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By J. P. Boisseau, C. N. J. Wagner, E. N. Aqua

An analysis ulas made of powder-paltern peaks from cold-rolled polycrystalline copper and from copper powders, compacted into briquets (1 in. diameter) with pressures up to about 106 psi. Powder-pattern peaks from both contact faces were measured with a diffractometer and CuKa radiation. Laltice-parameter measurements indicate the presence of residual stresses in the bulk specimen of the order of a - -10 kg per sq mm after 93 pct reduction in thickness, and give some evidence for the occurrence of deformation stacking faults (probability a - 0.003) in both bulk and powder samples. Fourier analyses of the line profiles were carried out on the (111) - (222) and (200) - (400) Pairs of reflections. The particle sizes decrease rapidly with increasing deformation and reach asymptotic values of De (111) = 550A and D, (200) = 350A at about 25 pct reduction in thickness or 80,000 psi pressure for compaction. The anisotropy of the particle sizes indicates the presence of microtwins and stacking faults on (111) planes. The rms strains increase also with deformation and reach limiting values of 2 x 10-3 in the [100] direction and 1 x 10-3 in the [Ill] direction at a distance L = 100A normal to the reflecting planes. THE diffraction of X-rays in cold-worked, polycrystalline, fcc metals and alloys yields Debye-Scherrer patterns in which the individual (hkl) lines may show a broadening, a shift, and an asymmetric shape.' These effects can be explained by the fragmentation of the small, coherently diffracting domains, the presence of residual elastic strains in the lattice, and the formation of stacking faults. X-ray studies of stacking faults in fcc metals and alloys have been methodically performed during the last few years, but so far most of the investigators dealt with cold-worked powder specimens obtained by filing.2-8,10-19 In such specimens, the crystals are randomly oriented and the average elastic strains are assumed to be zero, so that the observed peak shifts are due to stacking faults only. The agreement between X-ray diffraction theory1,20 and experiment is generally good. On the contrary, cold-worked, polycrystalline bulk specimens (after wire drawing, rolling, plastic deformation by tension or compression, etc.) contain residual elastic strains, which may not average to zero in the surface of the specimen and show very strong preferred orientation of certain lattice planes (texture) parallel to the specimen surface. Nonzero elastic strains also produce peak shifts, the magnitudes of which depend upon the crystallographic orientation of the reflecting lattice planes in elastically anisotropic materials as well as on the type of plastic deformation and which have to be taken into account when measuring stacking-fault probabilities in deformed bulk specimens.21-23 The purpose of the present investigations was to perform a detailed X-ray analysis on a bulk specimen of a fcc metal deformed by rolling at room temperature and on powder of the same material deformed by compaction, and to compare these results with those previously obtained on cold-worked filings.18 Pure copper was chosen for this study since it is known to produce only a small quantity of stacking faults by filing at room temperature.3,16,17,19 The residual elastic strain in the surface of the bulk copper should be the predominant factor determining

Jan 1, 1965

By F. W. Schremp, J. W. Chittum, T. S. Arczynski

This paper describes a laboratory study of causes of external casing corrosion and the test work that led to the use of oxygen scavengers to prevent this attack. External casing failures are classified as water-line, casing-casing, collar and body failures. A corrosion mechanism based on principles of differential oxygen availability is developed that is consistent with facts known about each kind of failure. The field use of oxygen scavengers is depicted as a direct result of the laboratory study. A part of the paper is devoted to reporting on the field use of hydra-zine to control external casing corrosion. Results of field measurements made over a period of several years are presented as evidence of the efectiveness of the hydrazine treatment. The first conclusion reached is that the use of hydrazine materially reduces the cathodic protection requirements for treated wells. This result is interpreted to mean that a reduction is taking place in the amount of corrosion on the casing. Results indicate also that hydrazine shows its greatest usefulness within the first 12 to 18 months after a well is completed when pitting corrosion is likely to be most active. INTRODUCTION According to surveys sponsored by the National Association of Corrosion Engineers,' the cost of repairing casing leaks caused by external corrosion may exceed $4 million per year. In addition, well damage and lost production resulting from casing leaks probably costs the petroleum industry an additional $5 to $6 million per year. Concern about the cost of external casing corrosion led to an extensive laboratory study of factors causing this external corrosion and to the development of a new approach to its prevention. This paper presents a discussion of various causes of external casing corrosion, details of laboratory studies and the results of the field use of an oxygen scavenger in well cementing fluids to prevent the external corrosion of oil-string casing. Measurements on test wells over a period of several years show that cathodic-protection current requirements are greatly reduced when hydrazine is used in cementing mud. Reduction of current requirements can be interpreted to mean that removal of oxygen by hydrazine has greatly suppressed corrosion cells on the external surface of the casing and thereby, has reduced corrosion. To date, hydrazine has been used by the Standard Oil Co. of California in more than 200 well completions. KINDS OF CASING FAILURES A survey of a large number of casing leaks disclosed four types of external casing failures — water-line, casing-casing, collar and body failures. These types are identified largely by their location on the casing. Water-line failures are found just below the surface of water or mud in the casing annulus. Casing-casing failures occur on the oil string just below the shoe of the surface string. Collar failures are found in the threaded ends of casing joints where they are screwed into casing collars. Body failures may occur at any point on the body of a casing joint. Ex- amples of each kind of failure have some of the general characteristics that are shown in Fig. 1. Water-line failures usually result in the circumferential severance of an oil-string casing. The corrosive action causing a water-line failure usually is sharply defined and is limited to a short length of the casing. Casing-casing failures usually are accompanied by pitting corrosion distributed around the oil-string casing for distances up to 100-ft below the shoe of the surface string. Casing-casing failures may also sever the casing. Collar failures seem to start on the first thread at the bottom of recesses between collar and casing joint. Corrosion proceeds across the threads by what appears to be a normal pitting mechanism. Both casing and collar are severely attacked. Body failures are the result of highly localized pitting at any point on a casing wall. Besides the pit that perforates a casing, a large number of other pits usually are found along one side of the casing joint. The pits occasionally are filled with corrosion products consisting largely of oxides and sulfides.' Frequently, the mill scale is largely intact on the rest of the casing. Examination of a casing failure does not always reveal the cause of the failure. Frequently, the necessary details are destroyed when the failure occurs. For example, formation water flowing through a perforation at high velocity may enlarge the hole and destroy any remaining evidence of the cause of the failure. One way to obtain undistorted information about a failure is to study the nature of other pits on the casing in the vicinity of the failure. A study of such pits frequently suggests that they are characteristic of an attack resulting from the differential availability of molecular oxygen.

By P. N. Nikiforuk, M. C. Zoerb

An analog computer model has been developed of a large, walking dragline. This model permits changes in the configuration of the dragline, or changes in its digging cycle, to be readily investigated on a computer. As a result, it is possible to determine ways of improving the dragline performance without having to carry out many expensive experiments on the actual machine. This model can also be used as a simulator for dragline operator training. INTRODUCTION The movement of large volumes of material is always a costly operation and the increasing trend towards the use of large capacity equipment does not necessarily produce the economy desired. This problem is of particular concern to the mining industry in its open-pit operations where large draglines are used to remove the overburden. Since this operation often forms a very large part of the total cost of open-pit mining it is particularly important that it be kept as economical as possible. This requires that the dragline be operated at its maximum possible productivity. In order to optimize the operation of a dragline it is desirable that a suitable model of the dragline be available for study. Once such a model is available the effects of changes in the configuration of the dragline, or changes in its digging cycle, could be readily investigated on a computer and methods of improving its performance could be determined without having to carry out expensive experiments on the actual machine. Such models would be of use not only to dragline users, but also to the manufacturers of draglines for design purposes. Presumably studies of this type could eventually lead to computer-con trolled stripping operations. As far as can be determined very little work1'2 has been done on the derivation of dragline models. Such models must be derived before work of the nature indicated in the previous paragraph can be carried out. As a small contribution to this field this paper describes work that has been carried out by the senior author during the past few years on the derivation of one such model. This model describes the drag, hoist and swing operations of a 35 cu yd, commercially available, walking dragline. This model was derived for use with an analog computer and can be used either for optimization studies, or for the training of dragline operators. DESCRIPTION OF DRAGLINE General: The particular dragline for which an analog computer model was developed is owned by the Great West Coal Company of Estevan, Saskatchewan. It is a walking dragline and its function is to remove 40

Jan 1, 1967

By G. L. Fisher, R. H. Geils

The effect of small amounts of columbium (<0.01 to 0.10 pct) on the ?-a transformation occurring during the continuous cooling of a low carbon Ni-Cu steel was investigated. Dilatometer specimens were aus-tenitized at 950" and 1068?C and cooled at 17? and 375 C° per min. Columbium caused a marked depression in the ?-a transformation temperature except when cooling at the slower rate from 950°C. The effec of columbium on the transformation temperature was greater the higher the austenitizing temperature and rate of cooling. A maximum depression of 92 C" was observed. Metallographic examination of specimens of <0.01 and 0.07pct Cb steels heated at 1200°C for 1 hr and cooled at various rates showed that columbium had a major effect on the ferrite morphology. The fer rite in the columbium -free steel remained equiaxed at cooling rates as high as 440 C? per min while the columbium-bearing steel exhibited mixed structures o equiaxed and bainitic ferrite at cooling rates as low as 130 C° per min. The ? grain boundaries in the columbium -free steel provided the ferrite nucleation sites in rapidly cooled specimens. There was a complete absence of nucleation at these sites in the colum bium-bearing steel. It is concluded that columbium depresses the transformation temperature by suppressing ferrite nucleation at the austenite grain bound-aries. In this respect the effects of columbium are analogous to those of boron in low C-Mo steels. It is well known that small columbium additions can substantially strengthen plain carbon steels. As little as 0.02 pct Cb can increase the yield strength of mild steels by 10,000 psi.1 A fine precipitate of CbC has been observed in columbium-bearing steels2 and is generally thought to be responsible for the strengthening. Little attention has been devoted to the effect of columbium on the ?-a transformation. Webster and woodhead3 have studied the effect of columbium on the isothermal proeutectoid ferrite reaction in mild steels. They found similar transformation behavior in steels both with and without columbium additions. However, as the austenitizing temperature increased, the incubation time for the start of the ferrite transformation became longer in the columbium-containing steel. Morrison1 found that the addition of 0.03 pct Cb to a C-Mn steel lowered the transformation temperature by 50 C° during cooling from 1200°C at a rate of 80 C" per min. The strengthening effect of columbium has recently been utilized in an age-hardenable, low-alloy steel containing copper and nickel.4 A small amount of columbium has a substantial effect on the as-rolled strength of this steel. By increasing the columbium level from <0.01 to 0.13 pct the as-rolled yield strength is increased by 15,000 psi. Columbium also significantly lowers the ?-to-a transformation temperature of this steel during continuous cooling from the austenitizing temperature. Because of the low carbon level in this steel (0.05 pct max), it is almost entirely ferritic. Thus, it offers the opportunity of studying the effect of small columbium additions on the proeutectoid ferrite reaction. Of particular interest in this study was the reason for the marked lowering of the transformation temperature by columbium during continuous cooling. EXPERIMENTAL PROCEDURE Materials. The compositions of the steels used in this investigation are shown in Table I. The steels were 30-lb air induction melts. They were forged to 4 by 8 by 1 in. plate at 1230°C, air cooled, and then reheated to 1230°C and cross-rolled in two passes to in. plates. Dilatometry. A Leitz Bollenrath dilatometer was used to record the transformation during continuous cooling from two different austenitizing temperatures. The dilatometer specimens were + in. in diam and 2 in. long. Oxidation and decarburization of the specimens was prevented by maintaining a small positive pressure of dry argon in the dilatometer furnace and by plating the specimens with 1 mil of Cu. For the lowest cooling rate, 17 C" per min, the temperature of the specimen was measured with a Pt-Pt 10 pct Rh thermocouple placed in a & in. diam well in the center of the specimen. During air cooling, 375 C° per min, this method of measuring the temperature interfered with the operation of the dilatometer. However, it was found that the temperature of the specimen could be measured accurately by placing a thermocouple in an identical specimen in a holder adjacent to the one being used to operate the dilatometer mechanism. The dilation-temperature curves were recorded on photographic film and then converted to volume percent ferrite-vs-temper-ature curves. The cooling rates obtained with the dilatometer are shown in Table 11. Cooling rates of

Jan 1, 1970

By L. C. Brown, E. B. Hawbolt

The formation of grain boundary precipitates has been studied in Ag-5.64 wt pcl Al alloys at 688°C. Large-grain specinzerzs were used and the boundary misorientation measured by X-ray diffraction. At low-angle grain boundrrries Primary sideplates form. u)hile abore a 17-deg misorientation lenticular precipitates predominate. Growth of the lenticular precipitates was studied on individual grain boundaries using a statistical technique. The thickening and lengthening rates appeared to be independent of &apos;pain boundary misorientation, indicating that grain boundary diffusion was not significant in this system. The precipitates grew urith constant shape, with both the length and thickness increasing parabolically with time. The parabolic lengthening rates were unexpected since previous theory and experimerztal results had indicated linear growth. By approximating the shape of the precipitate to that of an oblate spheroid grouling with constant shape an equivalent diffusion coefficienl was calculated. The zlalue obtained was in good agreement with nleasurements obtained fron, diffusiorz couples. IF a single-phase alloy is heated or cooled to a temperature such that the phase becomes supersaturated, there is a tendency for a second phase to precipitate from it in order to remove the supersaturation. Precipitation takes place initially on grain boundaries due to preferred heterogeneous nucleation, but subsequently Widmans kitten plates may form in the grain interiors if the grain size and supersaturation are sufficient. The type of grain boundary precipitate formed depends on the nature of the boundary. Aaronson1 and clark2 have shown that grain boundary misorientation can be characterized by the simple parameter R, where and X, Y, and Z represent the minimum rotations about three orthogonal axes required to bring the two lattices forming the grain boundary into coincidence. The maximum value for R is 60 deg. In using this parameter the orientation of the grain boundary itself is, of course, neglected. However it was found in both Fe-si3 and A1-Ag2 that the precipitate shape depended only on the parameter R. Clark found that the vast majority of precipitates formed were allo-triomorphs— lens-shaped precipitates that grew along the grain boundaries. At low-angle boundaries, however, (R < 15 deg) Widmanstatten sideplates nucleated at the grain boundaries and grew into the adjacent grains. It has been reported that the rate of growth of grain boundary precipitates is controlled by diffusion within the supersaturated phase.&apos; The theories which have been developed for growth rates have assumed the diffusion coefficient constant over the composition range of the supersaturated phase. This is a fairly good approximation if the composition range involved is not large. Thickening rates have been calculated using the theory developed by Zener4 and by Frank5 for the growth of planar precipitates. A parabolic growth law

Jan 1, 1968

By F. I. Grace, L. E. Murr

The mechanical responses and residual defect structures in 70/30 brass and type 304 stainless steel following explosive shock loading and cold reduction by rolling have been studied. A distinct relationship was observed to exist between the residual mechanical properties and micro structures observed by transmission electron microscopy. Shock-loaded brass deformed primarily by the formation of coplanar arrays of dislocations and stacking faults at lower pressures, and twin-faults (deformation twins and €-martensite bundles) at higher pressures (> 200 kbar). The micro -structures of cold-rolled brass were characterized by dense dislocation fields elongated in the rolling direction. Stainless steel was observed to deform by the formation of dense arrays of stacking faults at lower shock pressures and twin-faults at high shock pressures (>200 kbar). Lightly cold-rolled stainless steel deformed similar to low Pressure shock-loaded stainless steel, but transformed to a&apos; martensite in heavily cold-rolled stainless steel. Discontinuous yielding was observed for the heavily cold-rolled stainless steel, and stress reluxution in the weyield region for cold-rolled and shock -loaded stainless steel was interpreted as an indication of the ability of twin-faults and stacking faults to act as effective barriers to dislocation motion. A simple model for the formation of the planar defects and a&apos; martetnsite is presented based on the propagating of Shochley partial and half-partial dislocations. A considerable effort has been expended over the past decade in an attempt to elucidate the response of metallic-crystalline solids to the passage of a high velocity shock wave (e.g., smith,&apos; Dieter,2 and zukas3). While it has been possible to obtain relevant information pertaining to the residual defect structures and mechanical properties, there have been few rigorous attempts to draw a direct comparison between these structures and properties. In addition, numerous investigators have recently observed the occurrence of deformation twinning in shock deformed fcc metals (e.g., Nolder and Thomas,4 and Johari and Thomas5), but little attempt has been made to elucidate the mechanisms of formation of these defects. Comparative data for metals deformed by shock-loading and the same metals deformed by more conventional modes of deformation such as cold-reduction by rolling is also generally lacking. The present investigation therefore has the following objectives: 1) to examine the mechanical properties of some explosively shock loaded and cold-rolled fcc metals of low stacking-fault energy as a function of their residual substructures; 2) to present a simple model for the formation twin-faults and related defect structures in the low stack-ing-fault energy materials of interest (70/30 brass, ySFg= 14 ergs per sq cm; and 304 stainless steel, ySF = 21 ergs per sq cm); 3) to make some deductions with regard to the residual characteristics of dislocation and planar defect substructures in cold rolled and shock loaded 70/30 brass and type 304 stainless steel. In particular, it was desirable to characterize the residual hardening effects of particular deformation substructures. I) EXPERIMENTAL PROCEDURE Sheet samples of 70/30 brass (0.005 and 0.15 in. thick; annealed at 659°C for 2 hr) and type 304 stainless steel (0.007 in. thick; annealed 0.25 hr at 1060°C) of nominal compositions shown in Table I were cold-rolled in one direction only to produce reductions in thickness of 15, 30, 45, 60, and 75 pct in the brass; and 5, 15, 25, 35, and 45 pct in the stainless steel. Identical sheet samples in the annealed (unrolled) state were subjected to plane compressive shock waves to various peak pressures ranging from 0 to 400 kbar in the brass and 0 to 425 kbar in the stainless steel; and with a constant peak pressure duration of approximately 2 microseconds. A detailed description of the shock loading technique has been given previously.6 Tensile specimens 1.0 in. in length and 0.125 in. in width were cut from the cold-rolled sheets (tensile axis parallel to the rolling direction), and the shock-loaded sheet specimens. Stress (load)-strain (elongation) measurements on the tensile specimens were made on a Tinius-Olsen load-compensating tensile tester using a strain rate of 2.7 x 10-3 sec-1. Tensile tests were repeated at least twice, giving essentially the same results. Stress relaxation measurements in the preyield region were also made using an initial strain rate of 5.4 x 10-4 sec-1. In addition to tensile and stress relaxation measurements, Vickers microhardness measurements were made on all samples. A total of 100 microhard-ness readings were obtained for each specimen following a light electropolish to ensure uniform surface conditions for all tests. The hardness averages ob-

Jan 1, 1970

By Harold A. Krueger

FACILITIES and mining operations of the National Lead Co., St. Louis Smelting and Refining Division, near Fredericktown, Mo., are situated in a famous mining area. Copper, lead, nickel, and cobalt have been mined here for more than 100 years, work having been started on a high sulphide copper outcrop in 1847. Lamotte sandstone is characterized by differential compaction on a rigorously eroded pre-Cambrian surface. The Bonneterre formation was therefore a good host for minerals not generally found in mineable quantities in these midwestern areas. Unusually complex minerals, however, make beneficiation difficult, and because of irregular ore thicknesses and elevations many engineers and operators have not attempted to mine the property. Others have tried who failed. This paper deals with economic, efficient, and competitive methods of mining these highly irregular orebodies, as compared to the open-stope, room-and-pillar methods normally used for horizontal-bedded lead deposits. For the purpose of this study it should be understood that the ore is found in two distinctly different types of occurrences, one to be designated as basin ore and the other as contact ore. Mining of basin ore is complicated by many faults, fractures, cross faults, and breaks. Contact ore is complex because it is found on flanks or slopes of pre-Cambrian knobs or highs. The dip of the mining floor for the latter type varies between 18" and 45". Occurrences of both types of ore are complicated by water courses or solution channels which carry unconsolidated shale, lime, sand, and dolomite. This material is also found between the bedding planes of the members of the Bonneterre formation. The water found where there are fractures, faults, and channels makes it very fluid and tacky, see Fig. 1, particularly after it has been blasted and handled by loading and hauling machines. Much of the ore can be wadded and thrown without dispersing. During early operations by the Buckeye Copper Co. in 1861 and the North American Lead Co. from 1900 to 1910, conventional narrow-gage railroad and side dump mine cars were used with hand shoveling. The complications of mining the contact ore, the only type attempted at this time, can be appreciated when it is realized that operators were obliged to use mules for haulage. Haulageways constructed on these slopes were of necessity similar to wagon trails or goat trails up the side of a mountain. In other words, it was merely a matter of going from side to side of the strike length of the slope, gaining a little in elevation on each shuttle trip. Production totaled only one to two tons per manshift. A few years later, about 1913, the property was purchased by combined Canadian interests known as the Missouri Cobalt Co., and the use of trolley locomotives was initiated. Between 1900 and 1928 a land agent using churn and diamond drilling methods prospected scattered sections of the area. In 1928 the first property was purchased by the present company, then operating as the St. Louis Smelting and Refining Co. Check drilling and prospecting was carried out by the company at various times between 1928 and 1939 to correlate the erratic mineralization. Much information about both types of orebodies was accumulated, but it was still questionable as to whether money should be invested to work these occurrences. In anticipation of high lead and copper prices, about the time World War II started, it was decided to develop and bring into production some of this ore. In 1942 No. 1 shaft was put down on the largest basin-type orebody and in 1943 No. 2 shaft was put down on contact-type ore. Operations were expanded when No. 3 shaft was completed in 1943, and progressed further in 1948, when National Lead Co. dewatered and opened No. 5 and 6 mines, old workings of the North American Lead Co. and the Missouri Cobalt Co. Because of the differential compaction of Lamotte sandstone over the pre-Cambrian porphyry, in some instances mineable thicknesses of basin-type ore occurred 20 to 30 ft above the sand. This is the exception rather than the rule, since most of the mineralization starts at the sand and is variable in thickness. The ore was attacked, therefore, by development drifts and crosscuts at the lowest possible elevation, where the ore immediately overlying the Lamotte sandstone could be drained and made accessible for mining. It was planned to connect to the drifts and crosscuts with raises to mine ore deposited 20 to 30 ft higher. The higher orebodies were thus mined as slusher levels. Slusher hoists were used to drag the ore into the raises, which were made into hoppers. The ore was then loaded into 32x32-in. ore cans, hauled to the shaft by battery locomotives, and hoisted by the conventional Tri-State method. The rate of efficiency was 5 to 6 tons per manshift underground. The contact-type ore was attacked in a similar way, except that the orebodies were not nearly so wide, so that they were more flexible for slusher loading into cans. This advantage was offset, however, by haulage complexities, since the railroad was constructed on steep slopes. Through experience and ingenuity, many improvements were made in mining both types of ores. The two levels, so-called, in the basin-type ore-bodies were connected as previously planned, more efficient locomotives replaced the older ones, and a

Jan 1, 1954

By Nicholas J. Grant, A. W. Mullendore, Paul Predecki

The Duwez technique of splat cooling in which a molten droplet of metal is accelerated and made to impact on a cold, highly conducting substrate was investigated.- An apparatus for producing "splat" was constructed employing an explosive powder charge to accelerate the molten metal. Transport of the molten metal just prior to impact with the substrate was studied by means of high-speed photography. The molten particles are small spherical droplets from about 1 to 50 µ diameter. The average cooling rates for aluminum, silver, and a gold alloy splatted on nickel substrates at room temperature were determined experimentally and were found to vary from 18 to 5 x 10&apos; C per sec. The heat-transfer coeficients for pure aluminum and pure silver splats cooled on nickel substrates at room temperature were found to be 2.7 to 6.8 and 13.6 to 54.2 cal per sec sq cm &apos;C (2 to 5 x 104 and 1 to 4 x 18 Btu per hr sq ft OF), respectively. Solidification rates in pure aluminum and silver splats were calculated. "SPLAT cooling" is a term describing a technique for extremely rapid freezing and cooling of molten metals and alloys to room temperature or below. The technique was developed by Duwez et al.&apos; in 1960, and after refinement2 consisted in transferring a few tenths of a gram of molten metal to near sonic velocity to strike a suitably placed cold copper surface. Upon impact, the metal spread into a thin nonuniform film called a splat, about 10-4 cm thick. The splat particles produced in this manner were thin enough in some areas to be suitable for transmission electron microscopy, without further treatment, and, together with X-ray data, yielded a variety of structures which would be classified as follows: 1) supersaturated solid solutions (increase in solubility limit), 2) metastable crystalline stoichiometric and non-stoichiometric intermediate phases ( in Au-20.5 at. pct Si and in Au-14 at. pct Sb, respectively), 3) amorphous alloys, 4) retained high-temperature phases, 5) alloys having equilibrium phases present, but with unusual, markedly altered structures. The crystalline phases present in splats were usually extremely fine-grained and had low dislocation densities. Present interest in splat cooling centers around a study of the unusual structures produced by the technique, their contribution to alloy theory, and the possibility of the development of new or unusual properties. In addition, the technique is being examined for the production of bulk quantities of new high-strength alloys for low- and high-temperature use. Although a number of alloy systems have already been investigated by the technique, relatively little is known about the mechanism of splat formation and the physical conditions encountered by the metal during solidification and cooling. The purpose of this work was: 1) to determine the velocity, shape, and size of the molten metal droplets just prior to impact with the cold substrate; 2) to try to estimate or measure solidification rates, heat-transfer coefficients, and cooling rates in splats. EXPERIMENTAL TECHNIQUE Splatting Apparatus and Procedure. An apparatus similar to the type originated by Duwez et a1.,2 but employing an explosive charge to accelerate the molten metal, was used. A "Ramset" fastening tool (a gun normally used for driving studs into concrete, steel, and so forth) was mounted vertically above a resistance-heated graphite crucible as shown schematically in Fig. 1. A splat product was produced by melting a few tenths of a gram of metal at the position shown in Fig. 1, and then exploding a powder charge in the breach. The shock wave thus generated traveled down the barrel into the furnace, ejecting the molten metal through the 0.06-in.-diameter hole at the bottom of the crucible. The ejected metal was impacted on a high-conductivity metallic substrate where it formed a splat. High-Speed silhouette Photography. In order to investigate the size and shape of the ejected, molten metal just prior to impact with the cold substrate, high-speed silhouette photographs were taken, and are shown in Figs. 2 and 3. These photographs were obtained with the aid of an Edger-ton, Germeshausen, and Grier microflash unit and a submicrosecond flash drive equipped with a variable time delay. Two types of triggers were

Jan 1, 1965

By Ming-Kao Yen

A considerable amount of work has been reported in the literature in regard to the texture and earing behavior of copper strip. The rolling texture of copper has been confirmed as (110) [112] and (112) [111], which yields ears of a drawn cup at the position 45" from the rolling direction.1-3 The recrystallization texture has been established as the cubic or (100) [001] texture, where the earing positions are at 0" and 90" to the rolling direction.4-8 It has also been reported that in the development of cubically aligned grains of copper strips, the percentage of this cubic texture increased with an increase of final reduction and final annealing temperature.8,9 A comprehensive study on H.C. copper (British commercial copper of high-conductivity quality = Cu 99.95 pct, O2 0.03 pct, Ag 0.003 pct, Fe 0.005 pct and Pb < 0.001 pct) was made by Cook and Richards.6 They concluded that the recrystallization textures could be described as one or more of the following textures: (1) a single texture (100) 10011, (2) a twin texture (110) [112] and (3) a random orientation, depending upon the previous history of the specimen concerned. The effect of various alloying additions in copper was reported by Dahl and Pawlek.10 They found that certain alloying additions, such as 5 pct Zn, 1 pct Sn, 4 pct Al, 0.5 pct Be, 0.5 pct Cd, or 0.05 pct P suppressed the formation of cubic texture. Brick, Martin and Angierll reported that the cold rolled textures due to various additions fitted a rather simple pattern. However, the recrystallization textures were subject to very considerable variations. In the discussion of this paper, Baldwin stated that deoxidized copper containing 0.02 pct P gave a complicated recrystallization texture at lower temperature. When this copper was annealed at high temperature, a single texture appeared which was described as (110) [ill] but. according to a pri- vate communication from Baldwin, this orientation reported was in error and should have been reported as (110)[112]. He also reported that the earing positions of drawn cups were at 60" to the rolling direction.12 Recently, Howald, in his discussion on the paper by Hibbard and Yen,13 reported that the rolling texture of phosphorus deoxidized copper, containing from 0.006 to 0.020 pct phosphorus, was of the pure copper type. When these coppers were annealed at lower temperatures, they exhibited a random orientation, and when they were annealed at higher temperatures they had a mixed (111)[110] and (100)[001] texture, depending on the severity of the final reduction and annealing temperature. However, the specific influence of phosphorus and other impurities on the recrystallization textures and the deep drawing properties of copper strip has not been thoroughly reported. Therefore, an attempt has been made in the present work to determine the rolling and recrystallization textures and also the earing behavior of five types of commercial copper and thereby to evaluate the effect of phosphorus and some other significant impurities on the development of texture for cold reductions of about 87 to 89 pct. Materials Used The five types of copper employed in the present investigation were two phosphorus deoxidized coppers of different phosphorus content (0.007 and 0.013 pct P), an oxygen-free copper (OFHC), an electrolytic tough-pitch copper, and a fire-refined tough-pitch copper. These materials were subjected to a thorough spectroscopic and chemical analysis. The designations and the chemical compositions were as shown in Table 1. The coppers, FA1, FA2 and FA3. were hot-forged from 3-in. billets into a ½ X 6-in. plate and cold rolled to the ready-to-finish gauge indicated below. FA4 and FA5 were hot rolled and scalped to ready-to-finish gauge. The grain size of all the materials in the ready-to-finish condition was about 0.030 to 0.045 mm. Table 2 shows the last stage of the production schedule for each copper strip used. Experimental Procedure ANNEALING, GRAIN SIZE AND HARDNESS DETERMINATIONS Specimens of each type of copper were finally annealed in air for periods of one hour at temperatures ranging from 300 to 1600°F and were subsequently cooled in air. The average grain diameter of the annealed specimen was estimated by comparing with a standard grain size chart. Hardness was determined on the Rockwell 15 T scale. CUPPING TESTS Cups were made in a blanking and drawing set, in which blanks of 2-in. diam were drawn to a cup of 1.25-in. diam with an average depth of about 0.75 in. The clearance between the punch and die was about 0.032 in. The ears of the cup were measured with a special fixture which read the height of ears to one-thousandth of an inch on every ten-degree interval along the circumference of the cup. POLE FIGURES The usual transmission diffraction method with unfiltered copper radiation was employed to determine the pole-figures of the specimens cold-rolled or annealed at 900°F. All the pole-figures were derived from the positions of intensity maxima on 111 diffraction rings of the X ray photo-grams taken at 10 rotation of a

Jan 1, 1950

By J. R. Long, T. R. Graham

This report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau&apos;s War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. Preliminary Work In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, o to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By John C. Bilello

The brittle fracture behavior of cold-worked sintered tungsten was studied over the temperature range 4.2° to 298°K using a high-sensitivity strain measuring system and electronfractography. Similar observations were made on a swaged electron beam zone-refined monocrystal. In sintered tungsten irreversible plastic deformation was observed during cyclic load-unload tests at stress levels well below the fracture stress for all temperatures, but general microyielding could be detected only down to 202°K. For the zone-refined samples macroyielding occurred at all test temperatures with evidence for twinning below -202°K. The fracture stress of the sintered tmgsten was virtually independent of temperature, while the zone-refined crystal showed a 2.3 times increase over the same temperature range. Electronfractography confirmed the presence of numerous rod-shaped and spherical submicroscopic voids which ranged in diameter from 1400 to 4300A in the sintered tungsten; no voids could be found in the zone-refined tungsten. Contrast effects observed on the replicas in the vicinity of certain voids indicated that plastic deformation could be induced by the local stress concentration. It has been suggested that the presence of these voids may be responsible for the low-temperature brittle failure of sintered tungsten. Based m this suggestim und on the evidence obtained here, a dislocatim model is presented to account for the brittle behavior of sintered tungsten. In this model slip, which is induced by the local high stress concentration in the region at the edge of a favorably oriented void, could cause the void to grow to a microcrack of critical size. STUDIES of brittle fracture in bcc metals have led to the well-known experimental relationships between grain size, yield stress, fracture stress, and temperature which have formed the basis for the various dislocation pile-up1-3 or interaction4&apos;= models for slip-induced microcrack nucleation. While microcracks can be nucleated by deformation twins,6,7 there has been no direct evidence furnished by transmission electron microscopy to support conclusively either the Zener pile-up or Cottrell dislocation reaction models for producing micro-cracks in all "brittle" materials. In addition to the "inverse" grain size relationship for yield and fracture stresses the cottrel14 theory predicts that the fracture stress below the transition temperature should behave in a fashion similar to that of the yield stress above this temperature. Such behavior has been verified for several bcc metals.8-10 With reference to both grain size effects and the tem- perature dependence of the fracture stress below the transition temperature, the behavior of sintered tungsten appears anomalous. Early work by Bechtold and Shewrnon 11 showed no apparent temperature dependence of the fracture stress below the ductile-brittle transition temperature (DBTT). They attributed this result to the intergranular nature of the fractures observed. More recent work by Wronski and Four-deux12&apos;13 on considerably purer material did not show any systematic relationship between the fracture stress and temperature below DBTT. The dependence of flow and fracture stresses on grain size is also not clearly established for sintered tungsten. Koo, for example, has shown that the DBTT for sintered tungsten depended chiefly on the annealing temperature and was relatively insensitive to the actual grain size achieved. Using electrofractography and transmission electron microscopy, Wronski and Fourdeuxl3 showed that numerous spherical and rod-shaped submicroscopic voids could be found in sintered tungsten but not in melted tungsten of nominally the same purity. They suggested that these voids could be responsible for the temperature insensitivity of the fracture stress below the DBTT. In the present work the temperature dependence of the fracture stress for high-purity commercially sintered tungsten has been determined. The presence of submicroscopic voids in sintered materials was confirmed, and these were studied in detail to examine the role they could play in nucleating brittle fracture. A dislocation model is suggested which could cause an inherent spherical void to lengthen into a Griffith crack of critical size. EXPERIMENTAL PROCEDURE Commercially sintered tungsten rod was obtained in the as-swaged condition from Sylvania. A zone-refined crystal was obtained from the same source. This crystal was grown by giving three zone passes (at 25.4 cm per hr) to a sintered rod of high-purity tungsten. The rod axis prior to cold working was -15 deg from the [110] direction. Originally the zone-refined rod was -6 mm in diam; it was reduced to -3 mm by eight swaging passes, at high temperatures, with each step having about the same reduction of area. The final swaging step gave a 7.5 pct reduction of area at 1050°C. All swaging operations were performed in a hydrogen atmosphere. For the sintered rod a similar working schedule was employed. Metal-lographic examination of the sintered material revealed that the cold-worked structure had an apparent grain diameter of -25 u transverse to the swaging direction (obtained by the intercept method). In the longitudinal direction cold-worked grains were approximately 1.5 to 2 times their diameter. No distinct fiber structure could be observed optically for the zone-refined rod. The cold-worked structure in the

Jan 1, 1969

By Fred C. Bond

MOST investigators are aware of the present unsatisfactory state of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which are useful for predicting machine performance and give, acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary in commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed&apos; in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted. In its first form, as stated by P. R. Rittinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include .the concept of surface energy; in this form it was precisely stated by A. M. Gaudin2 as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended. According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps, 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported&apos; that support the theory in its first form by indicating that the new surface produced in. different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work" done on. the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading since it does not follow the regular breakage pattern of most materials but is relatively harder to grind at the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory&apos; is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr/log 2.5 The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in. reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-1.5 If a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The&apos;evaluation in terms of kw-hr per net ton of 200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of -200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned, with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying

Jan 1, 1952

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg&apos; have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck&apos; established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By H. W. Mead, C. E. Birchenall

The rates of growth of graphite nodules in cast irons are calculated for a model of a growing graphite sphere surrounded by a shell of austenite through which carbon and iron are diffusing. The carbon is supplied by a cementite-austenite mixture at the outer edge of the shell. The calculated rates from carbon diffusion agree fairly well with the measured values, but the rates based on iron self-diffusion are much too low. Because the iron must be removed for the process to continue, o plastic deformation mechanism is suggested. THERE has been an unfortunate tendency in the literature of growth and dissolution reactions to identify the slope of a plot of the logarithm of the growth or dissolution rate vs reciprocal of temperature with the activation energies determined by diffusion measurements in chemically similar systems. If the solubility limits at the growing or dissolving phase interfaces change appreciably with temperature, such procedures may lead to serious errors in specifying the mechanisms controlling the rates of these processes. A reaction involving the simultaneous growth of graphite from and dissolution of cementite in austenite will be discussed here to show that substantial oversimplifications have been made in earlier studies of this process. From a dilatometric study of the overall y-range graphitization process, Bunin and Danil&apos;chenko&apos; found an apparent activation energy of 90 kcal per g-atom. They concluded that, since this value was much nearer the approximately 68 kcal per g-atom observed for self-diffusion in pure iron than it was to 32 kcal per g-atom for diffusion of carbon in iron, the rate-controlling process must be the diffusion of iron away from the growth interface to provide space for graphite to grow. Bunin and Salli&apos; bolstered this agreement with the observation that graphite forms preferentially at surfaces, cracks, and pores where free volume is present initially. Ziegler, Meinhart, and DeaconQ ad found an apparent activation energy for graphitization of 98 kcal per g-atom. This value, like that of Bunin and Danil&apos;chenko, applies to nucleation and growth occurring simultaneously. It is not generally assumed that nucleation is entirely diffusion-controlled. Treatments such as prior cold-working and prequenching, which strongly affect the rate of graphitization, would be expected to have little effect on diffusion processes occurring at the graphitization temperature. In any case 90 kcal per g-atom is not particularly close to the 54 kcal or lower to be expected for diffusion of iron which is carbon-saturated.&apos; The presence of silicon in iron is said to reduce the activation energy for diffusion,&apos; so its presence in cast irons would be expected to have a similar effect. The growth rates of nearly spherical graphite nodules have been studied by Brown and Hawkes." The initial rate of growth before impingement of adjacent carbon-depleted areas was found to be parabolic, and rate constants were measured at several temperatures. Their apparent activation energy for the growth process only was roughly 45 kcal per mol. Burke and Owen&apos; made growth-rate measurements on several alloys, recording appreciable induction periods, initial nucleation rates, and average radial growth rates based on an assumed linear rate of radial growth. They found that increased silicon content increases the ovel-all reaction rate and the initial rate of nucleation, and decreases the induction period. Assuming 1) spherical nodules. 2) constant volume rate of nucleation, 3) austenite in equilibrium with cementite at positions where the cementite is not depleted, and 4) a constant diffusion distance during the growth of a nodule, they calculated an apparent overall activation energy of 68 kcal per mol, which was related to an activation energy for nucleation of 79 kcal per mol and activation energy

Jan 1, 1957

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.&apos;&apos;2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3&apos;4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-&apos;Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of &apos;irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.&apos; beryllium,&apos; magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.&apos; A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By P. A. Fisher, J. B. Wilson, D. J. Whitehead, C. J. P. Ball, A. C. Jessup

The properties of a new magnesium alloy ZT1 containing 3.0 pct Th, 2.5 pct Zn, 0.7 pct Zr are described. The alloy possesses good creep and fatigue resistance up to 650°F, is free from microporosity, and is readily sand-cast. ZT1 is shown to be superior to zinc-free Mg-Th-Zr alloys. THE advent of the jet engine created a demand for a light sand-casting alloy capable of being cast into large complex shapes and capable of resisting creep at temperatures up to 500°F. This demand has been largely met by alloys of the magnesium-cerium mischmetal-zirconium types, containing about 3 pct Ce mischmetal and 0.7 pct Zr, typified by Elektron magnesium alloys MCZ and ZREI, the latter alloy also having a zinc addition of 2.5 pct. These alloys utilize the valuable properties at elevated temperatures conferred by the addition of rare earth metals to magnesium, a fact which has been known for many years and discussed by several investigators.1-1 Murphy and Payne8 showed that the addition of the powerful grain-refining element zirconium to Mg-Ce mischmetal alloys produced alloys with attractive room temperature properties combined with good creep properties and castability. With the increasing power of modern jet engines the temperatures to which some of the magnesium parts are subject are likely to exceed the safe working range of the cerium-mischmetal-containing alloys, and at the beginning of the research considerable interest had been shown by aeroplane engine designers in a magnesium sand-casting alloy suitable for service at higher temperatures, e.g., 600°F and above. At an early stage in the development of this type of alloy a check on the fatigue properties at elevated temperatures indicated that, since the fatigue limit even at 108 eversals was appreciably higher than any permissible creep stress, the main emphasis of the research could be concentrated on creep behavior. The primary aim in developing the new alloy has therefore been to attain maximum creep resistance; but due consideration has also been given to other important properties such as castability, tensile strength, and cost. It is by now well established that it is not possible to correlate creep strength with other short time mechanical properties such as are obtained in tensile

Jan 1, 1954

By D. H. Thompson, A. W. Tracy

Season-cracking is a type of failure of brass that results from the simultaneous effect of stress and certain corrodants. The object of this paper is to present data that will aid in a more complete understanding of the mechanism of season-cracking and related phenomena. Results presented show that certain high copper alloys are susceptible to season-cracking or stress-corrosion cracking, and possible explanations are discussed. Starting at least as far back as 1906, many papers have been devoted to this subject but the symposium1 held in Philadelphia in 1944 is the richest source of information. In order to study season-cracking, several of the many variables were held constant so as to learn the effects of others. Season-cracking is generally understood to refer to the corrosion cracking of brass having internal stresses;²,³ it is a special case of the general stress-corrosion cracking. Inasmuch as applied stresses are more readily produced and controlled, they were used exclusively in this research and the resulting phenomenon must he called stress-corrosion cracking.²,³ Only constant tensile stresses were used. The agents believed to be most frequently responsible for season-cracking are ammonia. amines and compounds containing then]. Both moisture and oxygen also appear to he necessary. Therefore, an atmosphere containing ammonia, water-vapor and air was selected for these tests. Briefly, the work consisted of exposing sheet metal specimens, having a reduced section ¼ by 0.050 in., of copper-base alloys to the effect of static tensile stresses between 5,000 and 20,000 psi and simultaneous contact with a. continuously renewed atmosphere containing 80 pct air, 16 pct ammonia and 4 pct water vapor at 35°C. The gas mixture and the speci- mens were maintained above the dew-point. The time-to-failure in minutes was the primary measure of results. In order to limit the experiment to finite time, it was considered that a specimen which had neither failed nor undergone microscopically detectable cracking in 40,000 min. (4 weeks) while under a stress of 10,000 psi or more could be considered immune to cracking. This is merely a convenient limit and is not to be considered proof of immunity. Supplementary tests in the absence of stress using weight loss or microscopical appearance as measures of attack were made. Apparatus The apparatus used in this research is shown in Fig 1. To facilitate the description it may conveniently be divided into six parts: stress-producing units, test chamber, gas train, electrical controls, timers and gas analysis device. A stress-producing unit is shown in an exploded view at the left in Fig 2. At the right is an assembled unit with a specimen in place in the lower portion; it is this part that remains in the ammonia atmosphere during a test. The upper part contains a spring, a central threaded rod, a large nut and necessary washers, pins, and so forth. Stress is produced in the specimen by screwing down the top nut against the spring, thus putting a tensile load on the central rod and so on the specimen. The wrench that turns the nut by extending through the upper cap, is seen at the upper right of the figure. The magnitude of the load is gauged by measuring from the pin that extends through the side of the tube, to a fixed point on the large flange. Measurement is made with a vernier beam caliper, shown at the right of the figure. The necessary spring compression to give a desired stress is calculated from the calibration curve of the spring and the dimensions of the specimen. The test chamber, center Fig 1, consists of a thermally insulated steel box 32 in. long by 10 in. high by 7 in. wide. A horizontal baffle reaching nearly to each end divides the chamber equally. Below this baffle are inlets for air and ammonia, a heating coil and a fan. Thus the gases are warmed and mixed in the lower level and flow past the specimens in the upper level. A thermo-regulator and thermometer project into the upper space. The top is pierced by 12 ports flanked by 3/8 in. threaded studs. A test starts when a port is opened and a unit containing a stressed specimen is thrust through it and bolted down against a neoprene gasket. The test chamber is held at 35°C. The gas train, right rear Fig 1, carries ammonia and air continuously to the test chamber. Tank ammonia passes through two reducing valves, a needle valve, a flow meter and into the test chamber. The air from either the plant compressor or a small laboratory compressor passes through wool towers and flow controls to the flow-meter. It then bubbles through water at 34°C and through a heated line to the test chamber. Electrical controls, left rear, Fig 1, provide rectifiers and mercury relays for the test-chamber and humidifier-heating-control circuits and outlets for

Jan 1, 1950

By A. Chakravarti, C. C. Harris

First-order kinetics adequately describe the recovery of a single floatable species. The conditions under which cell behazior can be simulated by a single-phase model are discussed; deviations from the multiphase model are accountable. The rate coefficient depends upon operating conditions besides particle size and mineralogy and the physicochemical properties of the pulp constituents. The model for a real flotation system combines the first -order, single-phase model with a distribution of noninteracting species. Methods for determining the distributions are discussed. Applications of the procedure to flotation studies are outlined. The mathematical description of flotation as a rate process can be traced to Garcia1 who reported cases in which the fraction of solid remaining in a cell in semi-batch operation, F (for Notation used throughout, see Table l), decays exponentially with experimental time T. F = e-k>r. (1 The differential equation leading to Eq. 1 is dF ----= -k,F (2) dT which is recognized as the algebraic analog of the chemical kinetics first-order reaction equation.&apos; This has led to suggested mechanisms for flotation and mathematical relationships other than first order: with very little foundation other than analogy. The flotation rate coefficient kl can be accounted for as the product of several probabilities concerning bub-ble-particle attachment and detachment, aggregate entry from pulp into froth and return from froth to pulp, and removal from froth as concentrate. These factors clearly contribute to the magnitude of the overall flotation rate, and there are others also, but describing flotation merely as the overall probability of consecutive gross events hardly appears a significant advance in understanding. More recently, it has been described in terms of a stochastic process, which promises to provide a more satisfactory approach? The present paper will be more concerned with a phenomeno-logical description of the flotation process than with an account of the internal mechanics of the process. This is not a statement of priorities, or a judgement of the relative importance of these options but rather an assessment of what is presently possible. Previous investigators&apos;" have developed methods for interpreting semi-batch flotation data in terms of species distribution. These methods have been used in an attempt to explain flotation behavior in response to changes in operating conditions." Inspection of examples given in the literature" reveals discrepancies between theory and experiment, and data obtained in the Colum-

Jan 1, 1971