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By David Moskowitz, Ira Binder, Robert Steinitz

THE hard refractory borides of the transition elements of the 4th, 5th, and 6th groups of the Periodic System have been the subject of a number of recent investigations.'-' It is well known now that most of these elements form several different borides, and Kiessling8 has summarized the rules which govern to some extent the arrangements of the boron atoms in the various structures. Melting points of a few borides have been published." The systems Fe-B, Ni-B, and Co-B have been reported," but, as these borides are rather low melting, they are outside of the groups of boron compounds considered here. Brewer' has tested the stability of various borides and estimated a number of eutectic temperatures between different borides, but in no case was the complete system of a transition metal and boron investigated. The phase diagram becomes of special importance if the preparation of the borides from the elements in powdered form is considered; the lowest eutectic temperature will determine the first appearance of a liquid phase. Also, the knowledge of high temperature phases, if they exist, is important for the preparation of bodies from these borides by hot pressing or sintering. During the investigation of various metal borides,7 it was found that there were more boride phases existing in the Mo-B system than reported by Kiessling." They occur, however, only at temperatures above 1500°C and were, therefore, not found by him. This led to a study of the equilibrium diagram of the Mo-B system. ranging from 0 to 25 pct B and from room temperature to the liquidus. Part of this investigation was reported during the "Research in Progress" session at the 1952 Annual Meeting of the AIME.11 Raw Materials and Preparation of the Borides The raw materials used were commercial molybdenum and boron powder, both supplied by the Molybdenum Corp. of America. The molybdenum powder was 99+ pct pure? while the boron powder contained about 83 to 85 pct B. A large percentage of the impurities in this powder was oxygen, with the rest formed by iron, calcium, and unknown substances. The low purity of the boron used was, however, not considered detrimental to the final product, as most of the impurities evaporated at the high temperatures at which the borides were formed. The final product always had a minimum purity of 96 to 98 pct (figured as molybdenum and boron), with carbon, iron, and probably oxygen being the remaining products. Carbon is usually present as graphite. The chemical analyses always confirmed the compositions which corresponded to the crystallographic structures as determined by X-ray diffraction, and the boron content of the finished product agreed closely with that of the starting mixture; no boron was lost during the boride preparation. The chemical analysis methods employed for molybdenum and boron were previously described by Blumenthal.12,13 The powders were mixed by hand in the desired proportions, compressed at room temperature under low pressure, and then heated under hydrogen to about 1500" to 1700°C in a graphite crucible to form the borides. Usually, the three well-known borides Mo,B, MOB, and Mo,B,, which are stable at room temperatures, were prepared in this way, and all other compositions were made by mixing these borides in various ratios or by the addition of molybdenum or boron powders for the very low or very high boron contents. Preparation of two-phase compositions directly from the elemental powders was tried only occasionally to check whether equilibrium could be reached in this way. Experimental Procedures The stable borides were mixed in the desired ratios and heated under hydrogen in graphite crucibles to various temperatures. The well insulated crucibles were heated in a high frequency induction furnace. Special care was taken to obtain exact temperature measurement, which proved much more difficult than originally anticipated. It is believed that individual temperature measurements have an error of less than ±25ºC, while melting or transformation temperatures are accurate within ±50°C. The temperatures were measured with an optical pyrometer which was aimed at the closed end of a graphite tube extending down into the crucible. close to the samples. Attempts to measure directly through the hydrogen exit stack failed. The crucible arrangement is shown in Fig. 1. Heating was done at a slow rate to be sure that the temperature inside the crucible was uniform. The specimens were kept at the final temperature for about 30 min. For the investigation of high temperature phases, some samples were quenched. They were heated, without atmosphere protection, in a very small graphite crucible which could be rapidly removed from the high frequency coil, and dropped into water. These quenched samples were afterwards annealed to establish the equilibrium at lower temperatures. The melting points or the positions of the solidus and liquidus lines were determined by heating the specimens to various temperatures and examining them at room temperature for evidence of a liquid phase. These results were checked later on by thermal arrest curves, especially to determine the exact position of the eutectic temperature line. For this purpose about 200 g of the boride were melted in a graphite crucible, in an arrangement similar to Fig. 1. Slow cooling was assured by very good

Jan 1, 1953

Jan 1, 1922

Jan 1, 1967

Jan 1, 1935

By George H. Cook

At first sight this subject seems to belong to pure theoretical geology, but examination will soon show that it has important practical and economic interest to the mining engineer. The conclusion that all the northern portions of our country, as well as of the eastern continent, have, in the later periods of geological history, been covered with a thick bed of ice, is now accepted by geologists. This bed of ice, except in its greater magnitude, was like the modern glaciers of the Alps, and other mountains which extend above the line of perpetual snow. The marks it has left upon the surface show that it was comparatively thin on its southern edge, but that its thickness was much greater a little further north, and that it was several thousand feet thick at its kenviest parts. This variation of its surface would give it a descending slope towards the south, and cause the mass of ice, like a semifluid substance, to move in that direction,

Jan 1, 1879

Jan 1, 1935

By M. Gell, G. R. Leveran

The high- and low-cycle fatigue properties of the nickel-base superalloy, Mar-MBOO, in columnar-grained and single-crystal forms were determined at room temperature. It was found that the fatigue lives of these materials were greatly affected by the size of preexisting cracks in MC-type carbides contained in the micro structure. Most of the data falls on two curves given by: (zN)'/A€= K, where Nf is the number of cycles to failure, Af is the total strain range, and K is a function of carbide size. No difference was observed in the fatigue behavior of the columnar-grained and single-crystal materials for the same MC carbide size. Matrix slip and crack initiation occurred at precracked MC carbides and, to a lesser extent, at micropores. Fatigue crack propagation was mainly in the Stage I mode, i.e., on cry stallo graPhic slip planes. The Stage I fracture in these materials was unusual in that distinct features were observed on the fracture surfaces. In high-cycle fatigue, these features resembled those commonly observed on the cleavage fracture surfaces of bcc and hcp materials. Yet, in this study, the cracks propagated slowly in a cyclic manner. In low-cycle fatigue, the Stage I facets contained equiaxed dimples, similar to those observed on the tensile fracture surfaces of ductile materials. These observations indicate that both local normal and shear stresses are involved in these Stage I fractures. A model is proposed to explain these results based on the weakening of the cohesive energy of the active slip planes by reversed shear deformation and the fracture of the bonds across the weakened planes by the local normal stress. RECENT developments in casting technology have produced cast nickel-base superalloys in columnar -grained and single-crystal forms.1'2 The tensile and creep properties of the nickel-base superalloy, Mar-M200, cast in these forms have been shown to be superior to the corresponding properties of the conventionally cast polycrystalline material.lp2 This improvement in properties results, in part, from the elimination of grain boundaries in the single crystals and the alignment of the grain boundaries parallel to the stress axis in the columnar-grained castings. As part of a program to evaluate the fatigue properties of nickel-base superalloys cast in single-crystal and columnar-grained forms, a study has been made of the cyclic deformation and fracture of Mar-M2OO at room temperature. M. fiFl I .hininr Mpmher AIMF ic ^pninr Rocoarrh Accn^iata anH I) EXPERIMENTAL PROCEDURE The composition range of Mar-Ma00 in weight percent is: 8 to 10 Cr, 9 to 11 Co, 11.5 to 13.5 W, 0.75 to 1.25 Cb, 1.75 to 2.25 Ti, 4.75 to 5.25 Al, 0.01 to 0.02 B, 0.03 to 0.08 Zr, 0.07 to 0.12 C, bal. Ni. All of the castings met the above specifications. The castings were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr which resulted in a 0.2 pct offset yield stress of 150,000 psi at room temperature. The microstructure of the material consisted of cuboidal, coherent particles of ordered, fcc Ni3(A1,Ti) (commonly designated y'), approximately 0.3 p on edge, distributed in an fcc y solid-solution matrix. MC carbides together with shrinkage and gas micropores were also distributed throughout the materials. The MC carbides and micropores were located preferentially in the interdendritic interstices, as well as in the grain boundaries in the columnar-grained castings. The (100) direction of all the single crystals and the common (100) axis of the grains in the columnar materials were aligned within about 5 deg of the specimen axis. Fatigue testing was carried out in the high-cycle (HCF) and low-cycle (LCF) fatigue regions, with the major difference being gross yielding of the specimen occurred during the first cycle in the LCF region. This division also corresponded with the more usual one in which the life of a specimen in LCF is less than lo4 cycles and that in HCF is greater than lo4 cycles. The designs of the high-cycle fatigue and low-cycle fatigue specimens are shown in Figs. l(a) and (c), respectively. The gage sections of both HCF and LCF specimens were electropolished prior to testing. The HCF specimens were tested in an MTS, closed-loop, hydraulic fatigue machine at 10 cps in air. The specimens were cycled between a tensile stress of 5000 psi and a maximum tensile stress which ranged from 35,000 to 125,000 psi, Fig. l(b). The LCF specimens were cycled under strain control from zero to a maximum tensile strain, Fig. l(d), in a Wiedemann-Baldwin testing machine. The experimental procedure has been described elsewhere.3'4 Both HCF and LCF tests were interrupted periodically in order to replicate the development of slip and cracking at the specimen surface. This was accomplished by placing plastic replicating tape around the gage section of the specimen while the specimen was in the mahine. The size of the MC carbides for all specimens was measured on a polished longitudinal section through the gage section after fatigue testing. The method of measurement consisted of carefully scanning the entire polished section in order to locate the largest MC carbides. Photographs were then taken of the six longest carbides oriented approximately normal to the

Jan 1, 1969

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Jan 1, 1940

By Benjamin N. Webber

THE peninsula of Nicoya contains virtually all of the known manganese deposits of Costa Rica. These are south and west of the Tempisque River, which flows across the peninsula near its juncture with the mainland. This peninsula forms the westernmost part of the province of Guanacaste, which is the northern of the two Pacific Coast provinces of Costa Rica. The larger villages are connected by ox-cart roads and trails. The area may be covered on horseback without difficulty except during the rainy season, when rivers are in flood and difficult to ford. This is particularly true of the Rio Seco-Guayjiniquil area, where there are no inhabitants and few open trails through the tropical jungle. Santa Cruz and Sardinal are served by the Taca Airlines, two planes a week from San Jose and Puntarenas. The port of Puntarenas has excellent loading facilities but none are available nearer the manganese districts; there ore must be lightered to vessels standing offshore. PHYSIOGRAPHY In Costa Rica there are three physiographic divisions: (I) the central plateau (Mesa Central), a somewhat dissected lava platform upon which are superimposed volcanic peaks, some of which are still active: (2) the Atlantic low-lands and (3) the Pacific lowlands. The peninsula of Nicoya and the larger part of the province of Guanacaste lie within the Pacific low lands. The term "lowland" indicates relation to the central plateau, as the peninsula of Nicoya is largely mountainous. The mountains of Nicoya form the southern extremity of a range of low hills, which are almost continuous along the Costa Rican coast to the Nicaraguan border. The coast line shows evidence of subsidence. The Gulf of Nicoya obviously is the drowned valley of the Tempisque River. The west coast of Nicoya shows many rocks, shoals, bays, inlets and small islands as evidence of a sea encroachment. The altitude of the manganese deposits ranges from o to 800 ft. Topography is of the mature type of wide valleys and low hills, often with abrupt slopes. The climate is tropical and humid; rainfall of 125 in. falls largely between Sept. I and Jan. I. Vegetation often is very dense, the Rio Seco-Guayjiniquil area being truly tropical jungle, containing many hardwoods. HISTORY AND PRODUCTION The production of manganese ore in Costa Rica apparently dates from the first World War. It reached a peak of about 10,000 tons in the year 1919, then declined rapidly. Evidence of this period of prospecting has rotted away or been swallowed by the jungle. The war now in progress apparently revived the interest in Costa Rican manganese and has encouraged further prospecting. Deposits long known have been redenounced and trails have been cut through the jungle to them. Many new deposits have been discovered in the last

Jan 1, 1942

By L. G. Laureau

This paper is presented to call the attention of steel-manufacturers to the need of further reform in the manner of casting and handling ingots. The problem of making the work usually performed in and around the casting-pit less dangerous to the men and less costly to the management is one which has occupied the minds

Jan 1, 1885

LIBERIAN ore has been called the richest iron ore mined in the world, and thus far, the output from the Liberian Mining Co.'s Bomi Hills mine has lived up to its reputation. Iron content has been variously given as 68.47 pct to 68.825 pct. A recent United Nations survey gave it first place, surplanting the previously top-rated Swedish product. The first shipment of Liberian ore to the United States reached Baltimore in June, 1952 and went into blast furnaces at Republic Steel's Cleveland plant, where excellent results were reported. The physical make-up of the ore was hard, dense lumps, free of fines and with ideal size distribution. The Bomi hills mines were scheduled to be in full operation by the end of 1952. At the close of 1951, 200,000 tons of ore had been delivered to Baltimore. Liberian Mining Co. states that production is about 90,000 tons of ore per month at present. Between 1200 and 1500 men are employed at the mine site, with about 25 pct of them Americans. The Bomi Hill project was financed with the aid of the Export Import bank, which loaned Liberia Mining part of the sum needed to initiate and put the development into production. No definite expansion plans are in the making but extensive diamond drilling is being pursued. Original estimates of annual production for Bomi Hills ran in the neighborhood of 1.5 million tons, but the figure is no longer applicable. Liberia's potential as an iron producing country has been known for a long time, but the physical obstacles in the way of large scale production were such as to prohibit even contemplation of the project. Until recent years, the only route from the mine site to Monrovia was a foot trail. Once to the coast, over swamps and unbridged rivers, the ore was still useless because of the lack of loading facilities. Transportation Solved One problem was solved with the completion of the artificial harbor at Monrovia. Harbor construction was well under way when the mine project began in 1948. The island location of Monrovia also made the building of a bridge across the St. Paul River necessary. The 980 ft reinforced concrete structure, accommodating railroad and vehicular traffic, was opened in 1949. Meanwhile, preliminary work on railroad construction started. Grading was completed quickly. In April, 1951, the first train made the trip from Monrovia to the Bomi Hills. About half of the cost of the entire project went into railroad construction. More than 2200 men, often forced to resort to primitive methods, were engaged in clearing a path through the heavy forests between the mine and port. Swamps were drained and filled, and bridges, including the William V. S. Tubman, named for the Liberian President, were constructed. At the port, a Robbins Conveyor Belt Co., orehandling plant was installed. Ships can be loaded from the stockpile at the rate of 3000 tons per hr and vessels need spend only one day in port. Liberian Mining is operating under an 80 year lease, giving the company exclusive mining rights to all minerals, except gold, platinum, and diamonds, within a 40 mile radius of Bomi Hills. The contract provides a fixed royalty to the Liberian Government of five cents per ton of ore extracted, and a premium -based on the New York market price for Bessemer-grade pig iron. The entire project started because an American,

Jan 1, 1952

By G. E. Pellissier, P. H. Salmon Cox, B. G. Reisdorf

Banding that occurred in plates rolled from the early production heats of 18Ni(250) maraging steel is described and related to the segvegation of certain alloying elements (nickel, molybdenum, titanium), the extent of which was quantitatively evaluated by means of electron-microprobe analysis. The effect of banding on mechanical properties is discussed, with particular reference to observed directional differences in plane-strain fracture toughness of plates. It is shown that banding originates as interdendritic segvegation during ingot solidification and persists in some degree through normal soaking and hot reduction to plate. The results of the study showed that heating sections of small laboratory-cast ingots at 2200°F for 4 hr was sufficient to markedly reduce microsegregation and to considerably improve mechanical properties. Hot rolling of 7-in.-thick ingot sections to 1/2-in.-thick plate effected a similar reduction of microsegregation, but resulted in even greater increases in ductility and toughness than that obtained by homogenization treatment alone. DURING the past few years, considerable attention has been directed towards the low-carbon, high-alloy maraging steels and in particular towards the 18Ni-8Co-5Mo-0.4Ti alloy. The steels of this group, having an excellent combination of high strength and toughness, have a number of advantages over their more conventional medium-carbon low-alloy, quenched-and-tempered counterparts. In the annealed condition, the maraging steels are in the form of a ductile marten-site; aging at a relatively low temperature, typically 900°F for 3 hr, increases greatly the strength through the precipitation of intermetallic compounds. One problem in the early production heats of maraging steel was that the finished plate frequently displayed a banded structure. Previous work on other steels1-' had established that banding in wrought products is either a direct or an indirect consequence of chemical segregation, which occurs during solidification and persists to some extent through normal thermal and mechanical treatments. For example, Smith and others: in a study of low-alloy steel, were able to correlate the severity of banding in the wrought product with the degree of interdendritic segregation of nickel and chromium in the as-cast ingot. The effect of banding on the mechanical properties of steels is usually considered to be detrimental, although there is only limited evidence to suggest that a marked improvement in properties can be obtained with less heterogeneous structures. Comparison of the longitudinal and transverse tensile properties of banded and of homogenized 4340 steel showed that only the transverse ductility was improved by homogenization, but even then the improvement was not commercially significant.' Conversely, homogenization of through-the-thickness tension specimens of quenched-and-tempered steel plate, containing 1.47 pct Mn, increased the strength by as much as 10 pct and the tensile ductility by at least a factor of twos5 This improvement was related to the elimination of manganese-rich bands, which also are one of the factors responsible for cold cracking in the heat-affected zone of metal-arc welds.7 In the present study the nature and severity of banding in early commercial 18Ni(250) maraging steel plate and in laboratory-melted 18Ni(250) maraging steel plate was determined. The effects of banding on plane-strain fracture toughness and the effects of thermal homogenization treatments on the strength, tensile ductility, and toughness of 18Ni(250) maraging-steel as-cast ingots and rolled plate were evaluated. In addition, the effects of hot deformation by rolling on the mechanical properties of ingots were determined. 1) STUDIES OF BANDING IN EARLY PRODUCTION PLATE The chemical composition of the steel (A) used in this part of the investigation is shown in Table I. Banding was not clearly evident in either as-rolled or annealed* plate, but annealed and agedc** plate had a banded structure. The typical banded condition, Fig. 1, consists of layers of unetched austenite (white) and dark-etching martensite in a light-etching martensitic matrix. X-ray diffraction measurements showed that this steel contained more than 6 pct austenite. An electron-probe X-ray microanalyzer (using a focused beam of electrons) was used to determine the composition of the bands and of the material between the bands with respect to the main alloying elements— nickel, molybdenum, titanium, and cobalt. The recorded X-ray intensities were converted to concentration values with the use of a standard of similar composition. To facilitate probe positioning, all analyses were conducted on specimens that had been given a light etch. The influence of this etching on the analytical results was negligible; analyses made on the identical area before and after etching yielded essentially the same concentration values. The results of the electron-microprobe analyses at selected points revealed that the layers of austenite and adjacent dark-etching martensite contained greater amounts of nickel, molybdenum, and titanium than did the surrounding matrix, Table 11. The austenite layers

Jan 1, 1968

By W. W. Whitaker, C. W. Manry, R. H. McLean

In an eccentric annulus, cement may favor the widest side and bypass slower-moving mud in the narrowest side. Tendency of the cement to bypass mud is a function of the geometry of the annulus, the density and flow properties of the mud and cement and the rate of flow. Bypassing can be prevented if the pressure gradient protluced from circulation of the cement and buoyant forces exceeds the pressure gradient necessary to drive the mud through the narrowest side of the annulus at the same velocity as the cement. In the absence of buoyant forces, one requirement for this balance is maintenance of the yield strength of the cement greater than the yield strength of the mud multiplied by the maximum distance from the casing to the wall of the borehole and divided by the minimum distance. If the yield strength of the cement is below this value, bypassing of mud cannot be prevented unless buoyant forces or motion of the casing significantly aid the displacement. INTRODUCTION Successful primary cementing leaves no continuous channels of mud capable of flow during well treatment and production. Prevention of channels requires care. Tep-litz and Hassebroek provide evidence of channels of mud after primary cementing in the field.' Channeling of cement through mud in laboratory experiments has also been reported.'-' Recommendations for improving the displacement of mud include (1) centralizing the casing in the borehole,'-" 2) attaching centralizers and scratchers to the casing and moving it during displacement,18 "3) thinning the isolating the cement by plugs while it is circulated down the casing,%( (5 establishing turbulence in the cement," and (6) holding the cement slurry at least 2 lb/gal heavier than the mud and circulating the cement slurry at a very low rate of flow.' Although much has been written about the above parameters, the relative importance of each has not been well defined. In this investigation, the mechanics of mud displacement are described through results from analytical models and experiments. The model chosen — a single string of casing eccentric in a round, smooth-walled, impermeable borehole — is analagous to casing centralized in a borehole which is not round and to placing more than one string of casing in a borehole. In each, some paths for flow are more restricted than others. A fluid flowing in the borehole may seek the least restricted, or most open, path. This tendency for uneven flow can lead to channeling of cement through mud unless preventive measures are taken. The analytical models describe channeling and give means of balancing the flow. Experimental data test the analytical models and illustrate effects of motion of the casing, differences in density and mud's tendency to gel. Results are encouraging. Piston-like displacement of mud by an equal density cement slurry is possible through proper balance of the flow properties of the mud and cement slurries to the eccentricity of the annulus. The more eccentric the annulus, the thicker must be the cement relative to the mud. If proper balance is not achieved. bypassing of mud by cement cannot be prevented without assistance from motion of the casing or buoyant forces. Increasing the rate of flow can help to start all mud flowing but cannot prevent channeling of cement through slower moving mud in an eccentric annulus. Thinning the cement slurry tends to increase channeling although the extent of turbulence in the annulus may be increased. Description of flow in an eccentric annulus begins in the next section. It is assumed that (1) the casing is eccentric and is stationary, (2) the mud and cement slurries have the same density and (3) the gel structure of the mud has been broken and the mud and cement follow the Bingham flow model. Effects related to these restrictions will be discussed. FLOW PATTERNS SlNGLE FLUID IN ANNULUS Flow of a single fluid through an eccentric annulus is illustrated in Fig. 1. Part A shows laminar flow of a Newtonian fluid. This distribution of flow was calculated by Piercy, Hooper and Winney.' In fully developed turbulent flow, the velocity distribution around the annulus is less distorted, but the flow still favors the widest part of the annulus Parts B, C and D of Fig. 1 are a qualitative representation of the flow of a Bingham fluid. The yield strength of the fluid increases the severity of bypassing compared to Newtonian flow. At a very low rate of flow, all flow is confined to that portion of the annulus which has the minimum perimeter-to-area ratio. The fluid shears on the perimeter of that area when the pressure gradient multiplied by the area just exceeds the yield stress of the fluid multiplied by the perimeter. Whether or not the minimum perimeter-to-area region encompasses all of the annulus or only a part (as shown in Part B) depends on the geometry of the annulus. If only a part begins to flow, increasing the rate of flow increases the area flowing until finally there is flow throughout the annulus.

By Louis Jordan

THIS paper presents in an abbreviated form the chief points of interest in an investigation of the tarnish-resistant qualities of silver alloys, an investigation which has been carried out as a joint research by the Bureau of Mines and the Bureau of Standards and will later be reported in detail in an official publication from these bureaus. In 1923 a Commission of Gold and Silver Inquiry was created by a Resolution of the U. S. Senate to study the causes of the depressed condi¬tion of the gold and silver industry. In cooperation with this commission the Bureau of Mines made a preliminary survey to determine in what ways, if any, it might be possible to increase the uses of silver. One of the possibilities indicated by this survey was the development of silver alloys which should be non-tarnishing, or at least less-tarnishing, than the usual sterling silver (copper-silver). The preparation of a rather wide variety of silver alloys and the determination of their behavior under accelerated tarnish tests in the laboratory was therefore undertaken by the bureaus, of Mines and Standards as a joint investigation. PREVIOUS WORK ON TARNISH RESISTING SILVERS At about the time this work was undertaken interest in tarnish-resisting silvers was rather keen due to announcements from England that there had been developed a new silver alloy, "Silanca," which was resistant to tarnish. It was even frequently described in the popular press as "non-tarnishing." A few samples and several analyses of "Silanca" which were available indicated that it was an alloy of sterling fineness, that is, it contained about 93 per cent. of silver, with approximately 4.5 per cent. of antimony and either cadmium or zinc, or both, to make the remaining 2.5 per cent.

Jan 1, 1927

By C. Feng, W. E. Krul

A study was made of the development of texture and the anisotropy in plastic flow of Ti-8Al-1Mo-1V alloy. Based on Pole figure determinations, the shifting of texture induced by rolling at approximately 400°C was found to be due primarily to slip rotation for the major Portion of the material. Grain boundary shear is believed to be an important factor. The anisotropy of the textured alloy was examined in terms of the variations of yield stress under tension and the ratio of bi -axial strain increments µp, in the temperature range 25" to 290°C. The results were related to Hill&apos;s theory on plastic anisotropy. The Schmid factors of (1100)[1120], (1101)[1120/, and (1101)[1120] slip systems were analyzed and found to be compatible with the observed anisotropy. Cross-slip between these planes was proposed as a possible deformation mode. In a number of published articles, considerable interest has been directed to the possible achievement of texture hardening in hcp metals. Following Backofen, Hosford, and Burke,&apos; this phenomenon was related to the yield criteria of the material and was expressed in terms of the biaxial strain ratio, r = d?w/d?l. The higher the value of r, the greater is the expected potential for texture hardening under certain loading conditions. For a given material, r varies with direction. Such variation can be traced to the anisotropy in plastic flow and can be explained within the framework of the various modes of deformation. Hatch2 found that a high r value coincides with a texture whereby the (0001) pole is closely aligned with the surface normal for sheet materials, Based on the analysis of the slip on the {1010}, {1011}, and (0001) planes, Lee and Backofen3 and Avery, Hosford, and Backofen4 concluded that the resistance to thinning is reduced by the operation of the (0001) <1120> slip system; with this reasoning they were able to explain the low r values (i.e., r « 1) observed in magnesium alloy sheets in the rolling direction and in commercially pure titanium in the transverse direction. The general equation, dealing with plastic flow in a polycrystalline aggregate has been used to correlate the plastic anisotropy and texture. In this expression, T and s are shear and normal stresses, and dri and d? are shear and normal strain increments, respectively. Assuming that five slip systems are operative within each grain and applying the principle of maximum work,5,6 one can determine the m value among the available systems. On this basis, Hosford7 and Chin, Nesbitt, and Williams&apos; were able to correlate m with yield stress under plane-strain compression, and Svensson9 was able to predict the variation of yield stress in textured aluminum. These workers made their analyses from materials in which slip operation is known to be associated with plastic flow. Questions remain regarding the derivation of Hill&apos;s theory on plastic anisotropy,10,11 since it was formulated on von Mises&apos; yield criterion.&apos;&apos; Its ability to deal with other forms of deformation has been in doubt.13 Others have discussed the validity of Hill&apos;s quadratic equation relating strain and yield stress.14&apos;15 For hcp titanium, deformation by various modes of slip and twinning operations has been reported.16-20 If all possible modes of deformation operate and contribute substantially to the plastic flow, it is difficult to imagine how the quadratic expression can suitably describe the anisotropic plastic flow of titanium alloys. Backofen and Hosford15 considered that Hill&apos;s is a macroscopic theory and implied that the major mode of deformation by slip mechanism will adequately describe anisotropy of the material. In the present investigation, slip operation will be shown to play the major role in the development of sheet texture induced by rolling of a commercial titanium alloy. Although twinning and other modes of deformation may also operate, their operation is believed to be secondary. The anisotropic properties of the sheet, which can be expressed in terms of directional variation of r, µp = -d?w/d?l and the yield stress will be shown to be governed primarily by slip operation. MATERIALS AND EXPERIMENTAL TECHNIQUES The titanium alloy chosen for the present investigation had a nominal composition of 8 wt pct Al, 1 wt pct Mo, 1 wt pct V, and 0.1 wt pct interstitial impurities. Sheets varying between 0.1 and 0.15 in. thickness were used. The alloy was received in a condition which was prepared by rolling at 900°C and annealing at 700°C. Subsequently, the sheets were subjected to further reduction in thickness by rolling at 400°C. A total reduction in thickness of 65 to 70 pct was obtained by a series of quick passes in a rolling mill with intermediate reheating. Further reduction in thickness was not possible due to cracking developed at the edges of the sheets. X-ray measurements were conducted in a Siemens and a Norelco unit to determine the texture of the sheets. Reflection techniques were used exclusively with CuK, radiation and a nickel filter. The loss of X-ray intensity due to geometric defocusing was calibrated with a technique described previously." The (0001), (1010), and (1071) pole figures were plotted from 0 to 80 deg, and to present the texture elements quantitatively, inverse pole figures were constructed following the technique described by Jetter, McHargue, and Williams.22 Tensile experiments were carried out at 25", 175",

Jan 1, 1970

By Nicholas J. Grant, Joseph T. Blucher

High-purity aluminum and an Al-10 pet Zn alloy zvere tested in axial fatigue from 80" to 900oF, at struzn vales of 5 and 150 pct per min, at a strain amplitude of 1 pcl. Cycles to failure were recorded as well as the load per cycle during the entive test. Several grain sizes were examined in each material. Examination was made of modes of deformation, initiation and growlh of&apos; cracks, and vecovery mechanisms such as srbgrain formation and boundary migration. Strain rate effects on cycles to failure are first observed ahoi&apos;e 50O0F, the highev vate vesulting in longer lije. Crack initiclion at room temperature may be truns-or iutercrystalline but fructures are transcrystalline. Abore 600&apos;F, crack iniliation and growth ave largely inlercvystalline. Boundary wzigratiotz to 45-deg positions is observed above 70Oo F, and fractrrves are a combination of grain bol~ndary voids and cvacks. It is only in recent years that studies of deformation and fracture which prevail in fatigue at elevated temperatures have attracted significant attention.&apos; Of such studies considerably less attention was given to high strain-low strain rate fatigue. Moreover, the majority of high-temperature fatigue studies were performed at conventional machine speeds (1000 to 10,000 cpm). As it is well-demonstrated in uniaxial creep-rupture series, at high strain rates, even at high temperatures, metals undergo work hardening with little or no attendant recovery or recrystallization thus the nature of deformation and fracture which is observed is similar to that encountered at lower temperatures.&apos;-" Thus, for example, fatigue testing of a stainless steel at 750°F does not involve high-temperature deformation processes,2 and might more correctly be termed "fatigue testing at an elevated temperature". It was the purpose of this work to study deformation and fracture in fatigue as a function of low strain rates and temperature, selecting conditions which would result in grain boundary sliding, migration, fold and subgrain formation, and intercrystalline cracking in high-purity aluminum and a high-purity A1- 10 pct Zn alloy. Grain size was an additional variable. Extensive studies of the deformation and fracture behavior of these aluminum materials in simple creep had been done in the authors&apos; laboratory, and were to serve as a basis of comparison for the observed effects in fatigue:&apos;-&apos;&apos; the range of the creep test temperatures was 80° to 1150oF. MATERIALS AND EXPERIMENTAL PROCEDURE The compositions of the 99.99 pct pure A1 and the A1-10 pct Zn alloy are shown in Table I. Button-head specimens, with a liberal fillet, of 0.20 in. diam and of gage length 0.40 in. were machined from wrought bar stock. The ratio of 2:l gage length to diameter was selected after preliminary tests showed that a shorter length gave a shorter life, probably due to end effects, and after evidence of buckling in longer gage length specimens. After machining, the specimens were chemically polished to remove the worked outer layer, and were subsequently heat-treated to stabilize the selected grain sizes. Both the high-purity aluminum and the A1-10 pct Zn alloy were heat-treated to produce grain diameters of approximately 0.5 and 2 mm in each case. These grain sizes are referred to in the text as fine and coarse grain, respectively. One lot of the high-purity aluminum was heat-treated to produce a still coarser grain size in which the cross section was occupied by 2 to 3 grains. This structure is referred to as very coarsegrained. After heat treatment, the specimens were again electropolished. To avoid complications of both stress and strain gradients in the cross section of the specimen, a hydraulic, axial fatigue machine was designed and built. A button-head specimen, 1/2 in. diam at the head, was firmly gripped in a split-type holder free of any play in the grips. The test temperatures varied from 80" to 900°F. The strain amplitude in all of the reported tests was 1 pct for a total strain amplitude of 2 pct. The strain range was set by precision micrometers and measured by a precision dial gage. Constant strain rates of 5 and 150 pct per min were selected so that high-temperature type deformation and fracture would occur in the higher-temperature tests5,6 The strains and strain rates must be regarded as nominal values because they are based on the original specimen dimensions, which changed significantly as a result of necking and crack propagation, as can be observed from Fig. 8. For the elevated-temperature tests, a thermocouple was inserted into a well in the head of the specimen; the selected temperatures could be maintained with less than ± 5oF fluctuation during the entire test. To avoid changes in grain size before the test, specimens were heated to the test temperature in less than 15 min; similarly, they were cooled to room temperature after fracture with an air blast to avoid or minimize recovery or recrystallization. During the fatigue tests, load vs strain curves were recorded by a strain gage load cell for each fatigue cycle. In addition, the maximum values of load amplitude were recorded for the entire test.

Jan 1, 1968

By H. Biloni, R. Morando

The surface structure and substructure of Al-Cu alloys solidified as conventional ingots and under particular conditions such as those used by Bower and Flemings are studied. The influence of lampblack coating on the mold walls is especially considered and the results compared with those obtained in copper and graphite molds where no coatings exist. When high heat extraction conditions exist the observations show that mechanism of copious nucleation is responsible for most of the chill zone. When the heat extraction through the mold walls is low, a coarse grain structure with dendritic morphology arises, with a size that depends on the degree of convection present, analogous to that analyzed by Bower and Flemings. In both cases the effect of the convection on the macroscopic and microscopic appearance is discussed. The ingot macrostructure consists of one or more of three zones: "chill zone", "columnar zone", and central "equiaxed zone". The mechanism of the columnar-equiaxed transition has been subject of considerable interest and at present at least three theories exist about the formation of the equiaxed region: 1) the constitutional supercooling theory1 maintains that the equiaxed crystals nucleate after the columnar zone has formed, as a result of the constitutional supercooling of the remaining liquid; 2) chalmers2 pointed out, however, that there were several objections to this proposal, and that consideration should be given to the possibility that all the crystals, equiaxed as well as columnar, originated during the initial chilling of the liquid layer in contact with the mold; 3) Jackson et aL3 and O&apos;Hara and ~iller~ suggested that a remelting mechanism of the dendrite arms is responsible for the formation of the equiaxed region. After the work of Cole and Bolling and other authors6 it became evident that convection (natural, reduced, or forced) plays a very important role in the transition from columnar to equiaxed and on the size of the resultant equiaxed structure. Until recently the accepted explanation of the chill zone was that it occurs as a result of copious nucleation in the liquid layer in contact with the mold walls.798 The columnar region is a subsequent result of the growth of favorably oriented grains and, as a result of a selection mechanism studied by Walton and Chalmers,9 elongated grains with marked texture are formed. Recently, however, Bower and Flemings" using an ingenious laboratory experiment introduced the idea that the "copious nucleation" mechanism is not responsible for the formation of the chill zone and that the presence of convection, introducing some form of "crystal multiplication", plays a decisive role in the formation of the chill zone. Unfortunately, it is important to consider that for their conclusions Bower and Flemings extrapolated the results obtained in their special experiments to the case of conventional ingots, and that these authors only analyzed the macrostructures of the specimens. Let us consider the work by Biloni and chalmers" concerning predendritic solidification. These authors were able to show that a study of the segregation substructure of A1-Cu gives information about the nucleation and growth of crystals formed in contact with a cold surface. A spherical predendritic region characterizes the first part of every grain nucleated in contact with the surface as a result of the chill effect. The aim of this paper is to elucidate through the observation of the segregation substructure the conditions under which (in the Bower and Flemings type of experiments and in conventional ingots) either the nucleation or the multiplication mechanism gives rise to the structure in contact with the mold walls. I) EXPERIMENTAL TECHNIQUES The experiments were performed on two alloys: Al-1 wt pct Cu and A1-5 wt pct Cu. The purity of the aluminum was 99.99 pct and the copper 99.999 pct. The results obtained with both alloys were similar. In the Bower and Flemings type of experiments the apparatus employed to obtain rapid solidification against a surface was similar to that used by those authors. The liquid was drawn by partial vacuum into the thin section mold cavity. Plate casts were 5 cm wide and usually 7.5 cm high. The thicknesses of the cast were 0.1 and 0.3 cm. Two different materials were used for the mold, copper and nuclear-grade graphite. The internal mold surfaces were polished and left uncoated for some experiments. In other experiments, the copper or graphite surface was coated with a thin film of lampblack material. In some of these particular experiments one of the mold walls was left with an uncoated region (usually in the form of a cross). The conventional ingots were cast in graphite or copper molds. In different experiments the mold walls were sometimes uncoated or coated with lampblack material. The results obtained in conventional and Bower and Flemings copper molds were compared with those obtained with copper molds coated with a very thin film of graphite; the results obtained were essentially similar. The size of the conventional ingots was 5 cm diam and 7 cm high in all cases. The cast surfaces produced by the Bower and Flemings type of experiments and conventional methods were observed macroscopically and microscopically without any metallographic preparation. As Biloni and Chalmers showed," the observation of the chill surface can give considerable information about the structure and segregation substructure.

Jan 1, 1969

By G. S. Cole, H. Biloni, G. F. Bolling

An experimental investigation of sovlze low .melting point alloys sJtows that a substvucture of isolated depressions can be the first manvestation of constitutional supercooling on solid-liquid interjaces veuealed by decanting. Electron-tni cvop vobe and wletallo gvaplic esanzinations, in tlze bulk belzind the interjace, oj the segregation associated with these isolated areas substantiate tlzei&apos;v depressed nature, since a solute of ko < 1 is enriched, and a solute of ko > 1 depleted. In contrast, the pox structuve, a set of projections often veported in the literature, leaves no trace oj. segvegation. These obserl;atims, accovlrpanied by a brief review of recent literature, point to inconsistencies between experirrental obsevvation and the idea that the fornzation of a projection is a causal step in the development of a cellular substructure. An argument is presented to show instead how it is plausible for substantial depvessiom to form in the pvesence of constitutional supercooling at dislocations threading the solid-liquid interjace. THE development of constitutional supercooling during growth from the melt leads to the formation of the cellular solidification substructure. This well-founded association between structure and instability has been basic in understanding cellular substructure and micro segregation; however, the initial formation of structure seems unclear. Rutter and Chalmers,&apos; in definitive experiments and theory, noted that in the presence of constitutional a planar interface might break down: "resulting in the formation of a small projection on an initially plane or uniformly curved interface." That is, the breakdown from a planar to a cellular interface was implied to be initiated via a projection into the unstable liquid. Later, Walton et (11. found that a structure of isolated projections, termed "pox", appeared at solid-liquid interfaces decanted under growth conditions near the onset of constitutional supercooling; the pox were taken as the indication of the instability promoted by the supercooling. Tiller and Rutter4 in their extensive work studied the shape transitions at decanted interfaces which were generally observed to proceed as— pox, "irregular cells", elongated cells, regular (hexagonal) cells, and so forth. The pox varied in size from lo-&apos; to 1CT4 cm, and tended to disappear as cells increased in number and regularity, but as noted,4 the first real array of cells did not seem to be a development from the pox. In fact these authors implied a lack of connection because they stated that the pox are denser on "irregular cells", and as cell boundaries increase in number (i.e., the cells become smaller) there is less need for the pox which do dis- appear. Thereafter, most authors dealing with either experiment or theory have accepted the reality of pox and have used them as a criterion for the onset of constitutional supercooling. In contrast, Spittle, Hunt, and smiths have now suggested that pox are irrelevant artifacts comprised of such things as entrapped oxide. This proposal invokes the observations of weinberg6 and chadwick7 each of whom have shown that the act of decanting leaves a residual liquid on a decanted interface; the remnant solid layer of the order 10 p may thus contain particles that might have been transported from the external surfaces, or elsewhere, during decanting. With the incentive of this suggestion,= some further experiments and a reexamination of the literature have been conducted, in order to question the validity of pox as evidence of an instability and to examine the initial development of the cellular substructure. 1) EXPERIMENTS Single crystals of zone-refined tin (-99.9999 pct) were grown from the melt in a controlled fashion with various, small concentration additions of lead and antimony, for which ko < 1 and > 1, respectively. The crystals were decanted at conditions near the onset of constitutional supercooling and were thus appropriate for observation of slight perturbations. It was possible to observe two types of small departure from smooth or "planar" interfaces in both cases of lead or antimony additions. Some were projections and others, if in regular array of any type, were depressions. The crystals were etched with suitable reagents progressively dissolving the decanted interface surface; projections left no record, but depressions were continuously associated with spotlike areas contrasting with the rest of the interface. Traverses were made with the beam of an electron microprobe across the regions of contrast; with lead addition the persistent spots were lead-rich, and with antimony addition the persistent spots were antimony-poor. This is consistent only with a dominant role for depressions, because if the projections had left spots but were incorrectly catalogued, a reversed observation should have been made; that is, the Pb(ko < 1) should have been depleted and the Sb(ko > 1) enriched. In the work of Cole and inegard, and elewhere, regular arrays of structure associated with the initial stage of instability have been shown, in photographs and represented as pox or projections. We believe this to be erroneous, by inference, since whenever a regular array was observed, in the present examination, it consisted of depressions, regardless of the nature of the solute, ko 1. Fig. 1 is reproduced8 as an ideal example of the possible optical illusion involved; the observer can satisfy himself from the distribution of illuminated areas that the markings are depressions. Fig. 2 from the present investigation is an interference photograph of an interface similar to that in Fig.

Jan 1, 1967

By Henry Howe

(New York Meeting, February, 1913.) THE transformation which steel undergoes in glow cooling, from the condition of austenite when above the transformation range into that of pearlite plus either ferrite or cementite below that range, is subject to great lag. This transformation is essentially the pearlitizing of the austenite. Indeed the hardening of steel is due to this lag, which is made so great by extremely rapid cooling that a very large part of the transformation itself is restrained, so that the rapid cooling catches the metal in an only partly transformed state, that of martensite, and under favorable conditions even in an almost wholly untransformed state, as in the cases of Maurer&apos;s austenitic manganese steel. Hadfield&apos;s austenitic manganese steel, 25 per cent. nickel steel, and other austenitic alloy steels, are austenitic even after slow cooling. It has long been known that this- lag increases (1) with the rapidity of cooling, (2) with the presence of certain retarding elements, notably manganese and nickel, and (3) with the temperature from which cooling starts. The present inquiry touches the last. of these influences, but incidentally it throws light on the first also. This influence of higher heating in increasing lag manifests itself in different ways which, though they may at first seem unrelated, are in fact but different, aspects of one and the same thing. Thus, among heatings to different high temperatures, all of them above the transformation range, the higher the temperature to which the steel is heated (1) the lower is the temperature it which the transformation occurs in cooling slowly down, (2) the shorter is the time occupied in the actual cooling from above the transformation range to the room temperature under given external conditions, whether of slow or

Jan 3, 1913

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970