based upon these compositions. Consequently, an investigation of the phase equilibria in the yttrium-rich portion of the Y-A1-C phase diagram was undertaken. The limiting Y-A1 binary diagram determined by Lundin and Klodt3 and the results of Spedding et al.4 governing the Y3C phase were used as guides in , constructing the diagram. EXPERIMENTAL Alloys weighing about 10 g were prepared by arc-melting powder compacts made from the various components on a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. Good homogeneity was obtained by melting the alloys three times. The purity of the yttrium used was 99.9 pct (0.07 pct rare earths). The purity of the aluminum and the carbon was 99.99 pct. The results of chemical analysis on five representative alloys showed that losses during the alloying process were predominantly carbon losses and that in no instance did the measured concentration of this component differ by more than 3 at. pct from the intended composition. For this reason the alloy compositions which are reported are those of the charges prepared for melting. Three alloys which were analyzed for copper, tungsten, nitrogen, and oxygen compositions showed that no contamination had occurred either during casting or during the subsequent annealing treatments. For the major part annealing treatments were carried out on specimens which were placed in

Jan 1, 1965

By C. E. Lundin, D. T. Klodt

The binary alloy systems, Y-Ti, Y-Zr, and Y-Hf, have been investigated throughout their entire composition regions. There is no compound formation in any of the systems, and each system is characterized by a single eutectic reaction. The eutectic compositions and temperatures are as follows: A eutectoid reaction pct Y and 870°C occurs in the Y-Ti system, whereas a peritectoid reaction,: pct Y and 880°C occurs in the Y-Zr system. Peri-tectic-type reactions at temperatures above the eutectic levels are postulated for the yttrium and hafnium transfovmations. The development of the technology of yttrium has been given considerable attention during the past few years, and studies of binary phase equilibria have, of course, taken a prominent position in this development. In many respects yttrium, in the third group of metals of the periodic table, is similar to the adjacent group of metals, titanium, zirconium, and hafnium, and the knowledge of the phase relationships of yttrium with these metals is basic to their technology. MATERIALS AND EXPERIMENTAL PROCEDURES Materials. The metals for this investigation were supplied by the General Electric Co., Aircraft Nuclear Propulsion Department. The yttrium was in the form of an arc-melted ingot, and the other metals were in the form of high-purity, iodide-Process crystal bar. Table I lists the purities of these materials. Alloy Preparation. Melting was done by conventional techniques in a nonconsumable electrode arc furnace in an atmosphere of purified argon. Melting conditions for each binary system were the same. Each alloy button was inverted and remelted several times to assure homogeneity. Accurate weights of the charges and resultant alloy buttons were obtained to indicate deviations from intended compositions. No chemical analyses were obtained since melting weight losses were consistently in the range of 0.1 to 0.2 pct of the total weight. 10- or 20-g buttons for each 5.0 wt pct composition increment were melted to survey the three individual alloy systems. Additional alloys differing in composition by 1.0 or 0.1 wt pct increments were also melted to study selected regions of the systems. Metallograpllic Techniques. Standard metallo-graphic techniques were followed for mounting and rough grinding. Preliminary polishing was accomplished using 6-u diamond paste as an abrasive on a Metcloth Lap. Final polishing was done on a Microcloth-covered wheel using 1-u diamond abrasive paste. Purified kerosene was used as a lubricant for both polishing stages. • sothermal- Annealing. Alloys were sectioned for as-cast structlure examinations and then homogenized in preparation for isothermal-annealing treatments. Homo{:enization was accomplished by cold pressing the alloy buttons followed by 72-hr anneals at 1100c. The alloys were encapsulated in Vycor or quartz for the homogenization treatments or for isothermal anneals. Resistance-wound or resistance-element tube furnaces were used for the annealing treatments. The homogenized alloy buttons were cold rolled until cracking occurred or until a -in. specimen thickness was obtained. Small -in. square) specimens for the isothermal anneals were then sawed from the alloys. Each specimen was wrapped in tantalum foil before being sealed in the capsule. Temperatures during the anneals were controlled The time at temperature necessary to equilibrate the structures during the anneals was determined for each alloy system by holding triplicate specimens of alloys at a constant temperature for three different periotls. The specimens were quenched and examined microscopically to determine the number and amounts of phases present in the micro-structure as a function of time. Melting Studies. Eutectic temperatures of the three alloy systems were established from the results of incipient-melting studies conducted on as-cast alloys. Specimens to be melted were suspended on a tungsten wire inside a graphite cylinder placed in a glass vacuum chamber. An optical pyrometer was used to follow the temperature of the specimen as it was inductively heated in a high vacuum. The temperatures were corrected for emissivity losses by standardizing the pyrometer with known-melting-point metals. Accuracy of the temperature measurements is estimated to be + 10°C. The melting point of the yttrium was determined to be 1550°C by this technique. The invariant-temperature levels were also checked by an anneal-quench technique. This technique consists of annealing a series of

Jan 1, 1962

By P. Chiotti, J. T. Mason

Metallographic, thermal, X-ray, and vapor-pressure data were employed in establishing the Ce-Zn phase diagram. Nine compounds and three eutectics were observed. The eutectic compositions in weight percent zinc and temperatures are 10 pct and 495"C, 37 pct and 795°C, and 56 pct and 810°C. Three of the compounds, CeZn, CeZnn, and CeZne.5, melt congru-ently at 825°, 87.505°, and 980°C, respectively; the other six compounds, CeZns, CeZns.67, CeZn4.5, CeZn5.25, CeZn,, and CeZnll, decompose peritectically at 820°, 840°, 870°, 885", 960°, and 795"C, respectively. The compound CeZn5.25 is an AB5 type with a small range of composition which lies on the zinc-rich side of the 1 to 5 stoichiometry. Zinc vapor-pressure data obtained by the dewpoint method were employed in calczilating the thermodynamic properties of both the liquid alloys and solid compounds. The data for the A critical review of the information available on the Ce-Zn system up to 1960 has been given by K. Gschneidner, Jr.' Of particular interest is the work by J. schramm2 who investigated the region between 55 and 100 wt pct Zn and reported a CeZn,, compound which decomposes peritectically at 785"C, a CeZn, compound which melts congruently at 972"C, and five temperature horizontals at 79@, 817", 840", liquid alloys were fitted to the relation from which the relation was obtained by integration. In these relations F XS is the excess partial molal free energy, N is atom fraction, and the constants c and d have the values c = (-22,000 + 7.0T) and d = 6171,000 + 74.0T). Relations for the standard free energy of formation for the solid compounds were derived from the data. At 973°K the enthalpy in kilocalories per gram-atom z)aries from —11.3 for CeZnz to —8.21 for CeZn~l and the free energy in the same units varies from —7.1 joy CeZn, to -3.82 for CeZn11. and 942°C in the region between 55 and 75 wt pct Zn. No attempt was made to identify other features of the system. I. Johnson and R. yonko3 used a fused-salt cell to measure the electromotive force between pure cerium and an alloy consisting of zinc-rich liquid in equilibrium with CeZnll. Solubility data for cerium in zinc has been reported by J. Knighton et u1 .4 Johnson and Yonko give the following equa-. tions for the mole fraction of cerium in zinc and the standard free energy of formation of CeZnll:

Jan 1, 1965

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 W. D. Forgeng, P. F. Wieser

MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,' Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,' Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.

Jan 1, 1964

By R. M. Waterstrat, B. N. Das, Paul A. Beck

The central region of the Ti-Mn system was studied by means of x-ray diffraction and metallography. The following intermediate phases were found: an MgZn2-type Laves phase having a wide range of homogeneity, the p-phase of unknozvn structure, and the + -phase with a large tetragonal unit cell, stable at 930°C and lower temperatuves. MaYKUTH, Ogden, and jaffee1 determined the soh-inh bility limits of manganese in and titanium. They also confirmed the structure of the intermediate phase TiMn2 which was previously identified as a Laves phase of the MgZn2 type.2 In the equiatomic region they found an additional intermediate phase, y, which presumably formed by a peritectic reaction at approximately 1200°C. This last observation was disputed by Rostoker, Elliott, and McPhers0n,3 who reported the formation of TiMn by a peritectoid reaction between 900" and 1000° C, but found no evidence of any intermediate phase other than the Laves phase at higher temperatures. Elliott and Rostoker4 reported furthermore that the X-ray diffraction pattern of TiMn could be identified as that of a o phase, although their data were not consistent with this inter~retation. Margolin and Ence6 presented X-ray diffraction data for the and TiMn, phases, and obtained metallographic indications for the existence of additional intermediate phases. They concluded from metallographic observations that two Laves phases are formed, separated by another phase, designated as &. A phase diagram for the Mn-Ti system has recently been published by Savitskii and Kopetskii,' which shows considerable disagreement with the work of Hellawell and Hume-Rothery,' in particular with regard to the terminal solid solutions based on the allotropes of manganese. The present investigation was undertaken primarily to clarify the phase relationships in the equiatomic region of the Ti-Mn system. The metals used in preparing the alloy specimens Were iodide titanium and electrolytic manganese, the latter having a nominal purity of approximately 99.9 pet. The electrolytic manganese was covered with a thick coating of a brown manganese oxide which was reduced by heating the manganese flakes for several hours at a temperature of 1100°C in an atmosphere of dry hydrogen. Three alloys, see Table I, were made using sponge titanium and manganese not treated in hydrogen. The alloys were prepared by arc-melting in an atmosphere of helium or argon. The composition of each alloy was calculated by assuming that the entire weight loss during melting was due to evaporation of manganese. Subsequent chemical analysis of certain alloys indicated that the compositions calculated in this manner were usually correct within 1.4 pct, as shown in Table I. All alloy specimens were wrapped in molybdenum foil before sealing them in silica tubes containing argon at a pressure of 1 atm at the annealing temperature. After quenching in cold water, the alloy specimens were bright and clean, with no evidence of any surface reaction. The alloys listed in Table I were examined metallographically, using an etchant consisting of 20 pet HNO3, 20 pet HF, and 60 pet Glycerine. powder for X-ray diffraction examination was prepared by crushing a portion of each annealed alloy

Jan 1, 1962

By M. Kaufman, A. E. Palty

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

Jan 1, 1962

By A. D. Marlin, A. J. Gentile, E. F. Jordan

Metallurgical changes in SAE 52100 ball-bearing components resulting from overload testing are described. Changes in microstructure, hardness, and resiclctal stresses crre discussed zuitlz re.ference to material cleanliness obtained by various steel-melting practices and are compared with work by otlzer investigators. Evidence is presented to show that the initialion and development of microstruc-tural alterations are characterized by two separate reactions: the appeavance of a "dark etchingJ' constituent, and "gray lines" or a light etclzing constituent. The dependency of these tzvo reactions on material cleunliness, running tirne, and contact stresses is discussed and a failure mode related to material cleanliness and microstructural transformation is proposed. THE study of ball- and roller-bearing contact fatigue has been paced by a strong emphasis on bears ing application performance. Particular attention has been paid to conditions that effect the spalling-type failure that is characteristic of rolling contact fatigue in through-hardened components. Some of the conditions investigated are lubrication and atmosphere,1-3 material characteristics and finish,475 and speed and design fa~tors."~ A typical spalling-type failure is shown in Fig. 1. The arrow shows the motion of the ball relative to the inner-ring race surface. The leading edge of the spall is usually sharper than the trailing edge. The race surface near the trailing edge also shows small dents caused by debris from the spall. In this type of testing very little metallurgical investigation is done on failed bearings. Emphasis is placed on test conditions and statistical analyses of endurance data. More basic work has been done relating micro-structural changes to fatigue performance. Dyer" and Wood, Cousland, and sargant9 have used mostly simple materials, such as single crystals and single-phase polycrystalline specimens, under simple alternating strain to identify a systematic process of fatigue damage. drutowski" was concerned primarily with the relationship between steel structure, contact stress, and energy losses in rolling contact. dones11 and Bush, Grube, and Robinson12 utilized changes in microstructure and residual stress in overload-tested rolling contact elements as a means of investigating the fatigue process. Work is being done on an ASME-sponsored contract,13 using both simple and complex materials, but there is still a long way to go before such theories as pore and void growth in simple structures can be applied to the relatively complex bearing steel microstructure. The purpose of this paper is to report on an investigation into the effect of steel cleanliness on the structural alteration and residual stress changes found in overload-tested ball bearings. Using these results and those of previous investigators, we will propose probable failure mechanisms in both overload- and normal load-tested ball bearings.14,15 PROCEDURE Ball bearings? 3208 size, were fabricated from SAE 52100 steel obtained by five different melting practices. The melting practices, chemistry, and inclusion ratings for the five lots of steel are summarized in Tables I and 11. The nonmetallic inclusion ratings were determined by the Jernkontoret method described in ASTM E45-51 Method A. This technique consists of microscopically examining a series of polished samples taken from specified locations in the ingots, billets, or bars. Each sample is surveyed at XlOO magnification and the inclusion types and sizes are compared to standard fields. Because of the nature of these ratings all values in Table I1 are rounded to the nearest half. The elec-

Jan 1, 1965

By H. I. Aaronson

ONLY limited studies have been made of pro-eutectoid a morphology in hypoeutectoid Ti-Cr alloys during previous investigations, 1-3 The nature of the eutectoid reaction, ß?a + TiCr2, has been considered in somewhat more detail.1,2,4,4 Inasmuch as the proeutectoid ferrite reaction in plain carbon steels has recently been extensively investigated in this laboratory, advantage has been taken of the opportunity to compare the morphologies developed in two rather different eutectoid systems in order to permit a preliminary estimate to be made of the degree of generality which may be ascribed to the various results obtained. Experimental Procedure The chemical analyses of the alloys used are given in Table I. The 7.22 pct Cr alloy was prepared by the Battelle Memorial Institute from iodide titanium and high purity chromium. The initial ingot was made by arc melting a master alloy and iodide titanium. The resultant ingot was twice remelted. by the consumable electrode technique. Upset forging at 950°C reduced the final ingot to 3/4 in. sq bars. The 10.94 pct Cr alloy was prepared by the Titanium Metals Corp. of America from sponge titanium and chromium of ordinary purity. This alloy was melted twice by the consumable electrode technique, forged at 1200° to a 3/4 in. sq bar, and rolled at 815°C to a 1/2 in. round. Specimens 1/4 in. x 1/4 in. x 1/16 in. were cut from the 7.22 pct Cr alloy; halves of disks 1/2 in. in dlam and 1/16 in. thick served as specimens of the 10.94 pct Cr alloy. These specimens were individually encapsulated in Vycor, Each capsule was evacuated three times to a pressure of 2 to 6 x lo-' mm Hg and flushed twice with a reduced pressure of argon prior to sealing. The inclusion of two small packets of zirconium chips permitted the capsules to be outgassed and internally gettered, without heating the specimen, prior to heat treatment. The specimens were solution annealed for 40 min at 1000°C, isothermally reacted in deoxidized lead pots, and quenched in iced water. Most of the isothermal reaction treatments were carried out at 25" intervals between 725° and 550°C on specimens of the 7.22 pct Cr alloy and at 650°C on specimens of the 10.94 pct Cr alloy. Results and Discussion Morphologies of Proeutectoid a*—Kinetics of the ß?a Reaction: Fig. 1 shows the TTT-curves for the beginning of the proeutectoid a and the eutectoid reactions in the temperature range investigated in the 7.22 pct Cr alloy. The M, temperature in this alloy is below 0°C. The curve for the beginning of the proeutectoid a reaction is in good agreement with that of Frost, Parris, Hirsch, Doig, and Schwartz' for a 7.54 pct Cr alloy, appears at considerably earlier reaction times than the corresponding curve presented by Rostoker4 for a 7 pct Cr alloy, and lies athwart the curve of Spachner and co-workers11 for an 8 pct Cr alloy. Differences in criteria for the beginning of the a reaction and the relatively high rate of this reaction at lower temperatures presumably account for some of these divergences and may also explain, in part, the apparent failure of an iodide-base 7.22 pct Cr alloy to react more slowly than sponge-base 7 to 8 pct Cr alloys. Grain Boundary Allotriomorphs: Crystals of this morphology nucleate at and grow preferentially and more or less smoothly along the matrix grain boundaries.5-7 Allotriomorphs are the first morphology to precipitate at most grain boundaries at reaction temperatures from 725°C, the highest temperature studied, at least through 575°C. Fig. 2 Shows typical allotriomorphs, formed during an early stage of transformation at 725°C. Grain boundary allotriomorphs are not the predc=iaant morphology at late reaction times at any temperature studied. However; from 725" through

Jan 1, 1958

By J. Gordon Parr, D. H. Polonis

High purity alloys of titanium and iron, made by a technique of levitation melting, have been investigated with particular reference to martensite formation and decomposition in the hypoeutectoid range. A preliminary study has been made of the occurrence of the phase corresponding to the structure Ti2Fe. MANY of the previous investigations of Fe-Ti alloys have been made using Kroll sponge as a source of titanium; and the subsequent heat treatments to which alloys have been subjected has, on occasion, led to further contamination. Worrier,',' who suggested a part of the equilibrium diagram for the binary system, and Wallbaum and coworkers,3-5 who worked largely with iron-rich alloys, all used Kroll sponge. Van Thyne, Kessler, and Hansen,6 in their determination of the equilibrium diagram, used iodide titanium for alloys up to 30 pct Fe. Duwez,7 who measured the M. temperature of titanium binary alloys with many solute elements, used iodide titanium in all cases except in his work on Ti-Fe alloys for which he used Kroll sponge. The investigation of the supposed phase Ti2Fe by Rostoker8 nvolved the use of iodide titanium. A section of the constitutional diagram, after Van Thyne et al., is reproduced in Fig. 1. Frequently too much stress is placed on the effect of contaminants in equilibrium and nonequilibrium systems, but there is no doubt that titanium alloys are extremely susceptible to interstitial atoms. Consequently, the main purpose of the work to be described was to determine those features of phase transformations in pure Ti-Fe alloys that were considered of importance in commercial heat treatments. For, although commercial alloys may not be of high purity, the investigation of a system uncomplicated by traces of impurity is a desirable starting point. Another incidental feature, the occurrence of Ti2Fe, was also investigated. The entire study was carried out using powders obtained from alloy ingots, for diffusion reactions are often more rapid in small particles than in bulk specimens. The frequently adopted practice of ascertaining phase constitutions by X-ray analysis of powders, and relating these to the microstructures and mechanical properties of bulk specimens, is considered by the authors to be open to criticism. In the martensite reactions in the Fe-Mn system, for example, it has been shown- hat similar phase distributions in solid and powder may result in different hardness values and appearance under the microscope; and it is possible that similar anomalies might occur in the Ti-Fe system. Consequently, in order to

Jan 1, 1955

By J. Gordon Parr, D. H. Polonis

The formation and subsequent decomposition of metastable phases in Ti-Ni alloys containing up to 11 pet (atomic) Ni have been studied. The decomposition of a completely retained ß phase and of a completely transformed 8 phase in a 6 pet alloy has been followed by X-ray diffraction and metallographic methods and by hardness determinations made during the process. The possible mechanisms of the reactions are discussed. PREVIOUS investigations of the Ti-Ni system have usually been limited to phase diagram studies; but little attention has been given to metastable phases and tempering processes. These are important, however, since equilibrium conditions are rarely achieved—nor, perhaps, are they desired—in practice. Up to the present time the available transformation data for titanium alloys appear to be restricted to isothermal transformation curves for selected binary and ternary systems. No quantitative studies have been made of the mechanism by which equilibrium is approached. Several independent investigations have been carried out to determine the Ti-Ni phase diagram. Early work by Wallbaum' and later by Long et al.' produced tentative phase diagrams which were not representative of true binary conditions, since the alloys were contaminated with oxygen and nitrogen. The most recent diagram (Fig. 1) is due to Margolin et al.," and a slight modification of the a + ß/ß boundary (shown dotted) has been proposed by McQuillan.' The structure of the phase Ti,Ni was shown by Duwez and Taylor" to be face-centered-cubic, with 96 atoms per structure cell. The formation of a martensitic ß phase (close-packed-hexagonal) in Ti-Ni alloys has generally been observed when specimens of low nickel content are rapidly cooled from the 0 (body-centered-cubic) range. Margolin et al. reported an increasing tendency for P to be retained in lump specimens as the nickel content increases. McQuillan' has studied the effect on the microstructure of delay time in quenching, and has reported the formation of pro- eutectoid a precipitate in a quenched hypoeutectoid alloy. In a previous study of Ti-Fe alloys," experiments were made on powder specimens produced by filing alloy ingots. Techniques were devised for the preparation and heat treatment of alloys, and X-ray diffraction methods were used both for structure determinations and phase ratio estimations. A similar approach has been made in this study of Ti-Ni alloys. Experimental Methods Ten alloys ranging from 0.25 pet to 18 pet Ni* * All compositions are in atomic percentages unless otherwise stated. were prepared from iodide titanium bar stock (hardness Rf 72) and Johnson-Matthey spectrographic standard nickel by levitation melting.' As a check

Jan 1, 1957

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-'. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5'9 for these high concentrations of phosphorus do not follow Fick's laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1' that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7'8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964

By R. I. Jaffee, C. T. Sims, C. M. Craighead

The fabrication of rhenium metal by powder metallurgy techniques is discussed. The following physical and mechanical properties have been measured and are reported: lattice constants, melting point, electrical resistivity, thermal expansion, spectral emissivity, modulus of elasticity, tensile properties and ductility at room and elevated temperatures, work hardening, recrystallization, grain growth, and oxidation resistance. IT is only occasionally that a metal reaches present-day technology with as little known about its properties as element No. 75, rhenium. Relatively scarce to date, it has been studied only infrequently and used less. Previous work on rhenium has been carried out primarily by European scientists. However, realization that rhenium occurs in commercial quantities in the United States recently has focused attention on this metal. Rhenium is a very dense high melting hexagonal-close-packed metal. Like tungsten and molybdenum, its highest oxide is volatile. However, when protected by reducing or inert atmospheres, its strength at high temperatures is greater than that of tungsten. Rhenium work hardens more than any other known pure metal, but, on annealing, becomes quite soft and ductile. Its vapor pressure is approximately that of tantalum, but it does not enter into the so-called "water cycle" nearly as readily as does tungsten. (The water cycle is a deleterious phenomenon causing blackening of lamp bulbs and vacuum tubes with subsequent failure of the filaments.) These and other properties, some already known and some found as a result of the current researches, have indicated that rhenium has many potential uses, primarily of an electrical or electronic nature. Rhenium or its alloys soon may be found in service as electron-tube filaments, cathodic emitters, or as electrical contact materials. In addition, rhenium or its alloys have potential use in such devices as high temperature thermocouples, and high wear-resistant parts such as precision instrument points. Rhenium, in the form of potassium perrhenate, was made available for this study by the Kennecott Copper Corp. The potassium perrhenate was reduced to rhenium metal in two stages, accompanied by leaching to remove potassium in the form of hydroxide. This impure metal was then oxidized to rhenium heptoxide and dissolved in water. The solution was neutralized with ammonium hydroxide to produce highly purified ammonium perrhenate, a typical analysis of which is shown in Table I. The ammonium perrhenate was ground to —325 mesh in a rubber-lined ball mill with Burundum balls. This operation caused a certain amount of impurity pickup, as reflected in the rhenium analysis shown in Table I. The fine ammonium perrhenate was reduced to metal with hydrogen. Particle size of the powder ranged from 1 to 25 microns, as illustrated by Fig. 1.

Jan 1, 1956

By R. J. Reynik, F. R. Meeks

IN the classical paper1 of Mehl and Rhines entitled "The Rates of Diffusion in the Alpha Solid Solutions of Copper", the authors state: "It has been mathematically demonstrated that the treatment of the data as though the diffusion were taking place between two flat plates instead of radially in a cylinder has no appreciable effect upon the results. Were the bars of a much smaller diameter, a modification of the analytical treatment would have been required." Unfortunately, the errors in the reported concentrations are much too large to neglect, as shown in the results below. A planar treatment of diffusion data assumes that the reference planes separated by a nominal distance (AX) have identical areas. An adjustment must be made on the concentration data should the successive diffusion planes differ in area. The Mehl-Rhines' diffusion samples were cylindrical with copper electroplated onto copper-based alloys. Successive surface areas through which diffusion occurs are in the ratio ri/r1, where ri is the radial distance between the center of the sample and the center of the i th shell to which the host (alloy) atoms diffuse, and r1 is the radial distance between the center of the sample and the center of the innermost (i = 1) experimentally reported shell from which the alloy atoms diffuse. Hence, ri/r1 (i = 1, ..., n layers) is a dimensionless correction factor to be multiplied by the reported concentration data before planar-data analysis is attempted. In the forty-seven samples reported, the original interface between the copper alloys and the electroplated copper was located at a mean distance of 8.255 mm from the center of the samples. The successive layers, machined off the samples, were approximately 0.0762 mm thick. The distance (xi) at which concentration (ci) was reported was always a distance measured with respect to the original interface, that is, with respect to the fixed distance of 8.255 mm. Hence, the as yet undiscovered Kirkendall Effect was precompensated. The values of ri and r1 are therefore given by ri = 8.255 + xi and Y, = 8.255 + x,. The illustrative table below lists the position xi (mm), ri (mm), the value of ri/r1, the reported concentration (ci) in weight percent (only valid for radial analysis of data), and the corrected concentration [c'i = (ri/r1)ci] in weight percent (only valid for planar analysis of data). Similar tables can be constructed for the remaining forty-six samples. The corrected data can be used to re-evaluate the diffusion coefficients for the reported systems.

Jan 1, 1965

By L. C. Chang, T. A. Read

Diffusionless transformation in Au-Cd single crystals containing about 50 atomic pet Cd was investigated by means of X-ray analysis of the orientation relationships, electrical resistivity measurements, and motion picture studies of the movement of boundaries between the new and old phases during transformation. The nucleation of diffusionless transformation by imperfections and the generation of imperfections by diffusionless transformation were discussed. THAT connections exist between plastic deformation and diffusionless phase changes has long been recognized. Thus it is often possible to produce a diffusionless phase change in a temperature range, above that in which the change occurs spontaneously, by cold-working the initial phase. Certain aspects of the dislocation theory of the plastic deformation of crystalline solids also provide for a rather direct connection between the processes involved in plastic deformation and in diffusionless phase changes. Heidenreich and Shockleyl have pointed out that simple edge dislocations in f.c.c. metals are probably unstable, and that the more probable lattice imperfections, called extended edge dislocations, consist of two half dislocations separated by a distance of the order of magnitude of 100A. The region about two atomic planes thick between the half dislocations because of this stacking fault may be described as having the hexagonal close-packed structure. Presumably the stacking faults observed by Barrett" fter cold-working f.c.c. Cu-Si alloys resulted from the passage of such half dislocations through the lattice of the initial phase. It is now becoming clear that the development of a detailed theory of the atomic movements involved in diffusionless phase changes will require a consideration of the role played by lattice imperfections, just as such considerations are necessary to the understanding of plastic deformation mechanisms. This point of view has been recently set forth, for example, by Cohen, Machlin, and Paranjpe3 who pointed out the role which might be played by screw dislocations in nucleating diffusionless phase changes. The present paper reports on some aspects of the diffusionless phase change in single crystals of the beta phase alloy Au-Cd which serve to emphasize further the importance of lattice imperfections in diffusionless phase changes. The diffusionless phase change of Au-Cd possesses several remarkable features. One of these is that the interface between the high-temperature beta phase and the low-temperature orthorhombic phase typically moves with a low velocity, in contrast to the behavior observed in the transformation of austenite to martensite. Motion pictures of this slow interface motion have been prepared in the course of the work reported here. Another important feature of the Au-Cd transformation is the small amount of undercooling observed. The reverse transformation occurs on reheating to a temperature only 20" higher than the transformation temperature observed on cooling, and under some circumstances the hysteresis observed is substantially less than this. This narrow temperature range between transformation on heating and cooling is presumably in part a consequence of the fact that the transformation requires a lattice shear of only about 3". Finally, the orthorhombic product phase possesses unusual mechanical properties, as was first pointed out by olander' and Benedicks." After completion of the transformation on cooling the specimen can be severely deformed, yet on the release of load it springs back to its original shape in a rubber-like manner. Explanation of this phenomenon will require an understanding of the lattice imperfections in the orthorhombic structure and, correspondingly, of those in the initial body-centered cubic structure. Single crystals of Au-Cd alloy containing 47.5 and 49.0 atomic pct Cd were prepared from fine gold (99.95 pct purity) and chemically pure cadmium (99.99 pct purity) by melting the alloy in an evacuated and sealed fused quartz tubing and growing into single-crystal form by the Bridgman method. The Au-Cd alloy containing 47.5 atomic pct Cd undergoes a diffusionless transformation from an ordered body-centered cubic structure to an orthorhombic structure when it is cooled to about 60°C, while the reverse transformation takes place when the alloy is heated to about 80°C, according to electrical resistivity studies. The structures of these two phases have been studied by Blander,4 reinvestigated by Bystrom and Almin.e he lines of Debye photo-gram of powdered samples of Au-Cd alloy containing 47.5 atomic pct Cd prepared in this laboratory were identified and agreed fairly well with those of

Jan 1, 1952

By Henry R. Piehler

Continuous seven- and nine teen -filament close-packed silver-steel filamentary composites mere tested in tension. For purposes of comparison, the tensile behavior of the composite was predicted from the measured properties of the individual com-ponents. It was assumed that the axial strain is the same in both components and that the contribution of each component to the composite flow stress is proportional to its volume fraction. Good agreetnent was obtained between the observed and predicted tensile behavior. However, the composite elongation at fracture was about twice that observed when the individual steel wires were tested alone. Composites in which the filaments were widely spaced failed by the consecutive fracture of the filaments. In composites with closely spaced filaments, a composite instability preceded frachcre. These effects are explained in terms of a lateral restraint to the necking of the filaments which develops in the deforming composite. TWO-COMPONENT or composite materials are increasingly being developed and used as structural materials. Of all the composite geometries used, the filamentary configuration has proved to be the most successful. Polymer-bonded fiber-glas, the most common of the filamentary composites, has been investigated most extensively to date. One explanation of the behavior of fiberglas1 suggests that the load transfer between the glass fibers and the polymer matrix occurs primarily through friction. Bond separation between the fibers and the matrix is presumed to occur at very low stresses. Subsequently, only frictional bonding can provide for the transfer of load from the matrix to the fibers. The force normal to the fiber-matrix interface which gives rise to this friction is assumed to arise from the matrix shrinkage which occurs during solidification. The behavior of metallic filamentary-composite materials would be expected to differ from that of fiberglas in several significant aspects. Residual stresses resulting from differences in thermal contraction can be kept to a minimum by proper heat treatment. A strong wetted bond is formed between the two phases. In brazed joints,2 for example, the interphase bond is sufficiently strong that the weaker material will fail before separation occurs at the interface. Most metal filaments can undergo appreciable amounts of plastic deformation before failure. Failure by plastic instability or necking frequently occurs in metallic filaments, but not in glass fibers tested at room temperature. Differences between the behavior of fiberglas-polymer and metallic filamentary composites have indeed been observed in composites containing various types of metallic filaments in a silver matrix.3,4 At strains of the order of 10-2 pct, all the deformation was accommodated by the silver matrix. Hence, the strength of the composite depended only on the fiber concentration and not on the nature of the fiber. At higher strains, the strength of the composite increased when filaments with higher work-hardening rates were used. Surface slip line observations on a silver-mild steel composite that had been stretched 4 pct showed that an appreciable amount of deformation occurred in the filaments. Work on tungsten-copper filamentary composites5 has shown that the ultimate tensile strength for varying filament fractions followed a linear mixture rule. Assuming that the axial strains in both filaments and the matrix are equal, this linear mixture rule can be expressed as: The subscripts c, f, and m refer to the composite, filaments, and matrix, respectively. A and V are the area and volume fractions of each component. sc and of are the ultimate tensile strengths of the composite and the filaments. sm is the flow stress of matrix at a strain equal to the elongation at failure of the filaments. However, the tungsten filaments can undergo only a limited elongation before they fracture without an appreciable reduction in area. A composite containing more ductile filaments might indeed deviate from this linear mixture rule for the ultimate tensile strength, since filament failure by necking might be arrested by the matrix. SPECIMEN PREPARATION Specimens were prepared from 0.8 pct carbon steel piano wires of 0.015 in. initial diameter. The wires were given a thin nickel flash and a silver plate varying in thickness from 0.015 to 0.007 in., depending on the filament fraction desired. In order

Jan 1, 1965

By C. Elbaum

Specimens consisting of several crystals, each with a prescribed geometry and a controlled orientation with respect to both the extermally intposed stress and the highboring crystals, werer deformed in tension at room temperature. It is shown that the influence of a grain boundary on the plastic defolrmation of a mullicrystal depends on the extent to which the presence of the grain boundary, contributes to the necessity 01. multiple slip in the component crystals. MANY investigations were carried out in the past on the plastic deformation of aluminum single crystals, bicrystals, and polycrystals. The various studies of bicrystals aimed primarily at elucidating the influence of grain boundaries on the mechanisms of plastic deformation. In the earlier studies the emphasis was placed primarily on finding the "strength" contributed by a grain boundary. In more recent investigations it became apparent that the grain boundary does not contribute any strength per se but rather acts by influencing the mechanism of plastic deformation in the adjoining grains. The concept thus emerged of the plastic properties of a bi-crystal, and by extension of a polycrystal. depending solely on the mechanism of deformation prevailing in each grain. The contribution of the grain boundaries thus becomes limited to the type of restrictions imposed on each grain by its neighbors. The present investigation of the behavior of specimens consisting of more than two crystals was designed for the purpose of studying the influence of the grain boundary in simple aggregates. The findings of this study further support the concept that the restriction imposed on a deforming crystal by its neighbor constitutes the predominant factor in the plastic deformation of polycrystals. The term "multicrystal", in contrast with single and polycrystals, is used to describe specimens consisting of several crystals. Each one of the component crystals has a prescribed geometry and a controlled orientation with respect to both the externally imposed stress and the neighboring crystals. Two groups of multicrystals were prepared. All the component crystals of both groups of multicrystals had the axial orientation (isoaxial multicrystals) shown in Fig. 2, with the primary slip plane and slip direction both at 45 deg to the specimen axis. In the first group (hereafter referred to as group I) the component crystals were symmetrically oriented with respect to the plane of the grain boundary; the primary slip plane and slip direction were respectively at an angle of 60 and 30 deg to this plane. For the second group (group 11) the axial orientation remained the same and the relative positions of the primary slip plane and slip direction are shown in Fig. 3. EXPERIMENTAL METHODS The material used was aluminum 99.993 pct pure, according to the manufacturer. The specimens were produced by growth from the melt in a horizontal graphite container. In order to maintain the prescribed geometry of the individual crystals of a multicrystal, a technique described elsewhere was used.' The specimens were grown under a small, positive pressure of helium at a rate of approximately 1 mm per min. annealed in air for 24 hr at 640°C and cooled over a period of several hours to room temperature. All the multi-crystals were rectangular in cross-section, 6 by 18 mm (see Fig. 1) and from 150 to 170 mm long. In each group bicrystals, tricrystals and quadru-crystals were prepared as shown in Figs. 1 and 4.

Jan 1, 1961

By E. S. Greiner

Germanium and silicon have been plastically deformed in torsion at elevated temperatures. Slip took place on the four {Ill} planes. Dislocations, revealed by etch pits on a (111) face, occurred in rows that were traces of operative slip planes. THE plastic deformation of germanium and silicon by bending and tension at elevated temperatures has been reported by Gallagher.&apos; Transla-tional slip during plastic flow in these materials, according to Gallagher&apos; and Treuting,&apos; occurs on (111) planes. Recent work by Treuting&apos; indicates the direction of slip to be <1l0>. The present paper describes the plastic flow characteristics of germanium and silicon deformed by torsion. Torsional deformation was accomplished by twisting 1/4x1/4x2 in. specimens held in molybdenum grips and contained in an atmosphere of helium in a transparent quartz tube and heated by an external resistance furnace. The angular displacements were measured on a graduated circle with a pointer attached to the movable grip. Temperatures were measured with a chromel-alumel couple; the hot junction was within the quartz tube and in close proximity to the specimen. Photographs of samples of germanium and silicon twisted at 850" and 1180°C, respectively, are shown in Fig. 1. The germanium was twisted 230" per in. and the silicon 80" per in. These deformations are larger than those used in experiments to be described later and are presented only to emphasize the extensive plasticity of these materials. Germanium A single crystal specimen of germanium (n-type, 7 ohm-cm resistivity) with a (111) plane normal within 3" of the torsion axis, Fig. 2, was chemically polished with CP-4 solution" and then twisted 9" during the twisting of these specimens of germanium, the slip lines from the (lli) plane should have appeared in the four lateral faces instead of in only two. Perhaps the absence of rotational slip is brought about by the square cross-section. A cylindrical specimen would have a more uniform stress distribution in torsion than one with a square cross-section, and may deform by rotational slip. A specimen of germanium (n-type, 5 ohm-cm resistivity) twisted less than 8" per in. at 550°C, was cut to expose the (111) face 19" 28&apos; from the torsion axis, Fig. 4a. This face, after metallographic

Jan 1, 1956

By W. J. Feuerstein

Plastic deformation of the germanium adjacent to the re-growth material has been observed after alloying single crystal germanium with tin. Of several solder alloys investigated, plastic deformution was observed only in the germanium samples in contact with a tin-doped regrowth material. Dislocations were observed to move on a viewed (111) plane following thermal cycling of tin-doped regrowth material on germanium. OBSERVATION of germanium samples to which solder had been fused indicated that plastic deformation, as evidenced by slip arrays of dislocation etch pits, occurred during the fusion of the solder alloy, Figs. 1, 2. The samples had been prepared by placing the solder in contact with the germanium and heating the assembly to approximately 575"C, followed by cooling to room temperature. During this process, the solder first melts, and then as the temperature is further increased, dissolves a portion of the germanium with which it is in contact. During the cooling portion of the thermal cycle, the dissolved germanium is precipitated, and provided

Jan 1, 1961

By D. F. Gibbons

THIS investigation was undertaken in order to gain further information on the mechanism of plastic deformation of iron at temperatures between room temperature and 77.2°K, and also to contribute to our understanding of the low temperature brittleness phenomenon that occurs in both the tensile and impact tests. It was decided to study as pure an iron as possible and to use the tensile test in order to simplify the problem as much as possible. Two series of iron were used throughout the investigation: iron A, obtained from the National Research Corp. and supplied as gas-free, high purity iron; and iron B, obtained from Fast&apos; and produced by melting iron under purified hydrogen. Typical analyses of samples of both irons, after fabrication, are given in Table I. The main difference in composition of these irons is in their nickel and oxygen contents. Nickel has a very large solid solubility in iron. However, oxygen has an extremely small solid solubility. An attempt was made to reduce the oxygen content still further by remelting under purified hydrogen. This was successful in reducing the oxygen content to -0.0006 pct. However, no results on tests of this iron are included, since difficulty was encountered in fabricating the ingot. Wire specimens 1 mm in diameter were used for the investigation. The wires were produced from the ingots, as supplied, by cold rolling and swaging, with intermediate vacuum anneals at 700°C. Care was taken to reduce preferred orientation in the wires to a minimum by keeping the percentage of reduction in area between anneals of 30 to 40 pct. X-ray transmission photographs showed no indication of preferred orientation. The final grain size of iron A was 20 to 24 grains per linear mm and of iron B, 16 to 18 grains per linear mm. All specimens were tested in the decarburized and denitrided condition unless otherwise stated. The procedure was to pass hydrogen, saturated with water vapor at 26oC, over the specimens at 730°C for 2 hr. The specimens were quenched in iced water and then annealed in a vacuum of - 5x10-6 mm Hg for one day at 560°C to remove hydrogen. Higher temperatures were used for the vacuum anneal but this temperature was found to be quite satisfactory in removing hydrogen. The specimens were slow-cooled after the vacuum anneal. Where it is stated that the specimens were carburized, the specimens were given an identical decarburizing treatment and then carburized by passing hydrogen, saturated with pure n-heptane vapor at 0°C, over the specimens at 730°C. The specimens were then homogenized at 730°C for 2 hr in dry hydrogen. After the carburizing treatment the specimens were given the same vacuum anneal as for the decarburized specimens. The carbon content was determined from the maximum value of the internal friction carbon peak.2 Apparatus Fig. 1 shows a diagram of the tensile apparatus, with half the cooling coil removed. The cooling coil enabled temperatures from 200" to 77.2oK to be obtained. The apparatus was designed to fit a standard Tinius Olsen Universal tensile machine. The apparatus consisted of the rigid plate A which carried two carefully machined hooks H. These hooks attached the plate firmly to the moving crosshead of the tensile machine. The lower grip B was rigidly suspended from the plate A by three stainless steel rods. The upper grip C was joined to the upper grip of the tensile machine by the stainless steel rod E. The lower part of the apparatus was surrounded by a Dewar vessel, which was made a sliding fit inside the brass collar D. The specimen was held in a clamp which fitted into the grip, forming a ball and socket joint (see inset a). This was to attain as nearly pure

Jan 1, 1954