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By R. M. Brick, R. G. Treuting

Despite the basic importance of slip in the plastic deformation of metals, and the considerable experimental investigation, thought, and speculation that have been devoted to the fundamental nature of these processes, surprisingly few data have been reported regarding the microscopic appear- ance and distribution of slip lines,‡ the external manifestation of the slip process. Photographs hitherto reproduced in the literature are in general at low or unspecified magnifications with no correlation to the prior shear. A single-crystal cylindrical tensile specimen of alpha brass about 1/2 in. in diameter, one of many previously prepared by H. L. Burghoff,1 was available for study. A plane about 3/16 in. wide, parallel to the specimen axis and normal to the plane containing the slip direction and the specimen axis, was ground and metallographically polished along the entire 5-in. gauge length. Heavy etching produced a surface free of both scratches and flow. The specimen was strained in tension until slip markings first became visible on the polished surface (Figs. 1 and 2). Re-stressing the crystal caused additional markings to appear at an initially lower stress than previously was required. Stretching the specimen to produce a dense concentration of slip lines caused such variations in level in the polished surface (normal to the slip direction) that microscopic study at higher magnifications became impossible. After annealing 15 hr. at 850°C, the specimen recrystallized to form two grains with a boundary approximately normal to the specimen axis and about midway along its length. Each was X-rayed, and two planes were again polished along the length of the specimen, in this case each parallel to the slip direction in one of the two crystals. A light longitudinal scratch parallel to the specimen axis was drawn down the center of each plane. A Huggen-berger extensometer was attached to the crystal A, whose slip plane would have the higher resolved shear stress of the two, and the specimen was again strained in tension.

Jan 1, 1942

By F. L. Bosqui

The history of the development of gold metallurgy in South Africa is divisible into two periods: That preceding the introduction of the cyanide process on a commercial scale in 1890; and the 24 years intervening between that important event and the present time. The period between the discovery of the banket reefs of the Witwaters-rand and the year 1890 was one of phenomenally rapid progress in mining development, but of no special interest to the metallurgist, There were no strikingly original or distinctly local advances in the treatment of gold ores. Californian practice in stamp milling and amalgamation prevailed, in mills ranging in equipment between 5 and 50 stamps, operating within a wide range of efficiency, and under the trying conditions usually encountered in a new and isolated field. The somewhat incomplete records of gold output of that period show that in December, 1887, there were 20 producing companies in the Witwatersrand district, of which 10 had mills, the largest being of 20 stamps. The only official record of returns for May, 1887, was that of the Wemmer mine, whose modest achievement with a 5-stamp mill was 100 tons crushed, producing 887 oz. 3 dwt. of gold. This is interesting in view of the present-day output of this field, which in 1913 reached 8,430,998 oz. The rapid increase of production during this first period (May, 1887, to January 1891) is shown by the following summary for the year 1890:1 Total tone crushed.................................. 702,828 Number of stamps in operation....................... 1,046 Average number of tons crushed per stamp per day..... 2.36 Yield of gold, ounces................................ 494,817 Yield per ton, pennyweights.......................... 13.36 The stamp duty ranged between 11/2 and 4 tons per day, according to weight of stamp, fineness of screen, and operating skill available. The prevailing weight of stamp was about 900 lb., and the screen, 900 meshes to the square inch.

Jan 1, 1916

By H. M. Howe, A. G. Levy

§ 1 Introduction.—This paper gives the results of our micro-graphic determinations of the position of Ae3 in a series of 14 hypo-eutectoid steels of varying carbon content, one of them very rich in phosphorus, and of SEe for one hyper-eutectoid steel. We have proceeded chiefly by noting the temperature at which the reabsorption of the pro-eutectoid element is found to be complete after a 30-min. holding, but in part also by noting the temperature at which its precipitation begins. Observations on these same steels by Messrs. Burgess, Crowe, and Rawdon, of the United States Bureau of Standards, are given in a paper1 issued simultaneously with this, while in a third paper2 one of us compares these data with those of earlier observers. These three papers are treated as one whole by numbering their sections, tables, and illustrations continuously, and by setting the folding plates of micrographs at the end of the last paper. The Composition of the Steels Experimented On is given in Table I. § 2. Notalion and Definitions.—Following Osmond's development of Tschernoff's notation, in which " Ac3 " is the upper limit of the hypo-eutectoid part of the transformation range as observed in heating up, and " Ar3 " is that same limit as observed in cooling down, and following the usual custom of calling the upper limit of the hyper-eutectoid part of that range " SE," we may go farther and call this latter limit " SEc" when observed in heating up and " SEr " when observed in cooling down. Further, we may call the equilibrium position of these lines, i. e., the position which they would have in pure iron-carbon alloys if all

Jan 1, 1914

By Frederick Rhines

PURE copper that has been allowed to oxidize at an elevated tempera-ture in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cupric oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig. 1a). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composed of oxide particles precipitated in a matrix of metallic copper that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,1 it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but will separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (1) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By R. H. Johnson

The Manual of the Oil and Gas Industry, under the Revenue Act of 1918, published by the Treasury Department for the guidance of oil companies in preparing their estimates of future recoverable oil for the purpose of calculating depletion, gives the first large public collection of comparative decline curves for the whole country. It is a matter of both scientific and practical interest to so arrange these data that the pools can be readily compared. There are certain difficulties in such a comparison, however: (1) The economic limit varies from 50 to 2000 bbl. a year in different pools taken. (2) Because of this variation in economic limit, the range of data shown makes comparison possible only for wells of intermediate size. In order to be as inclusive as possible, I have taken as an expression of the rate of decline the amount of oil produced in the period during which a well drops from 3000 to 2000 bbl. a year. No period of smaller production could be used because of the high economic limit in California; and no period of larger production and yet include the small well areas of the Appalachian. As it is, the Lima-Indiana wells are excluded. In a few instances, curves were extrapolated to obtain the reading, where the curve seemed regular enough to warrant it. In general, the amount of oil, in barrels, produced while a well declined from 3000 bbl. to 2000 bbl. a year is shown in Table 1.

Jan 1, 1921

By Richard Conkling

A SHALE layer, buried beneath two or three thousand feet of strata, in some instances, will upon folding become thicker in the synclines and thinner on top of the anticlines. This can be accounted for, in part, by the stretching on the crests of the fold and the compressing in the troughs; but this will by no, means account for all of it, as is shown in the example herein set forth. It is my firm belief that the rest of the thickness is due to flow. What causes the movement, however, does not concern us here, so long as there is movement, for this article purposes to show its effect upon the producing area of different sands. It is the author's hope, in this way, to drop a hint or two that may be valuable to the oil geologist, in making estimates of future productions and values of oil properties. An example will be given from property in the famous Cushing Pool in northeastern Oklahoma, where the author has had occasion to make a detailed study before recommending some property to his company, and has then been able to watch the results of this work. The author never mapped the surface structure in this pool, as this had been done by Frank Buttram when he was with the Oklahoma Geological Survey. We are using, therefore, a section of his map in this article for our surface contours. The main east clip comes farther east than this section shows.

Jan 10, 1916

By Schumacher, Earle E.

THE solidus line above the solid solution field in the lead-antimony system was originally determined by Dean and his associates1 from heating curves. They did not regard this line as having been accurately fixed and in their more recent publications2 the curves drawn do not follow closely the original data. The precise location of the solidus line is of importance in the extrusion of lead-antimony cable sheath, as the temperature of the metal in this process must be less than the lowest temperature at which any part of the alloy in the lead-press charge becomes liquid. It is very desirable, however, to operate at as high a temperature as possible, as the rate of extrusion for a given pressure is approximately doubled for an increase of 10" C. in temperature. The precise location of this line is also important in the investigation of ternary systems of lead, antimony and a third metal. For these reasons, and because of the differences reported in the literature, data were secured on the lead-antimony solidus line by the classical quenching-test procedure.

Jan 1, 1927

By Charles A. Ashburner

' I. Natural-Gas Explorations. The rapid development of the natural-gas* industry in Western Pennsylvania, and the great economy which results from its use, both for manufacturing and domestic purposes, has led to an inquiry as to the occurrence of this gaseous mineral in all thickly populated and large manufacturing centers of the United States. Natural-gas springs are to be found in almost every State in the Union, and in many States gas has been obtained in wells sunk either for water, oil, or gas, or in search of solid mineral deposits. The occurrence of natural gas is, however, not dependent upon mere chance, as is popularly supposed, but upon the existence of special geological phenomena; this fact is now recognized by professional men and by many practical men concerned either in the exploration for or in the use of this gas. The desire among our leading manufacturers, to emulate Pittsburgh, has led to the sinking of many wells in many localities, in search of natural gas. Some of these wells are now being located and drilled under the direction of professional experts, but many more have been, and are still being located by "quack " explorers, who often depend upon spiritualistic communications, or the diviningrod, or by intelligent persons, who are ignorant, however, of the geological and physical conditions under which gas has already been found. My attention has recently been directed to a number of these exploring operations where holes have been drilled, and, after failing

Jan 1, 1887

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

By R. G. Fenish

THE B-Ni system was chosen for this study because of the great interest being shown in boron-fiber-strengthened composite materials. Boron fibers were obtained from Texaco Experiment, Inc. They average 4.2 mils in diam with a 0.5-mil tungsten wire in the center. In order to make the diffusion couple, the fibers were included in the nickel matrix by electroforming. The samples were placed in a preheated furnace for the desired temperature and length of time. Sectioning and polishing the samples revealed concentric rings as shown in Fig. 1. The average penetration distance, X, was calculated by measuring the radius of the second phase (the white shell in Fig. 1) and subtracting the original radius. The second phase was identified as NiB by X-ray diffraction. This allows the kinetics of the formation of the phase NiB to be calculated by Eq. [I], which is taken from Hoffman:"

Jan 1, 1967

By H. R. Page, A. E. Jr Lee

From the inception of zinc retorting on a commercial scale in the United States in 1890,' the retort employed has undergone wide variations in its composition and manufacture, facilitating in part equally remarkable improvements in furnace capacities. The early day hand made clay retort was charged with carbonates or silicates or with coarse dead roasted concentrates mixed with a large proportion of charge fuel resulting in a relatively low zinc burden and fired 24 hr in direct coal fired furnaces. Its modern counterpart is fabricated in hydraulic presses from clay mixtures containing sizeable amounts of either silicon carbide or silica flour, charged with sintered flotation concentrates to more than three times the early day zinc burden and fired 24 to 48 hr in gas fired furnaces. This paper does not attempt to describe in detail the early day clay retort practice as it is well outlined in treatises by Ingalls,2 Lodin,3 Liehig,4 Hofman5 and others. A brief review of clay retort practice is presented together with a description of the major developments since 1912. Clay Retorts The Belgian type retort, both in the circular and elliptical forms, has been used almost exclusively. Typical dimensions of press made clay retorts around 1910 are shown in Table 1. Variations in these dimensions were used at different plants according to local conditions to a maximum inside diameter of 9 in. and inside length of 54 in. However, the effective heat penetration in a 24 hr firing cycle and the tendency of the retort to bend limited the retort size. Use of the elliptical vessel was an attempt to present a stronger cross-section resisting the tendency to bend and to increase the burden without increasing the depth of heat penetration. One exception to the 48-54 in. length was the 60 in. retort used as early as 1905 at Palmerton by means of supporting the last 12 in. at the butt end with a specially designed furnace back-wall. This backwall construction with the 60 in. retort had been developed and used at Bethlehem by G. G. Con-vers and A. B. DeSaulles. An attempt was made at Blende, Colo. to use even larger retorts of the Rhenish type based on European practice and requiring much higher furnace temperatures. Satisfactory plastic clays capable of withstanding these temperatures were not available, and the plant never operated successfully. PREPARATION OF BATCH Composition of the clay retort by weight was 40 to 50 pct raw clay and the balance "grog." Generally speaking the mix consisted of 7 parts plastic clay to 9 parts grog by volume. Principal source of the clay used was the Cheltenham vein—sometimes referred to as "St. Louis city clay." A typical analysis was A12O3-31.0 pct, SiO2-50.0 pct, Fe2O3-2.5 pct, MgO-0.3 pct, CaO-1.5 pct and loss on ignition 14.0 pct. At the smelter the clay was weathered whenever possible and then crushed to 0.08 in. or finer. Grog consisted of calcined adobies, cleaned retort scrap and cleaned refuse fire brick such as old furnace brick, blast furnace linings, and others. Saggers from ceramic plants and calcined flint clay were later used. The grog materials were ground to 0.12 m. or finer. Occasionally coke dust up to 10 pct of the mix was substituted for a part of the grog following European practice.² Particle size of the grog has a major influence on the retort properties—the larger the grain, the better can the retort withstand thermal shocks, resist bending at furnace temperatures and resist corrosion from slag; the smaller the grain, the lower the loss of zinc vapor through the retort walls. Grog forms the skeleton of the retort, and the clay shrinks around its grains to act as a binder. In the drying process, the grog has a stabilizing effect on the drying rate, decreasing shrinkage and giving up previously absorbed water to the surrounding clay to minimize the danger of cracking or checking.² Grog and clay were mixed through a horizontal pug mill with 10 to 20 pct water added, depending on whether the retort was to be formed by hand or mechanically, more water being required for the hand process. The batch or "mud" extruded from the pug mill was cut in convenient lengths for handling, stacked in piles or in special rooms, covered with wet burlap and allowed to "rot" or age from 1 to 8 weeks to increase plasticity. HAND MOLDING If the retort was to be molded by hand, the mud was repugged after the rotting period and given to the molders. Their molds consisted of 3 sheet iron or wood cylinders, each one third the retort length and defining the outer shape of the retort. Beginning with the bottom section, mud was placed in the form and tamped with a rammer

Jan 1, 1950

By Klaus-Peter M. Hanke

INTRODUCTION In early 1979 Jim Walter Resources, Inc. (JWR) of Brookwood, Alabama approached TMCI Construction, Inc (TMCI) to make a proposal on a program that involved the sinking of up to 10 ventilation shafts of approximately 6.7 m (22 ft) diameter and ranging in depth from 500 to 700 m (1650 to 2300 ft) for the JWR coal mines in Alabama. At this time TMCI was already constructing the first spiral underground bunker (capacity 2000 tons) in North America for the JWR organization at their No. 4 mine in Alabama. The TMCI proposal was based on the use of the mos modern large diameter shaft boring machine rather than sinking the shafts using the conventional drill blast-muck technique. The proposal was made based o: the experiences by the parent company, Thyssen Schachtbau, which has been using this type of machin in Germany for shaft boring since 1971. As a result of the TMCI proposal JWR issued a purchase order to TMCI for the construction of four 6.7 m (22 ft) diameter, concrete lined, unfurnished ventilation shafts ranging in depth from 500 to 700 (1650 to 2300 ft). An order was thus placed with WIRTH Machinen- and Bohrgeraete Fabrik GmbH, in Germany for the manufacture of a model 650/850 E/Sch "Schachtbohrmaschine" (Vertical Shaft Borer = V-mole which arrived on site in Alabama in early 1981. The first V-mole GSB 450/500 was introduced in Germany in 1971 and was capable of enlarging in one step a pre-drilled 1.2 m (4 ft) pilot hole to 4.5 - 5.0 m (14.7 - 16.4 ft). This machine has sunk 9 staple shafts and deepened one surface shaft for a total of 2360 m (7740 ft) of shafts. On the last shaft boring operation in 1978 the machine was converted as an experiment to drill without a pilot hol using a hydraulic pumping system to remove the cutting debris. A second generation machine, the SB VI 500/650, was introduced in 1977 for enlarging the pilot hole to a range of 5.0 - 6.5 m (16.4 - 21.3 ft) diameter. This machine is still in operation and has already drilled well over 2000 m (6500 ft) of shaft. The third generation of V-mole, the SB VII 650/85( for diameters from 6.5 to 8.5 m (21.3 to 27.9 ft) was: commissioned in May 1980 and has been used for two surface shaft deepenings totalling 606 m (1990 ft) with another scheduled for 1982. The main advantages favouring the use of such V-moles were identified as: 1) A reduction in manpower to the crew required in a conventional shaft sinking operation. 2) A considerable reduction in time to complete a shaft compared to conventional techniques. 3) The use of the V-mole eliminates many of the hazards encountered in conventional sinking. Based on the successful performance of the first three V-moles in Germany, Thyssen Schachtbau decided to employ this principle abroad. In 1980 a second machine of the third generation was built and is now operated by TMCI Construction, Inc. in Alabama. The first shaft was completed at the end of 1981 and this paper describes the method of operation including some unique aspects not attempted on prior V-mole operations and some of the statistics arising out of the experiences during the first shaft boring operation. THE NO. 7 MINE FAN SHAFT SITE Jim Walter Resources, Inc. was formed in 1970 to exploit the coal field in Alabama on the southern tip of the Appalachian coal field. The coal reserves amount to around 650 million tons of mainly good quality coking coal of which about 350 million tons are to be extracted over the next 30 years. Shaft sinking and preparatory work began in 1972, and at present 6 mines are producing around 5.4 million t.p.a. Annual production is to expand to 10 million t.p.a. as soon as possible, and the ventilation shafts to be sunk by TMCI play a vital role towards attaining this goal. The first shaft site is located at the No.7 mine, near Brookwood, Alabama. The actual location of the shaft relative to the production shafts is shown on the mine plan (Fig. 1), which also shows the room-and-pillar extraction system used at present. The mine plan further shows the conveyor route used for the muck removal. The geological survey showed that the strata consisted of horizontal layers of mainly sandstone, sandy shale and shale interspersed with several coal seams. The seam being extracted at the No. 7 mine is a combined seam made up of the Blue Creek and Mary Lee seams at a depth of 513 m (1682 ft) and having an average seam thickness of about 2 m (6 ft). At the beginning of September 1980 the surface site preparation and pre-grouting work was completed by JWR, and TMCI was able to commence with Stage I of the shaft sinking program - the drilling of the pilot hole.

Jan 1, 1982

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, 'pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.' However, the components which are strongest in the recrystallization texture are in this range.'________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,' 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.'~-'~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.' In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2'13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,'~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.' state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By J. E. Johnson

Discussion of the paper of Mark A. Amnion, presented at the Cleveland meeting October, 1913, and printed in Bulletin No. 70, October, 1913, pp. 1167 to 1 79. J. E. JOHNSON, JR., Ashland, Wis.:-Mr. Amnion's paper is of great value and it is not with any desire to reflect. on it that I wish to make some comments on the use of the scleroscope. We obtained one on trial some months ago and made very extensive tests with it, but without getting very satisfactory results. The readings on good car-wheels and bad ones were just about the same, but the factor in its use most likely to produce erroneous results is a variation in the thickness of the specimen being tested. In order to find out something on this subject we cut a thin disk, about -1,: in. thick, off a brass rod; then one 0.25 in. thick, and another about 1 in. thick, put the surfaces of all in about the same condition and tested them with the scleroscope. The readings varied widely; the resilience of the anvil evidently entered to a very high degree on thin pieces. By putting a soft cushion between such a thin specimen and the anvil, and forcing it up against the tube, the softness of the cushion cut off the resilience of the anvil and the results were more like those of the thick specimens. After a thickness of 1 in. was passed, the specimen seemed to have mass enough so that the resilience of the anvil no longer played an important part, and above that thickness results on different materials would be comparable, even though the thicknesses differed. But in order to get comparable results on thin specimens the thickness of those being tested should be the same. I should like to ask how the variations introduced in this way were overcome, so as to get strictly comparable results. Mr. AMMON :-.I have not had much experience in that, but the scleroscope is simply an indication of the surface harden-

Dec 1, 1912

By W. A. Tiller

The conventional techniques1 for determining the liquidus and solidus surfaces of an alloy system containing more than two components are extremely tedious to use and do not provide a complete picture of the equilibrium relations between solid and liquid alloys. These techniques are unable to yield "tie-line" information concerning solid and liquid phase equilibrium, a very important parameter in the solidification description of the liquid alloy and a very necessary parameter in the preparation of "zone-levelled" alloy crystals. The tie-line in a polycomponent system is analogous to the partition coefficient, k, in a binary system, it gives the composition of the solid, Cs, in equilibrium with a liquid of composition CL. That is, CS = kCL, where CL = [CO, c1,...Cn] denotes the concentrations of the n + 1 constituents, and k = [ko, kb ,...kon] denotes the gross partition coefficient for the elements between the two phases; thus, k is the tie-line in this system. To provide complete information concerning the two-phase equilibrium in a polycomponent system it is necessary to know both the liquidus surface and the gross partition coefficient. From these two the solidus surface is obtainable. The conventional techniques are unable to provide this information in other than a binary system so we must look elsewhere. In recent years considerable insight has been gained into the correct description of the liquid-solid transformation, 2,3 and controlled solidification experiments may now be designed to both facilitate and enhance equilibrium diagram studies. In the present paper consideration is given to two methods for obtaining the liquidus surface and the tie-lines in polycomponent systems. The methods to be described below deal with the solidification of an n + 1 constituent liquid alloy of initial composition [co, Co ,...Con], where the superscripts refer to the elements present and the Oth element is considered as the solvent in which the n solutes are dissolved. The general assumptions made in the treatment are the following: (i) the solid and the liquid at their interface are in equilibrium during the growth of the solid phase, (ii) there is no diffusion in the solid phase, and (iii) the liquid phase is completely mixed and is therefore homogeneous in concentration. METHOD I In this section a general experimental method will be described which, in principle, is capable of giving an exact description of the liquidus surface and tie-lines. Consider the unidirectional solidification of the liquid alloy specimens L cm in length (freezing either horizontally or vertically). Allow the sample to be frozen very slowly from one end, as indicated in Fig. 1, with complete mixing in the liquid, and then analyze the solid bar to determine its chemical constitution as a function of position, x, along the bar. Let Fig. 2 represent a possible distribution of the ith constituent along the bar. At the point x' the concentration of the ith constituent is C1/5(x'), and the average concentration of the rest of the bar between x' and L is given by C:(X' - L) where [ A(x) c1s(x)dx c1/s(x'-L) = f A(x) dx x * and A(X) is the cross-sectional area at x. In a similar manner. all the Cf(x' - L) may be determined. Thus, the gross artition coefficient k for liquid of composition [Cs(x - L),...Cs(X' - L)] is given by -ko= CUs')/Cos(x' - L)" k0 = csn{x')/cs(x'- L) During the freezing of a charge of length L, the liquid composition may vary over a wide segment of the phase diagram and the gross partition coefficient over this segment of the phase diagram may be determined from one, bar. Fig. 3 illustrates the magnitude of Cs(g)/C,' as a function of the fraction g of the bar which has Solidified.2 We can see that the concentration in the bar will vary over a range of about 15 wt pct for C,' = 10 wt pct and k0 = 0.5. It appears that 4 or 5 specimens would be adequate to study a simple binary eutectic phase diagram.

Jan 1, 1960

By J. L. Brimhall, R. A. Huggins, M. J. Klein

IN a recent paper1 it was shown that small additions of magnesium, copper, and oxygen decrease the stacking fault probability in plastically deformed silver. Correlation of :X-ray data with measurements of the twinning frequency and metallographic observation of slip lines indicated that this effect may be due to an increase in the relative stacking fault energy. It is the purpose of the present note to report experiments on these alloys of known stacking fault probability that relate to the stacking fault contribution to electron scattering in silver. There has been a considerable amount of disagreement in the literature concerning the contribution of dislocations to electrical resistivity in metals. Calculations relating to the scattering of conduction electrons by the dislocation core, its strain fields, and related effects have been made by several authors.2-5 In addition, experimental work on Cu,3,6-10 Ni,11 and Ni-Co alloys1:! has shown that dislocations in those materials exert an anomalously large effect on resistivity, this effect being related to the presence of extended dislocations. The problem of the scattering due to the stacking fault region between partial dislocations has been treated theoretically using several different procedures.13-'0 The results of these calculations show a wide range of predicted values, from rather large to completely negligible, due to the models and the approximations involved. Almost all of this work has been applied to the specific problem of scattering in copper. The more complete theoretical treatments depend rather critically. on the shape of the Fermi surfaces and the effective mass parameters. The scattering from stacking faults might therefore be expected to vary significantly from one metal to another. Unfortunately, sufficiently accurate information is not available .which would allow one to have any confidence in a theoretical prediction of the scattering in the case of silver. Resistivity measurements were made on small wire specimens of vacuum melted high purity silver and several dilute alloys. These measurements were made at approximately 20°C, with great care being given to temperature measurement and corrections. At such temperatures phonon scattering is significantly greater than imperfection scattering. However, the experimental technique was such that measurements on similarly treated samples were reproducible to better than 2.4 X 10-9 ohm-cm, which was satisfactory for this work. Values of the stacking fault probability and the increase in resistivity after severe plastic deformation are given in Table I. The increases in resistivity resulting from plastic deformation agree quite well with previous work on silver.14,21-26 In addition, it has been previously found that interetitials and vacancies in silver anneal out well below room temperature, so that the residual imperfection scattering in these experiments could be expected to be primarily associated with dislocations;. It is seen from the data in Table I that large changes in stacking fault probability are accompanied by differences in resistivity due to imperfection scattering of only a few percent. If the scattering of conduction electrons by extended dislocations is primarily due to the area of the stacking fault region independent of the stacking fault energy, and not the core and strain fields associated with partial dislocations, the resistivity increase should be proportional to the product of the dislocation density and the stacking fault width, as is the stacking fault probability. Therefore, the imperfection scattering caused by plastic deformation of the alloys should be considerably smaller than that found in the pure silver. Since this was not observed, these results sugegest the possibility that stacking faults do not themselves contribute appreciably to the electrical resistivity of silver deformed at room temperature. An alternative explanation of these observations is that the scattering by the stacking fault is roughly proportional to the stacking fault energy, rather than being determined by the total area of such faults. Sufficient evidence is not yet available to separate these two possibilities. This work was supported by the Office of Naval Research.

Jan 1, 1962

By J. J. Gilman

RECENT experiments have shown that the mar-tensite reaction in a standard tool steel is influenced by the history of the reacting austenite. The martensite reaction proceeds to a given extent at a higher temperature in austenite formed from an annealed spheroidal structure than it does in austenite formed from tempered martensite: that is to say, a prequench lowers the temperature range of the martensite reaction in this steel. Furthermore, a prequench alters the appearance of the martensite as compared to martensite formed from "virgin" austenite. The steel used for this work was a manganese nondeforming tool steel of the following composition: C, 0.85 pct; Mn, 1.43; Si, 0.23; Ni, 0.12; Cr, 0.59; and W, 0.59. A piece from a rolled bar was forged to Vz in. sq and annealed to a spheroidal structure. Disks 1/8 in. thick were used in the experiments. Several sets of the specimens were prepared and austenitized in lead at 1475°F. Three sets were held at 1475°F for 15 min, quenched in water, and immediately reheated to 1475°F. After this quench the three sets were held for 5 min, 30 min, and 3 hr, respectively, at 1475°F and then the individual specimens in each set were quenched in molten baths to 325", 300°, and 275ºF, respectively, and held for 15 sec. Immediately after the quenching treatments? the specimens were tempered at 600°F for 30 sec to darken the martensite and then were quenched in water. The holding times were short enough to avoid isothermal transformation. Three other sets of specimens were given the same final quenching treatments as the first three, but they were austenitized at 1475°F for 20 min, 35 min, and 3 hr and 15 min, respectively, without an intermediate water quench. The two individual specimens from each set were quenched together in order to eliminate quenching errors. Several experiments were run in this way but only the six sets referred to are described in detail because they all yielded essentially the same results. By means of the stated heat treatments the martensite reaction was investigated for: 1—austenite formed from an annealed structure, and 2— austenite formed from tempered martensite. The martensite reactions of the two types of austenite differed significantly. This is shown by Figs. 1 and 2. Comparison of the photographs on the left in Figs. 1 and 2 with those on the right shows that less martensite was formed by a quench to a given temperature from prequenched austenite than from austenite formed from an annealed structure, that is, the prequench suppressed the martensite reaction. The effect was observed for specimens austenitized 20 min, 35 min, and 3 hr and 15 min. A comparison of Figs. 1 and 2 shows that the martensite reactions in both sets of specimens occurred at lower temperatures with increased austenitization time. This was caused by the increased dissolution of residual carbides with time at 1475°F. However, the difference in amount of martensite formed in prequenched austenite as compared to virgin austenite was approximately the same for all three austenitization times. One further observation should be noted. The needles of the martensite formed from virgin austenite are somewhat longer on the average and show less of a tendency to cluster than those of martensite formed from prequenched austenite. This causes the martensite on the right in Figs. 1 and 2 to have a more acicular appearance than the martensite on the left. Since the sets of specimens used in this work were austenitized for identical total lengths of time and the effect of a prequench on the martensite reaction existed for specimens held at the austenitizing tem-

Jan 1, 1953

By G. Derge, Ling Yang, John Henderson

Self-diffusion coefficients of aluminum have been measured by the capillary reservoir technique in liquids of the CaO-SiO2-Al2O3 system containirg equimolar portions of CaO and SiO2, in the temperature range 1400o to 1520oC. For the melt containing 6.0 mole pct Al2O3 the results can be expressed by the equation D = [(4.3 * 0.3) x 104] exp [(-85,000 * 17,500)/RT]cm~sec-'; for the melt containing 12.5 mole pct Al2O3, by the equation D = (5.4 i 0.2) exp [(-60,000 * 10,00O)/RT] cm2sec-: A concept of the constitution of these melts has been developed which proposes that the ratios O/(Si +Al) and Al2 O3/CaO determine the dominant species present. In recent years considerable work has been done on the system CaO-SiO2-A12O3 with a view to elucidating the structure of liquids of this system. Conductivity,' electromotive force, 3 density,4 and activity5 measurements have all contributed to an understanding of the problem, but as yet there is no entirely satisfactory theory that can account for all the observed experimental results. In principle, measurements of self-diffusion coefficients should give further information which is not obtainable in other ways. Self-diffusion coefficients for calcium, silicon,6 and oxygen7 have been measured. The present investigation extends the series of self-diffusion coefficient measurements to include aluminum and develops a concept of constitution for liquids of this system which is compatible with all the observed experimental results. EXPERIMENTAL The technique used in the measurement of the self-diffusion coefficient of aluminum was the capillary-reservoir method,8 A126 being incorporated in the melt contained in the capillary and inactive aluminum in the reservoir melt. This method was chosen because it minimizes convection currents' in the diffusion zone. It has the further advantage that the boundary conditions are such that a slight modifica- tion of Anderson and saddington's8 solution of Fick's Law yields an equation which requires measurements only of the length and the initial and final average specific activities of the solidified melt within the capillary. where t is the diffusion time, Co is the average specific activity of the melt contained in the capillary at t = O, C is the average specific activity of the melt contained in the capillary at t = t, 1is the length of the capillary, and D is the self-diffusion coefficient. The equation is of somewhat different form than those previously applied to high temperature diffusion studies because the specific activity of the melt in the reservoir was negligible both before and after diffusion. The diffusion apparatus is shown schematically in Fig. 1. It consisted of a silicon carbide resistance furnace containing the inactive melt in a graphite crucible, internal dimensions 7/8 by 4 in., enclosed in a 1 1/4- by 1 1/2- by 30-in. McDanel tube. A 3/8-in. McDanel thermocouple sheath to which graphite radiation shields and a graphite protection tube were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube the capillaries could be lowered into or raised out of the melt. Temperature was measured with a Pt-Pt 13 pct Rh thermocouple which was calibrated periodically against a standard couple. The furnace temperature was controlled to ± 5°C through the thermocouple immersed in the melt. Temperature variation over the depth of the melt was less than ± 3°C. The inactive melts were prepared from pure native quartz, assaying better than 99.9 pct SiO2, A.R. grade A12O3 and A.R. grade CaCO,. The same quartz and CaCO3 were used in preparing the active melts, the

Jan 1, 1962

By H. Bartholomew, L. Bernstein

Experirmental bonds of Ag-In SLID to gold, copper, nickel, Kovar, Dumet, nickel-plated molybdenum, ALL-Pt vrzetallizing on ceramic, and nickel-plated Mo-Ti metallizing on Al2O3 ceramic have been made and exalnined. Metallographic taper sections were made of all bonds for Phase identification. In addition, failuve temperatltres were determined for bonds heated undev shear load. Sowe bonds were subjected to electvon-probe microanalysis. The ternary SLID system Ag-In-Sn was similarly evaluated. Plwtonticrogaphs and electron-probe data are discussed and related to over-all phase diagrams , diffusion effects, and wetting properties of the liquid. The rates of diffusion andor compound formation of gold, silver, and copper in indium and In-Sn liquids are found to descend in that order, as measured by the relatzve thickness of phase layers in the interfaces of bonds made at 200to 400°C. It is concluded that the SLID process enables one to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures, and meet most requirements for application in interconnection, silicon bonding, or hermetic sealing of electronic devices. In a previous publication by one of the authors, the theory and principle of SLID bonding in simple binary systems was discussed. SLID bonding can be defined as a joining process using a preform with a laminated structure: a low-melting material clad on a high-melting core. During the bonding cycle a metallurgical transformation occurs such that the resultant structure can withstand, without reliquefying, temperatures higher than those at which the bond was made. The phases present in the joint interface region are high-melting compounds or, if equilibrium is reached, solid solution. Properties will depend on the phases present, ultimately approaching those of the solid substrate core of the SLID preform. The high-temperature strength of bonds made in these systems was correlated to phase identification in the interfacial bond regions from metallographic cross sections and electron-probe X-ray microanalysis data. When complex electronic components are assembled, multiphase systems result at the interfaces of bond regions. In these ternary and higher-order systems very little diffusion and phase-diagram data is available with which to predict the nature of the interfacia1 region that will result from conventional fabrication processes and subsequent field use of the component. Clarke and Rhines did early work in the field using the Al-Mg-Zn system as a vehicle. Guy and co-workers studied a portion of the Cu-Zn-Ni system and some mathematical4 and general5 aspects of multiphase diffusion. irkald' and coworkerse recently studied diffusion in the Cu-Zn-Sn system. No diffusion studies have been made on ternary systems directly applicable to this investigation but some phase diagrams are available: g-u-n, u-i-n, and CU-i-n. I) DESCRIPTION AND EXPERIMENTAL PROCEDURE The elements Au, Ag, Cu, Ni, In, and Sn are found in alloy systems commonly used in fabricating and assembling electronic components. Reference to the appropriate phase diagrams9 and the previous publication will indicate that the binary systems of any of the two low-melting elements, indium and tin, with any one of the other four higher-melting elements are capable of producing SLID bonds. It is not unreasonable to assume that any ternary or higher-order alloy system containing at least one of the elements gold, silver, copper, or nickel and one or both of the elements indium and tin could be used to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures. Indeed, the liquidus contours and isothermal sections of those phase diagrams available7 do so indicate. The parameters affecting the bond and the equipment used in evaluating the bond were described in an earlier paper.' The current investigation used the

Jan 1, 1967

By W. C. Winegard, J. E. Gruzleski

The stages in the development of cells in the Sn-Cd eutectic have been studied by unidirectionally solidifying specimens under known conditions of growth rate, temperature gradient, and impurity concentration. By means of a quenching technique, the shape of the solid-liquid interface during solidification could be observed. Cells are shown to develop from defects or depressions which exist on the solid-liquid interface of even a pure eutectic. Th,e container wall, grain boundaries , and fault lines in the micro structure play an important role in cell development. A two-phase eutectic dendrite found at high impurity concentrations is described. L HE cellular or colony structure formed during eutectic solidification caused much confusion among early workers in their attempts to classify eutectic structure, and a major advance in our understanding of eutectic solidification was made when the colony structure was identified with a cellular interface caused by the presence of impurity elements.1'2 To date, however, no detailed investigation of the stages in cell development in eutectics has appeared, and little work has been done on the cell morphology. The present paper presents the results of such an investigation. EXPERIMENTAL The Sn-Cd eutectic was used in this investigation with lead as the impurity element to promote cell formation. Materials of 99.999 pct purity were zone-refined to an approximate purity of 99.9999 pct. Alloys as close as possible to the eutectic composition, 67.75 wt pct Sn, were prepared using zone-refined tin and cadmium. The alloys were then zone-melted to the exact eutectic composition, as described by Yue and Clark,3 using a total of twenty to twenty-five passes on each eutectic bar. Only those portions of the bars which contained no primary phases were used in subsequent experiments. Master ternary alloys were prepared by melting together the required amounts of lead and the Sn-Cd eutectic in a sealed Pyrex tube under argon, and these alloys were then diluted with pure Sn-Cd eutectic as required. Unidirectional solidification was conducted vertically upward using the two-element resistance furnace shown schematically in Fig. 1. With this apparatus, it was possible to obtain a range of growth rates and temperature gradients so that the cell structure could be studied under different growth conditions. Growth rates in the range of 0.4 to 9.1 cm per hr and temperature gradients from 2.25° to 1475°C per cm were used. To ensure steady-state solidification, power to the furnace was stabilized, and the entire apparatus was enclosed in a large box in which the temperature was controlled to within ± 0.2°C. The apparatus was arranged so that the specimen could be quenched in situ during solidification by pouring a large quantity of water down the central vycor tube. Excellent delineation of the solid-liquid interface at the time of the quench was obtained because of the structural changes accompanying the rapid solidification of the remaining liquid. The quenching rate was always extremely rapid as no evidence of a transition in the lamellar spacing at the interface was ever observed. The alloys to be solidified were contained in degassed, high-purity graphite tubes, 1 cm OD and 0.6 cm ID. The specimens were about 18 cm in length. After the alloy had been cast into the tubes, three 0.8-mm holes were drilled in the tube to the center of the specimen. One hole was placed 1 cm from the bottom of the ingot, and the other holes were placed at 8 and 9 cm, respectively, from the base of the ingot. Thirty-four-gage chromel-alumel thermocouples were sealed in the holes. The lower thermocouple was used to position the solid-liquid interface at the start of each experiment,

Jan 1, 1969