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By Eugene F. Broome, Hugh A. Walls

Self-diffusion coefficients were measured using the modified shear cell technique over a temperature range from 31" to 401°C. These data agree within experimental error with those of Petit and Nachtrieb, which were determined from 30°to 99°C. LIQUID self-diffusion behavior in gallium has been studied previously by Petit and Nachtrieb&apos; using their shear cell technique.&apos; Data were obtained in that investigation over temperatures ranging from 30.6 to 98.7"C, and these comprise the only published data for liquid gallium. In the work reported here, diffusion data were obtained from 30.8 to 400-9.Cusing a shear cell technique different from that of Petit and Nachtrieb. This modified shear cell method and the mathematical analysis for diffusion in a finite capillary geometry have been previously described.3 PROCEDURES AND ANALYSIS The segments of the modified shear cell were fabricated from types 304 and 316 stainless steel. No corrosion problems with gallium were encountered until attempts were made to obtain data at 500°C. The diffusion capillary diameter was 1.59 mm and capillary lengths for the four sets of cell segments used are given in Table I. Gallium with a purity of 99.999 wt pct was obtained from Var-Lac-Oid Chemical Co. The gallium-72 isotope used to measure the self-diffusion coefficients was produced from this inert gallium by irradiation in The University of Texas Reactor Facility, and was checked for radiochemical purity. Following a period of isothermal diffusion controlled to within 0.0l°C, the contents of each capillary section were emptied into a counting planchet, weighed to assure that gallium had not been lost during handling, and the radioactivity determined by windowless gas-flow proportional counting. Great care was taken to obtain a reproducible counting geometry for the samples. Diffusion coefficients were obtained from the solu-tion3 to the diffusion equation for the modified shear cell problem, viz.: in which B2= C2(t)Li + L2)- CSL1-COL2 P* (C0-Cs)(L1+ L2) and L, and L2 are the capillary segment lengths. The step-function initial concentration distribution was expressed as C(x,O) = C, for -L1 = x < 0 and C(x,O) = Co for 0 < x 5 L?. Also, C2(0 = ^- fcix,t)dx Computation of the diffusion coefficients was done numerically as described in our earlier paper.3 Because of the short half-life of gallium-72 (14.1 hr) and the relatively long counting times taken to give a precise value of the diffusion coefficient, it was necessary to account for the radioactive decay both during the actual count and between counts for different samples (before and after diffusion). Thus, the average count rate Cz(t) for a second sample counted from times t3 to t4 can be made consistent with the average rate Co determined for a first sample counted from times t1 to t2 by the relationship: N(e-»i-e-M») , , C2(f) " &-«,)(*-«.-«-»«) [21 in which N is the total number of counts taken and is the decay constant. RESULTS AND DISCUSSION The self-diffusion coefficients determined in this investigation are listed in Table 11. Values of the parameters used to calculate the coefficients are given in the table, as are values of the random counting error &apos; for the concentration ratio pz and the corresponding expected random variation AD in the diffusion coefficient. The quantity is calculable from: &apos;Cg — C2(t)} , „ ,2 .-„¦, M co-csl(ACs)J W in which AC is the error in the individual count rate. The mean values of the diffusion coefficients within each temperature group are also given in Table 11. Such temperature groupings of data are reasonable because of the small variations between the temperature~.~

Jan 1, 1970

By S. Storchheim

MORE and more attention is being paid to the bonding of metals in their solid states. For a better understanding of this technique for joining metals and how it is affected by changes in temperature, pressure, and time at temperature and pressure, a detailed report concerning nickel to aluminum bonding has been published.&apos; In order to broaden the knowledge accrued, some additional work concerning solid state joining of aluminum to copper and aluminum to zirconium was performed. The investigation of the Al-Cu system was considerably more extensive than the investigation of the Al-Zr system. For the A1-Cu system, not only were tensile sudies made but intermetallic penetration rate investigations also were carried out. The effect of temperature on intermetallic penetration rate for the A1-Cu system was determined at 11 tsi pressure, held 2 min. Procedure Apparatus: The hot pressing technique was the means of solid state reaction used and required the equipment depicted in Fig. 1. The following procedure was involved: The two metals to be reacted were placed in an aquadag-lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diam made of the same material. A thermocouple well was located in the die body 3½ in. down from the top of the die, while another well was located centrally in the bottom punch 8½ in. from the bottom of the die. This die assembly was located in three cylindrical ceramic heating furnaces placed in tandem. Each furnace was controlled individually by a Variac power transformer. In turn, the die and furnaces were placed in a water-cooled stainless steel pot which could be evacuated. A cover, which contained a centrally located Wilson seal with an 18-4-1 1 in. diam ram running through it, was bolted on the pot. After sealing, the pot was evacuated by a roughing pump to 200 microns pressure, after which a diffusion pump was used to bring the pressure down to 5 to 15 u. At this pressure, the furnaces were turned on. As soon as they started to heat, out-gassing of the entire unit raised the pressure to 30 to 400 p. By the time the specimens were at temperature ready to be pressed, approximately 4/2 hr, the vacuum pumps had re-established the 5 to 15 u pressure. Once the desired temperature was reached, the required pressure was applied for a predetermined length of time to the 1 in. ram, through to the top punch, and to the specimen. When the time for keeping the specimen under pressure had elapsed, the pressure was released, the energizing coil current turned off, and the assembly allowed to cool. After cooling, the die was removed from the pot and the specimen was ejected. Specimen Preparation: Two different types of specimens were made for this investigation. One was for subsequent tensile testing, while the other was for determination of intermetallic alloy zone penetration into the parent metals. Tensile Bars—Commercially rolled copper pieces in. thick or zirconium sheet pieces 1/32 in. thick and 1.366 in. diam were placed between commercial 2-S aluminum rod 1 in. thick and 1.366 in. diam. This sandwich in turn was slipped into a 2-S aluminum sleeve 1.438 in. OD and 1.370 in. ID. This sleeve lined the couple up and prevented the aquadag lubricant from getting in between either the A1-Cu or Al-Zr interfaces. Immediately prior to the specimen assembly, the copper or zirconium was abraded on the flat surfaces with 320 grit silicon carbide paper, producing clean smooth surfaces. The aluminum was chemically cleaned just before assembly by: l—degrease in acetone, 2—distilled water rinse, 3—immersion for 3 min in 5 pct NaOH at 70" to 80°C, 4—distilled water rinse, 5—immersion for 2 min in 50 pct HNO3 solution at room temperature, 6—distilled water rinse, and 7—drying in a blast of gas. After the A1-Cu sandwiches were hot pressed and ejected, the specimens were machined such that the aluminum sleeve was removed, and the remaining aluminum was then threaded; the bar so produced was tested later for tensile strength. In all the instances where Al-Cu couples were tested, the specimens broke during the test at the Cu-A1 interface and never within the aluminum or copper. The ultimate tensile strength values at times showed considerable scatter for a set of given reaction conditions. Because of this, as many as three to five specimens were made for a particular set of conditions. The trend of the average tensile strengths obtained was not as conclusive as was the trend of the maximum tensile strengths, the latter values being obtained under optimum reaction conditions. Therefore, the values of ultimate tensile strength given herein are maximums.

Jan 1, 1956

By Benny Langston, Frank M. Stephens

Although little information is available concerning small-scale equipment for dust collection in laboratories, it is possible to adapt standard equipment for laboratory use. Dust from laboratory processes may be collected by cyclone separators, filters, electrostatic separators, scrubbers, and settling chambers. IN recent years much attention has been given to recovery, treatment, and disposal of dusts discharged into the atmosphere from operations of industry. considerable data has been accumulated on both operation and design of dust-collector equipment for commercial installations. On the other hand, there is almost no published data on design and construction of small-scale equipment to handle dust problems that arise in the ore-dressing laboratory. Dust-collection equipment such as multiclones, single-cyclones, scrubbers, chemical and mechanical filters, settling chambers, and electrostatic separators has proved its efficiency for collecting dust in industry. In the laboratory, however, the engineer is faced with the problem of collecting small quantities of dust, inexpensively, without diverting the major effort from the metallurgical problem to the problem of collecting dust produced by the process. For most applications standard dust-collection equipment is too large for use in the laboratory; however, for control of dust in large working areas it is often possible to use a standard dust collector, such as an air filter, with branch ducts to eliminate a health hazard. For example, the well-furnished sample-preparation room containing small jaw crushers, rolls, and pulverizers, in addition to the riffles and screens necessary for preparation of samples, presents a perennial source of dust. The authors&apos; experience has shown that a combination system consisting of overhead branch ducts to the individual equipment and floor ducts with grills, where applicable, connected to a central dust collector effectively removes dust generated in preparation of samples. Fig. 1 is a sketch of a downdraft dust-collector for table installation. Similar systems can be built with floor grids. For portable equipment such as laboratory vibrating screens this type of installation with a steel grill to support the heavy load is reasonably efficient. Overhead branch ducts to individual crushing and grinding equipment, although efficient, must be carefully controlled by dampers to prevent excess loss or a change in the composition of the sample. Change in sample composition can result from excess velocity, which causes selective removal of constituents of low specific gravity. Fig. 2&apos; shows the theoretical effect of terminal velocity on spherical particles of different specific gravities in air and water under action of gravity. Fig. 3 shows the effect of air velocity on composition of CaCO, coal mixtures. Although the entrainment of dust particles in a moving air stream is the basic mechanism by which all dust-collection equipment functions, usually intake velocity of the dust-collection system must be controlled to prevent loss of part of the sample. As an example of what may happen when excess velocities are used, a mixture of 50 pct coal and 50 pct limestone was crushed to —10 mesh and fed to a pulverizer equipped with an overhead dust-collection system. Fig. 4 shows the overhead dust-collection equipment used in this test. The pulverizer was set to give a product 95 pct —100 mesh in two stages. Velocity of air passing over the lip of the pulverizer was measured with an anemometer. After grinding, the finished product was analyzed to show the amount of calcium carbonate present. Fig. 3 shows graphically the increase in calcium carbonate as velocity through the dust-collection duct was increased. These data show that at a velocity of 1 ft per sec little if any of the coal was entrained by the overhead draft. At the maximum velocity, about 6.5 ft per sec, approximately 7 pct more coal was entrained than calcium carbonate. From an operating standpoint, this problem can be remedied easily by dampering the line to control velocity. The lowest velocity commensurate with satisfactory dust control should be used to prevent excess loss and, in some cases, selective dust loss. Collection of Dust in Laboratory Processes As in industry, the engineer desires to collect efficiently the dust produced by processes being investigated on a laboratory scale. However, in the collection of laboratory dusts he is faced with two additional problems: 1—The volumes of gas and the quantity of dust that must be recovered are small when compared with the capacity of standard dust-collector equipment, which must be scaled down in design except for collection of dust from large pilot-plant operations. 2—In addition, because of the variety of problems studied in the process laboratory, the engineer cannot design today a dust collector that will meet the conditions imposed by the processes of tomorrow. Sometimes, therefore, he must compromise collection efficiency to minimize the cost of fabrication and the amount of time diverted from the metallurgical to the dust-control problem. For collection of dust from laboratory processes a cyclone separator, filters, electrostatic separators, scrubbers, and settling chambers can usually be adapted for small-scale operations. The following

Jan 1, 1955

By C. P. Sandberg

Having been occupied in inspecting and testing iron and steel these twenty years in England, and previous to that having served on the Board of Iron Masters in Sweden, I have naturally been very much interested in the subject of the use of steel for structures. I regret that I can offer but comparatively small experience on that had, having had principally to do with steel for railway plant and rails, but granting these to be a kind of "structure," and also that steel for rails has similar duties to perform in many respects, and is generally manufactured in the same way and at the same works as steel for stuctures, properly speaking, I may be entitled to offer an opinion on the use of steel in construction. In a paper recently presented to the Institution of Civil Engineers in London, Mr. Ewing Matheson has recommended that the Board of Trade rules should be amended so as to allow of a maximum straining of 8 tolls per square inch instead of 6 1/2 tons. But it is equally necessary to fix the amount of ductility or elongation of the metal for such a strain as 8 tons. Strength and ductility should always be spoken of together. Mr. Matheson says that steel can be manipulated in the factory in the same way and with the same tools as are used for iron. This can only be granted for mild steel; for hard steel would be spoilt by the rough mechanical treatment which iron can stand, such as punch ing, for instance; and the remedy for regaining the strength lost by punching hard steel, viz., annealing, cannot always be applied. Noth ing proves this fact better than the punching of steel rails of consid erable hardness, which caused fractures at an early period of steelunaking, and which resulted in the stipulation for drilling instead of punching the bolt-holes, which had been formerly applied to iron rails without any damage. In fact commissions to establish standard tests are now working on the Continent, principally in Germany, where

Jan 1, 1882

By D. C. Buffum, L. D. Jaffee

QUANTITATIVE measurements of the temper brittleness of steel are made by comparing the difference between embrittled and unembrittled specimens in the temperature of transition from ductile to brittle fracture. Since hardness affects the transition temperature, a study of the combined effects of hardness and temper brittleness appeared desirable. In this investigation a commercial SAE 3140 steel, which has been reported on previously in temper brittleness studies,* was used. Blanks from this steel were austenitized for 1 hr at 900°C and water quenched. The blanks were then divided into six groups and further heat treated as follows: Group 1—tempered at 675°C for 4 hr and water quenched; Groups 2, 3, 4, and 5—tempered at 675", 650°, 625&apos;, and 600 °C respectively for 1 hr and water quenched; and Group 6—tempered at 500°C for y2 hr and water quenched. Each of these groups was divided into two parts; one part was tested without further heat treatment, and the other was embrittled for 48 hr at 500°C and water quenched. Tempering treatments between 500" and 600°C were avoided because of the rapid embrittlement occurring in that range for this steel. The heat-treated blanks were machined into standard V-notched Charpy bars. Each group was tested over a range of temperatures on a 217 ft-lb Charpy machine. The energies necessary to fracture the bars and the percentage fibrous fracture of each bar were recorded. The transition temperatures were obtained from a plot of the percentage fibrous fracture as a function of testing temperature. They were taken as the lowest point on these curves at which the fracture was 100 pct fibrous. The transition temperatures for both embrittled and unembrittled specimens are presented in Fig. 1 as function of the hardness. It will be noticed in this figure that the point for the unembrittled condition at 21 Rockwell C is out of line. These specimens were tempered for 4 hr at 675 °C and this point indicated that under isothermal conditions at this temperature, as is well known, embrittlement may develop fast enough to more than offset the effects of softening. From this data, it was concluded that the difference between transition temperatures for the embrittled and unembrittled conditions at any given hardness, within the range of Rockwell C 24 % to 32lh, is constant. It is also concluded that, within the hardness range studied, the transition temperatures for embrittled and unembrittled specimens rise in a parallel fashion with an increase in hardness. The authors wish to acknowledge the assistance of Frank Carr in this work.

Jan 1, 1952

By the courtesy of Sir Robert Hadfield, we have received the fol¬lowing communication relating to the development and encouragement of science and research in Germany at present. These statements have been translated by Sir Robert from various German sources, and are presented here as an indication of what Germany is doing not only to further her military power, but also to prepare for the period of trade rehabilitation to which she is looking forward after the close of, the war. KAISER WILHELM TRUST FOR PROMOTION OF WAR SCIENCE The Kaiser has approved the foundation of a Trust with the name given above. The aim of the Trust is to further the development of scientific and technical aids to warfare, by uniting the scientific and the military forces of the country for work together. The scientific Work is to be carried on by the following technical committees (or commissions) (1) Committee for the chemical raw materials, for the production of munitions-manufacturing materials. (2) Committee for chemical war materials (powder, explosives, gas, and the like). (3) Committee for physics, including ballistics, telephony, telegraphy, determination of targets and distances, measurements, and the like. (4) Committee for engineering and communication. (5) Committee for aeronautics. (6) Committee for obtaining and preparation of metals.

Jan 8, 1918

By George M. Humphrey

It is indeed a pleasure for me to have this opportunity to discuss with you a subject which I find infinitely interesting and intriguing - namely, world-wide iron ore supply and demand. We will be examining the following: (i) current iron ore production and requirements; (ii) the major ore producing countries; (iii) the seaborne iron ore trade; (iv) ore grades or types; and (v) future requirements. For those who may not be familiar with the iron ore mining industry, it may be useful to know at the outset that our industry has been plagued with overcapacity for the past seven years. The optimism which prompted substantial expansion of productive capacity in the early to mid-1970&apos;s has unfortunately proved to have been unfounded. I shall begin by describing where we are today as well as a little about how we got there. In the latter regard, it&apos;s not so much that historical knowledge will solve any of the industry&apos;s problems or provide clairvoyance with regard to the future. Rather it&apos;s a feeling on my part that some knowledge of the past will provide a useful perspective capable of enhancing our analysis of future trends. At the time of writing, the most recent year for which we have definitive world-wide iron ore production and consumption statistics is 1980. In that year the world consumed approximately 859 million metric tons of iron ore to produce approximately 510 million metric tons of primary iron consisting of 502 million tons of pig iron and 8 million tons of sponge iron. Crude steel production for the same period attained a level of 719 million metric tons. Because it is possible in today&apos;s world to produce steel without consuming iron ore simply by melting scrap, the key statistic insofar as iron ore demand is concerned is primary iron production. In 1980 the ratio of iron ore consumption to primary iron production was 1.68:1.00. The comparable ratio over the past seven years has varied from 1.63 to 1.87 and averaged 1.72:1.00. All the same, as a practical matter crude steel production and iron ore consumption tend to parallel one another closely, and for the time being a good rule of thumb is that to produce an average ton of crude steel requires 1.20 tons of iron ore. Let&apos;s turn our attention now to the regions where the 859 million tons of iron ore necessary to support 1980 world-wide iron and steel production were produced. Not surprisingly, most of the ore was produced in the same region where it was smelted. In round numbers 65% of the world&apos;s iron ore production is currently consumed in the same general region as it is produced, while 35% enters the seaborne trade and is transported in ocean vessels to a more remote consuming area. Approximately 85% of the world&apos;s seaborne iron ore trade is directed to the Western European and Japanese markets, both of which are almost entirely dependent on off-shore sources for their mammoth iron ore requirements. The following tabulation lists, in order, the twelve leading iron ore producing countries in 1980 as well as their percentages of total and free-world production; in addition their export potentials are presented. As a group these countries accounted in that year for 89% of world-wide production which stood at 871 million tons. Leading World Iron Ore Producing Countries [ ] One will first note that world iron ore production is dominated by the top four producers - namely, the U.S.S.R., Brazil, Australia and the U.S.A. - which together accounted for nearly 60% of total 1980 production. Of these four major producers the U.S.A. and the U.S.S.R. produce almost exclusively for consumption in their own regions, whereas Australia and Brazil produce primarily for the seaborne export trade. In fact Australia and Brazil accounted for about 50% of all seaborne iron ore trade in 1980! It is also interesting to note that Australia, Brazil, the U.S.A. and Canada accounted for nearly 60% of free world iron ore production in 1980. Once again the importance of Australia and Brazil shows itself, with their share alone of free world production reaching 35%. As has already been noted, a significant 35% of the world&apos;s iron ore production in the year 1980 was

Jan 1, 1982

By A. P. Svenningsen

DURING the work at the test mill in Morenci, it was determined that a suitable feed for the ball mills could be made by a single pass through a short-head cone crusher. These crushers did not require a closed circuit delivering only a screen product to the mills, such as is the practice in some concentrators. By no means does this mean that the practice in these other concentrators is wrong, but just that the Morenci ore can be most economically crushed and ground in this manner. Therefore, the design of the secondary crushing plant was simply a problem of taking 25,000 tons of ore per 16 hour day from the primary crusher, this ore ranging in size from fine particles to 10 or 12 in., and reducing it to minus 3/4 in. Inasmuch as outages must be contended with in any crushing plant, it was assumed that the crusher would operate at full capacity for approximately only twleve hours per day, which is three-quarter capacity for the 16-hour shift. With this in mind, it was necessary to design a crushing plant which would average approximately 1600 tones per hour for the 16-hour day, or 2000 tons per hour for slightly over 12 hours per day.

Jan 1, 1942

By Craig S. Hartley

Expressions are obtained for the energy changes associated with the reaction of (a& (111) slip dislocations on intersecting (110)planes in anisotropic bcc metals. An energy criterion for assessing the likelihood of dissociation of the products of such reactions is also presented. It is found that the "burrier reactions" which form a(100) dislocations at the intersection of two active {110) slip planes are more energetically favorable in metals which exhibit a high value of Zener&apos;s anisotropy factor, A, than those which have a low value. The results are presented in a form which permits the stacking fault energy to be obtained from a measurement of the separation between par-tials in a dissociated configuration. However, until accurate calculations or measurements of the stacking fault energies involved are available, it is not possible to assess the physical importance of dissociated dislocations. In a recent paper,&apos; the energy changes associated with several types of reactions between two slip dislocations, (a/2)(111){110), in bcc structures were calculated.* Isotropic elasticity and the approxima- tion v = -3- were employed. The purpose of this work is to present calculations of the energy changes for many of the same reactions using anisotropic elasticity. The problem of dissociation of a(100) and a(110) dislocations is also considered, and maximum fault energies for which dissociation will be energetically favorable are calculated for several bcc metals. Two general types of reactions are considered; those for which the reactant (a/2)(111) dislocations have long-range attractive forces and those for which the reverse is true. An example of the former is: (a/2)[lll] + (a/2)[lll]-a[l00] while the latter are typified by: (a/2)[lll] + (a/2)[111] -a[011] Only reactants lying in different slip planes are considered; therefore, the products must lie along (111) or (100) directions, which are the intersection of two {llO} planes. It will be assumed that the reactants and products are infinitely long parallel dislocations, since in this case the energy change associated with the reactions is a maximum.&apos; THEORY The self-energy per unit length of a straight mixed dislocation in an anisotropic medium can be written? where b is the Burgers vector, K is an appropriate combination of the single-crystal elastic constants, and R and ro are, respectively, outer and inner cut-off radii of the elastic solution. The energy given by Eq. [I] does not account for any variation of the core energy with orientation. This could be manifested by an orientation dependence of the core radius or, equivalently, the Peierls width, of the dislocation. However, the energy contribution due to this source is expected to be small, and current models of the dislocation core are not sufficiently accurate to justify such a refinement. It has already been shown that for the isotropic case the energy contributions due to nonzero tractions across the cores of the reactants and products exactly cancel one another in the reaction.&apos; Accordingly, it will be assumed that this contribution to the total energy change in the anisotropic case is small. In the subsequent discussion it is also assumed that the core radii of the reactant and product dislocation are the same and that, where stacking faults are formed, the faulted region is bounded by the centers of the partials. Consequently only changes in elastic energy due to the reactions will be considered. When the dislocation is parallel to either the (111) or the (100) directions, K may be written:375 K = (Ke sin2 a + Ks cos2 a) [2] where K, and Ks are the combination of elastic constants corresponding to an edge and screw dislocation lying along the same direction as the mixed dislocation, and a is the angle between the direction tangent to the dislocation line and the Burgers vector. Eq. [2] should not be confused with the isotropic approximation to the variation in energy with line Orientation.6 It should be noted that the essentially isotropic expression for K is a result of the characteristic symmetry of the (111) and (100) directions and is not, in general, valid for other dislocation directions in anisotropic cubic metals. The energy* change for a reaction in which the re- actant and product dislocations are parallel perfect dislocations can be written: where Ep and E, refer to the self-energies of the products and reactants, respectively. For dislocations parallel to (100) and (111) directions, Eq. [3] becomes:

Jan 1, 1969

By E. N. Cameron

GRAPHITE has been included in U. S. lists of strategic minerals since the problem of mineral deficiencies was revealed during World War I. Since 1918 the domestic graphite industry has led a precarious existence, and there has been much uncertainty as to the amounts of usable graphite of various grades that would be available from domestic sources in time of emergency. In 1950-1951 therefore, the writer, assisted by Paul L. Weis, undertook a review of domestic graphite sources for the U. S. Geological Survey.&apos; The conclusions of this study are presented here, with a discussion of some technologic and politico-economic factors bearing upon the problem. Uses of Graphite: Natural graphite as marketed exhibits a wide range of properties, which determine the uses to which it is put. The most essential uses are in the manufacture of crucibles and related refractory articles, in lubricants and packing materials, and in the manufacture of batteries, foundry facings, pencils, and carbon brushes. Numerous specifications covering the mineral in its various applications must be met by producers and processors of graphite. The problem of supply is therefore not simply one of procuring a sufficient total tonnage, but the more difficult problem of procuring enough of each different grade to meet foreseeable needs. The amount of graphite required by American industry is not large. Ordinarily only a few thousand tons of strategic grades are consumed annually, yet the elimination of this small tonnage would have serious effects in several industries. Strategic Graphite: Since World War I, 60 to 100 pct of the country&apos;s annual supply of graphite has been furnished from imports. At present, natural amorphous graphite for use in pencils and batteries is produced largely from American-owned mines in Mexico. Graphite for foundry facings is obtained from a number of sources. Neither grade is a serious problem. High purity graphite for carbon brushes and for pencil leads, however, is imported, largely from Ceylon, in the form of amorphous lump graphite. Most of the flake graphite used for crucibles and related refractory articles is likewise imported, largely from Madagascar, and much of the lubricant and packing grade graphite used by industry is obtained from the same source. The strateg&apos;ic grades of graphite are therefore amorphous lump of the Ceylon type, crucible flake, and flake suitable for lubricants and packing. Ceylon lump and Madagascar flake have for many years been accepted as standard by domestic consumers of graphite, and various essential manufacturing processes are geared to the use of graphite from these sources. Ceylon graphite as marketed is classified into several grades based on particle size and purity. Processing methods are said to be simple, but the products marketed are carefully graded and are consistent in their characteristics, an important matter to the consumer. Nearly all the graphite produced in Ceylon is from veins. Resources are reported to be large, labor is cheap, production costs are low, and world competition is slight—factors accounting for the commercial success of the graphite mining industry in Ceylon. Madagascar is reported to have deposits of the Ceylon type, but its output consists almost entirely of flake. Madagascar graphite as received in the U. S. is further processed by importing organizations, and a large number of grades are produced to meet industry requirements, especially those for crucible flake and for lubricant and packing grade flake. Madagascar crucible flake as marketed is noted for coarseness, uniformity, toughness, clean-

Jan 1, 1957

By H. Shaw

GRAVITATIONAL measurements made by means of the Eötvös torsion balance over any area enable a representation to be obtained of the total gravitational effects over the surface of that area arising from the combination of all sources of gravitational disturbance. The investigation of gravitational anomalies occurring in the upper layers of the earth&apos;s crust, in this way, has been attended with considerable success, and, especially in areas in which no undesirable disturbing factors were present, it has been possible to locate geological structures and mineral deposits with remarkable accuracy and also to delineate their confines and to indicate their depth below the surface with a certain amount of precision. Before this can be done successfully, however, it is necessary to determine the gravitational effect arising from all other extraneous .anomalies in order that these may be satisfactorily eliminated. Disturbing features giving rise to these gravitational anomalies may be divided into two classes, according to whether they are situated at or below the surface. The former are determined readily by a detailed leveling of the ground surface, and may be satisfactorily eliminated provided the specific gravity of the terrain material is known, but the latter are generally unknown, and can only be ascertained with difficulty. When, therefore, the observations obtained by means of the Eötvös torsion balance have been corrected for all surface irregularities, known as terrain and topographical effects, there remain residual gravitational values which are due entirely to subterranean conditions. The task of interpreting these results consists in disentangling the various subsurface anomalies, and subsequently in computing and recombining the effects of these various masses in order to verify the interpretation. When the gravitational anomalies are due to large and comparatively simple structures it is a matter of little difficulty to arrive at a satisfactory interpretation of the subterranean conditions, but in more complex areas, where the geological conditions are more complicated and several irregular features exist, the process of disentangling the various constituents of the complex mass arrangement is more difficult and requires the expenditure of considerable time and labor.

Jan 1, 1929

By Albert E. Ketler

Introduction – The introduction of computerized monitoring and control (M/c) equipment into the U.S. coal mining industry may prove to be of truly revolutionary proportions in the 801s.Many of you are aware that the British have developed and have been using such sophisticated M/C equipment for performing production and safety related tasks in their coal mines for nearly a decade. The benefits of M/C systems in the mining industry are usually separated into those which improve productivity, and hence make money for the company, and those which improve safety, and hence cost money. The economic benefits of M/C are startling for the production related functions such as for monitoring and controlling conveyor belts, de-watering pumps, electrical power distribution, and the like. It doesn&apos;t take much analysis to show that hundreds and even thousands of tons of coal don&apos;t get mined every time a belt shuts down or when power is out due to circuit breakers tripping for any number of reasons. A flood, caused by a malfunctioning pump which goes undetected for lack of feedback monitoring of pumping parameters, can destroy literally millions of dollars worth of mining equipment. The M/C system would be justified or not based on whether or not the productivity benefits balanced the cost within a timespan commensurate with the return on capital philosophy of the company. The safety related benefits are easily underestimated or ignored completely and the purpose of this paper is to under-score some of these benefits, as well as to review the application of M/C to the coal mining industry. The companies involved are Transmitton Ltd of England and Minetics Corp of Pittsburgh, Pennsylvania. Transmitton is probably the most experienced manufacturer of M/C equipment in the world having some 200 installations to its credit. Minetics is the marketing and manufacturing arm for Transmitton in the U.S.A. and is responsible for all aspects of distribution and service. Plans are underway for manufacturing of the Transmitton hardware for U.S. sales to be transplanted into U.S. subcontractors by 1981. Thus our coal mining industry will benefit from British technology, but without the delays and additional costs usually involved in international shipments.

Jan 1, 1981

H. RIES, Ithaca, N. Y.-The part of Mr. Fiske&apos;s paper that interests me especially is that portion dealing with the raw materials, and the tests that were applied to the raw materials in order to determine their value in advance, if possible, because that, I believe, is a step in the right direction. For a number of years I have done my best to persuade different consumers of clay to develop standard methods for testing raw materials. We have in this country a large variety of clays which can be used for a great many different purposes, but in many cases the consumers either have no standard methods for determining the value of those clays in. advance, or if they have they do not publish them; consequently it often puts the clay miner at a disadvantage. If, for example, manufacturers of different types of refractory materials would state publicly just what physical tests their raw materials have to meet, it would, I believe, help them to find more easily the materials that they are looking for, and the clay producer would also be benefited. It would also encourage him to have his clays tested in advance, so that samples could be accompanied by certificates of physical tests that would be of convenience to the manufacturer. At the present time, in this country there are certain types of clay which seem to be rather scarce. There apparently are not many deposits of clay that are exactly suited for the manufacture of zinc refractories. So, too, there are not many deposits of clay that are suited for the manufacture of glass-pots, or the blocks for glass tank furnaces, or clays that can be used for graphite crucibles. Now, in many cases, no standard series of tests has been developed. I am also gratified to see that Mr. Fiske considers the tensile strength. tests of value. Some years ago the American Ceramic Society appointed a committee to draw up a series of recommendations covering standard tests. These recommendations were especially for the use of State geologists and the U., .S. Geological, Survey. Among the tests that were considered was the tensile-strength test, which Mr. Fiske has mentioned in his paper. Unfortunately, a majority of the committee turned it down, and the test was therefore not officially approved, but two of us, who formed the minority, believed in it. Since then the other members of the Committee have come to see that that is an important test to make and Mr. Fiske has emphasized it in his paper.

Jan 1, 1918

By J. J. Gilman, T. A. Read

S URFACE effects in the cleavage of brittle crystals have been known for some oftime,1, 2 but our knowledge of surface effects in the plastic deformation of crystals is of relatively recent origin. In 1936, Roscoe9 eported his observations comparing oxidized and clean cadmium crystals. He found that cadmium crystals 1/2 mm in diam when covered by an oxide film less than 1200 atoms thick had critical shear stresses about twice those for clean crystals. This effect is anomalous in that it cannot be caused by the inherent shear strength of a normal oxide film. Either an interaction between the film and the crystal causes the large increase in strength, or the oxide film has an abnormal mechanical strength. Several authors since Roscoe have studied surface effects in crystal plasticity. A complete review of the literature will not be presented, but most of the results may be summarized as follows: 1—The critical shear stress for slip is increased markedly by very thin oxide films on zinc4 and cadmium crystals;" &apos; also, the entire stress-strain curve is raised by an oxide coating;3,4 both effects increase with decreasing specimen radius. 2—Surface active substances such as oleic acid destroy the hardening effect of oxide films.4, 6-8 The time required for the reduction of the hardening effect to begin increases with the viscosity of the solvent4~ 3—There has been dispute in recent years about the effects of surface active substances themselves on plastic deformation. Rehbinder, Lichtmann, and Maslenikov9 state that surface active substances reduce the strength of metal monocrystals markedly and increase the number of slip lines per unit length at a given strain. The effect varies with orientation for tin crystals being smallest for x, = 0, largest for x, = 45", and intermediate as x, + 90°.10 Several workers claim to have disproved the results of Rehbinder&apos;)"." but Rehbinder and Lichtmann9 have defended themselves and Masing with his collaborators" has confirmed some of Rehbinder&apos;s results. 4—Immersion of metal specimens in electrolytes such as sodium chloride reduces their strength12,13&apos; and subsequent cathodic polarization increases the strength reduction. For noble metals, the strength reduction occurs for both anodic and cathodic polarization," increasing with increasing polarizing voltage. 5—Electroplated copper coatings effect the creep rates of zinc monocrystals. Poly crystals are not affected." 6—Immersion in dilute acid destroys the hardening effect of an hydroxide film. When an acid solution is applied to a steadily creeping crystal, the creep rate jumps to a very high value and then drops gradually to a steady value which is higher than the initial steady rate.*&apos; " If the hydroxide film to be removed is very thin (about 100A thick), the creep rate does not change measurably, but a small rapid strain-increment is observed when dilute acid is applied." 7—Crystal plasticity depends on specimen dimensions. This was observed by Lichtmann and Ven-stroml" for monocrystalline tin and by Andrade and Kennedy" for polycrystalline lead. 8—Immerson of copper crystals in mercury has no effect on their stress-strain curves.&apos;" 9—Bombardment of creeping cadmium crystals with a particles which penetrate the surface to only 0.005 mm may increase their creep rates as much as five times.&apos;&apos;&apos; The experiments which will be described in this paper pertain to: (a) the effect of a crystal&apos;s shape on its plastic deformation, and (b) the effect of metallic surface films on plastic deformation. For the work pertaining to (a), crystals of zinc, tin, and lead were grown which had various shapes. These were tested in simple tension. Macroscopic rotations about the tension axis which are unpredicted by the classical theory of slip were observed, and serrated edges were observed in tin crystals. For the work pertaining to (b), the effects of evaporated and electrodeposited films of copper, nickel, gold, and zinc on the mechanical properties of zinc, tin, and lead crystals were determined. The films influenced both slip and twinning of the crystals in creep and tensile tests. Experimental Details Chemically pure zinc, tin, and lead were used in this investigation. The zinc was 99.999t pct pure;

Jan 1, 1953

By C. C. Templeton, S. S. Rushing

Methods previously developed for the study of air-liquid displacements in microscopic capillaries (inner diameters of 3 to 40 microns) have been used to investigate oil-water displacements in capillaries initially filled with water. Displacement calculations assuming perfect displacement and no capillary pressure hysteresis yielded oil effective viscosities smaller than the macroscopic viscosities. For a given liquid pair, the oil effective viscosity decreased both with decreasing capillary size and with increasing oil-water viscosity ratio. This behavior can be explained by the existence of an annular water film (20 A to 260 A thick) on the capillary wall. When the capillary was first filled with oil, the ratio of the oil effective viscosity to the normal oil vircosity was highest for the first water displacement and decreased with subsequent displacements. Sometimes the oil effective viscosity ratio during the initial water displacement was greater than unity. INTRODUCTION In a previous paper1 a technique was described for studying air-liquid and liquid-liquid displacements in very small capillaries of uniform diameter, in the hope that such microscopic data would further the understanding of the nature of multiphase fluid flow through porous media. That paper contained comprehensive data for air-liquid displacements in Pyrex capillaries, with a few data for oil-water displacements in capillaries initially filled with water. The purpose of this paper is to present more complete results for oil-water displacements in capillaries initially filled with water, and to describe for the first time such observations in capillaries initially filled with oil. In this way the effect of the wetting history of the system upon the displacement process may be studied. METHODS The basic techniques employed were described in the previous paper.1 The measuring procedure and the working equations will be briefly summarized here and a few modilications will be pointed out. For the present study, temperature control within 0.l °C was obtained by placing the microscope and its immediate accessories in a thermostated air bath made of a steel frame covered with plexiglas. The water and oils used in this work were the same as in the previous paper,1 with the addition of "Medium Mineral Oil, U.S.P. supplied by the Harshaw Scientific Co. When the first liquid was introduced into the horizontal capillary, the air-liquid static capillary pressure Poc was measured along the observable length of the capillary. From the relation Poc = 4y cos 0/d, the capillary diameter d could be calculated from Poc if the "microscopic" air-liquid boundary tension, To = y cos On, was taken as equal to its known "macroscopic" value. This calculation involves assuming that cos 6 = 1 and that capillary size or the resulting high interfa-cial curvature has no effect on surface tension, or y cos 6, as was verified by our work, and also by that of Cohan and Meyers on air-liquid-solid systems. For several capillaries these calculated diameter values were compared with values measured visually with a filar micrometer eyepiece. For a given capillary the average values for the two methods agreed within 1 or 2 per cent, but the visual values were less reproducible than the calculated values. Further the calculated values were much less subject to personal bias and took into account any slight ellipticity that might be present. Hence diameters calculated from air-liquid Poc data were used throughout this paper. The second liquid was introduced in such a way that a single spherical interface separated the two liquids. Displacements were always made with a constant pressure, Pt, between the ends of the capillary. The times (t) at which the interface passed certain

Jan 1, 1957

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By Robert G. Nisle

In conducting a pressure build-up test on an oil well, it is often necessary to shut-in the well for a short time prior to initiation of the test. The effect of such a short tern shut-in on the resulting pressure build-up curve is derived. The derivation is based on the Kelvin point-source solution and is a straight forward extension of the fundarnental theory. The magnitude of the effect is evaluatecl and illustrated by an example. It is shown that if the production subsequent to the short term shut-in is at least 10 times the duration of the shrct-in, the effect will he less than 10 per cent. INTRODUCTION It often happens that before a pressure build-up test can be made an additional valve must be mounted on the wellhead, or on arrival at the well, it might be learned that the well had been shut-in several hours the previous day because of a shortage of tankage. In such cases the question is How will such an interruption of production affect the results of a pressure buildup test This work explains how to take account of such a short term shut-in in order that the test can proceed without further delay. The solution presented here makes use of the Kelvin point-source solution used by Horne1 in his treatment of the pressure build-up in wells. Use is also made of the super-position theorem. MATHEMATICAL DERIVATION The well is assumed to have been in production at a constant rate for a relatively long time (several days or more). It is then shut-in for a short time, after which it is again placed in production at the previous constant rate. It continues to produce at this rate until shut-in for a pressure build-up test. The Kelvin point-source solution is expressed by Eq. 1. The sequence of production rates is listed in Table I. TABLE 1 — SEQUENCE OF PRODUCTION RATES Time interval Production Rate At time AT the pressure will be the resultant of the sequence of production rates shown in Table 1. An expression for the super-posed effects may be derived from this table. (Effect of + q for T + ? T) + (Effect of - q for T + ?T-t,) + (Effect of + q for T + ? T - t,) + (Effect of - q for ? T) = Resultant........(2) The desired result is obtained by substituting the effect defined by Eq. 1 for the terms in Eq. 2. The result is Eq. 3. When the logarithmic approximation is made for the exponential integrals and the terms collected the result is Eq. 4. Let T — t2 = T = flowing time following short term shut-in t2 — t1 = 6 = duration of short term shut-in Then T - t1 = r + 6 Substitution of these quantities in Eq. 4 gives p(rw ?T) = P,, -When d<<t - AT then d—&apos;-, T— approaches 1. r + AT In this case the effect of the short term shut-in may be ignored. In order to get some idea of the numerical magnitudes involved take the worst possible case, when AT = 0, that is at shut-in. If the error is made less than some maximum acceptable value at this time, it will be less than the maximum for all subsequent times. d + r Let the difference between the value of y-— and 1 be less than 0.1. Then —6+r — 1 < 0.1 S < O.l T Therefore, if the flowing time following a short term shut-in is at least 10 times the duration of the short term shut-in, the error introduced by ignoring the short term shut-in will not exceed 10 per cent of T+AT A T

Jan 1, 1957

By George Krauss, Seth R. Thomas

One complete cycle, allstenite to martensite to aus-tenite, of Martensitic transformation was induced in a commercial 18 Cr-8 Ni stainless steel. Transmission electron microscopy showed that the reverse transfarmation, martensite to austenite, perpetuated the dense defect substructure of the martensite produced by the direct transformation, austenite to &apos;martensite, and reproduced the retained austenite matrix orientation. A general precipitation of lathlike M,,C, particles was noted to be present in, and is suggested as cause for, regions of martensite that Izad formed after a complete cycle of transformation. The habit plane of the precipitate particles was found to be within 5 a plane previously established as the habit of nitride precipitates of similar morphology in bcc iron. The direct transformation of austenite (y) to martensite (a) in metastable 300 series stainless steels has received considerable attention in the past,&apos;-8 and the martensite product given special emphasis in recent years,9"*u but little information has been published about the reverse martensitic transformation during which bcc a martensite is converted to fcc y austenite."-" The reversal mechanism and the resulting crystallographic relationship between parent and product austenite are of fundamental concern. The reversal product, fully austenitic, and hereafter referred to as reversed austenite, exhibits a defect structure far different from its virgin counterpart. Some studies have been reported in which the structure of reversed austenite in iron nickel alloys is compared to annealed austenite with respect to austenite strengtheningM and Stabilization.&apos; The martensite in these Fe-Ni alloys, however, shows a basic difference from that produced in stainless steels. Structurally, the Fe-Ni martensite is profusely twinned," while the (low-carbon) Fe-Cr-Ni martensite contains a high density of tangled dislocations and is apparently twin-free.I0 reediis" has recently shown in an Fe-16 Cr-12 Ni stainless alloy that this typical martensitic defect structure and the reverse transformation directly influence the structure of the reversal product. He found that much of the reversed austenite had returned to the orientation of the virgin austenite and that fine twins were formed in the austenite after the reverse transformation. This investigation was undertaken in order to describe as completely as possible the structural changes produced by a cycle of transformation in a typical 18-8 stainless steel. EXPERIMENTAL PROCEDURE The 301 stainless steel under investigation (17.44 Cr, 7.75 Ni, 0.80 Mn, 0.60 Si, 0.40 Mo, 0.40 Cu, 0.08 C, 0.03 N, bal Fe)was received as 0.060-in.-thick

Jan 1, 1968

By W. J. Houk, F. C. Hull

To clarify interpretations of grain structures and to assist in calculations of spatial grain size distributions, plane distribution curves have been determined for random sections through four regular polyhedrons approximating the shapes of metal grains. The characteristics of the distribution curve for the average metal grain are predicted. IT was realized early in the history of metallurgy that metals are polycrystalline aggregates and that the size and shape of crystals affects the properties of the material. Reaumur1 in 1722 employed the microscope to examine the fractured surfaces of steel and of white and gray cast iron and suggested a polyhedral arrangement of the crystals. The first extensive investigation of the form of crystal grains was carried out by Desch.2 He examined the disintegrated grains from a ß brass sample and noted that the number of faces per grain ranged from eleven to twenty and that the number of edges per face varied from three to eight and the maximum occurred at five. While it has been found practical to examine isolated grains only in exceptional cases, it is always possible to make a plane section through the metal and examine the shape of the grain sections on the plane of polish. Desch2 tried to determine the relation between the form of a polyhedron and that of its plane sections for comparison with distribution curves of numbers of sides per grain section of actual metal samples. The polyhedrons investigated were the rhombic and pentagonal dodecahedrons and the orthic tetrakaidecahedron. However, the frequency distributions of the number of sides of plane intersections were not sufficiently characteristic to decide which polyhedron most closely approximated the average grain in a metal. Determination of Statistical Shape of Grain in Space Scheil3 was interested in the problem of calculating the distribution of grain sizes in space from the easily measured distribution of grain section sizes on the plane of polish. Assuming that the grains were spheres and using the plane distribution curve for a sphere shown in Fig. 1, he employed a successive subtraction method to calculate the spatial distribution. In order to evaluate the accuracy of these calculations, Scheil and Wurst4 determined the actual distribution of grain sizes in space in their sample of ingot iron by polishing off successive layers and following every individual grain in a series of micrographs. From curves of mean radius of intersection of a given grain vs thickness of metal removed in polishing, Scheil and Wurst attempted to derive the statistical shape of a grain in space. Their calculated plane distribution curve for this shape is compared with the distribution curve for a sphere in Fig. 1. A table of values based on this curve was prepared for calculating spatial distributions of grains. The calculated and measured spatial distributions of their sample then agreed much better than when a spherical shape had been assumed. In the present paper, an attempt has been made to learn something about the average metal grain by studying in detail the effect of the shape of regular polyhedrons on the plane distribution of areas and shapes of areas produced by random sections through them. From the data presented below, it can be concluded that the plane distribution curve for the average metal grain differs in three fundamental respects from the curve derived by Scheil and Wurst. Polyhedrons Selected for Study The polyhedrons selected for the statistical study are illustrated in Fig. 2 and consisted of a cube, a figure formed by cutting off the corners of a cube at the midpoints of the original edges, a tetrakaidecahedron, and a pentagonal dodecahedron. The length of edge on any one figure is a constant. For the above models the edge lengths were 3.50, 4.00, 2.00, and 2.08 in., respectively. A cube was selected for one of the polyhedrons because of its simple geometry, because it is a form that by repetition can completely fill space, and because it represents a convenient degree of departure from compactness beyond which the shape of

Jan 1, 1954

By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959