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By Edward K. Landis

Our Transactions contain so many suggestions of apparently trivial, yet really important, contrivances for the saving of time and

Jan 1, 1893

By Kurt Kennedy

A method is described by which three elements can be condensed simirltaneously on a common substrate in such a way that the composition varies with position on the substrate. Almost all possible combinations of three solid elements can be formed in a single evaporation. The three elements are heated by magnetically deflected electron beams. The alloys and cornpounds formed by this method generally correspond to those trade by other methods; however, many exceptions exist. Simple symmetric crystallographic phases tend to form in preference to more complex phases. The Nb-Sn. Cr-Fe-Nt, and other systems of alloys made by this method will be discussed. Phases that form very slowly, such as the o phase in Cr-Fe alloys, may be formed rapidly by this method when certain substrate temperatures are used. STUDYING all the mixtures and compounds of two or more elements by the preparation of individual samples forces the investigator to make sampling sufficiently close together so that the properties of the intermediate compositions can be inferred. A completely unknown system will require a dis c our aging ly large number of preparations in order to fully know all its properties. For the purpose of expediting this type of investigation, methods have been devised to prepare samples that have a continuous variation in composition over some predefined area. The code-position of two elements onto suitable substrates has been used to produce alloys or compounds that have variable compositions depending on their positions on the substrates Composition gradients have been formed by depositing a wedge-shaped layer of one element and then depositing a second wedge-shaped layer on top of it such that the total film thickness is kept constant. Concentration equilibrium perpendicular to the surface is then established by annealing.4 This paper describes a method for the simultaneous condensation of three volatile components on a substrate such that there is a regular variation of composition with position on the substrate. The arrangement of the evaporation sources and the substrate is shown schematically in Fig. 1. Materials to be evaporated are placed in three water-cooled crucibles located at the corners of a 10-in. equilateral triangle. Electron beams from cathodes located below the crucibles are bent 180 deg by magnetic fields and focused on the material to be evaporated. The cathodes are connected in parallel to a constant-current 12-kv power supply. The distribution of emission current from each cathode is controlled by filament temperature. When materials that sublime are to be evaporated, the electron beam is deflected by an auxiliary ac magnetic field so that the beam moves over the surface of the evaporating material rather than digging a hole in one spot. The substrate is a 10-in. triangle of 2-mil stainless steel or molybdenum which is stretched against a slightly curved heat sink by a frame as shown in Fig. 2. This frame and heat sink are located so that each corner is directly above an evaporation source. The heat sink has three radiant heaters at each corner that can be separately controlled permitting the

Jan 1, 1967

By A. J. Jacobs

THE purpose of this note is to draw attention to a set of tables, recently compiled in Rocketdyne Research Report No. 64-19, under the title "Crystal-lographic Data for Indexing Cubic Twin Reflections and Cementite (Fe3C) Reflections in Electron Diffraction Patterns."' These tables were an outgrowth of electron-diffraction work conducted over the past several years on steels, precipitation-hardening aluminum- and nickel-base alloys, molybdenum, tantalum, and tantalum-base alloys. The first table lists the indices of possible twin reflections for all the possible twinning planes in bcc and fcc lattices. The twin reflections correspond

Jan 1, 1965

By Otto H. Henry, J. J. Cordiano

THOUGH powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. PURPOSE OF INVESTIGATION Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: I. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1945

EXCEPT for the material, the same method that you used in alloying gold is used in alloying silver, but its alloy is fine copper. Just as the silver does in gold, so copper in silver diminishes and lowers its fineness and increases its quantity. If half the value is surpassed it is no longer called silver but copper containing silver, as I told you of gold. But in my opinion one could also say silver of 5,4, or 3 leghe or even of one. How- ever, these terms are of no importance for our purpose. It is enough that you suppose that the whole quantity of silver that you have is twelve parts. If you put one part of copper in h with the melt, you will say [74] that you have 11-lega silver and that it is in weight thirteen of the first parts† and so on, when you add two to ten and four to eight, always naming the quantity of the fine silver just as you did with the gold, either

Jan 1, 1942

SAN FRANCISCO SECTION Roy H. ELLIOTT, Chairman - T. A. RICKARD, Vice-chairman W. H. SHOCKLEY, Secretary-Treasurer, 959 Waverley St., Palo Alto, Cal. D. A4. RIORDAN C. F. TOLMAN, JR. A joint meeting of the local sections of the several national engineering societies represented in San Francisco was held at the Engineers'. Club on Thursday evening, Sept. 26, 1918. The subject for the evening, "Fuel Conservation," was ably discussed by a-number of representatives of the Federal Administration and by engineers interested in the generation and utilization of all kinds of power on the Pacific Coast. The following extracts from papers presented at this meeting have been selected as being of the greatest interest and value to members of this Institute. Problems of the Fuel Administration ALBERT E. SCHWABACHER.-America's war needs call for 100,000,000 more tons of coal this year than in 1917, and 200,000,000 tons more than in 1914, when the war started, and this increase must come from a weaker man-power than that of 1917. It must be transported by a railroad system that has not been improved since the war started, and has been burdened with inconceivably greater demands than were made upon it before the war. This tremendous increased demand must be met by most intensive work in three directions; increased production, efficient conservation, and a distribution system which will insure against lost motion. While every European country has decreased its coal production since the war began, the United States has mined 50,000,000 tons more coal, during the first year of the war, and will increase this by another 50,000,000 the present year. Every 8 days there are being mined and transported as great a weight of coal as of the entire wheat crop of the United States. Of the 735,000,000 tons of coal which must be made available for consumption by our railroads, ships, war industries and people, 100,000,000 tons will come from the anthracite fields, the remainder from the bituminous fields. In 1917 there were produced about 330,000,000 bbl. of oil, and this year an additional amount over last year's production, of approximately 23,000,000 bbl. will be required. Water power developed 5,000,000 hp., the demand greatly exceeding the available supply.

Jan 12, 1918

By W. L. Finlay

Size effects in quenching steel are particularly prominent and well recognized because of the existence of a critical cooling rate separating nuclea-tion and growth transformations, as exemplified by the formation of pearl-ite, from the shear type of transformation characterizing the martensite reaction. The absence of a similar, sharply demarcating cooling rate is characteristic of precipitation hardening systems and size effects in these are correspondingly less prominent. This paper is concerned with a size effect in high-purity, precipitation-hardenable alloys which appears not to have been recognized previously. This effect is believed to result from the thermal fluctuations which inevitably occur in quenching a specimen of finite size into a cooling liquid rather than from the existence of a critical cooling rate. QUENCHING "ANOMALIES" The precipitation hardening literature contains many references to so-called anomalous quenching and aging results. By "anomalous", investigators usually meant that their alloys did not consistently harden on aging after quenching according to some anticipated pnttern: not infrequently virtually no age hardening occurred with compositions known to be precipitation-hardenable. Perhaps the most prominent series of anomalies was reported over a 15-year period by Gayler and coworkers on aluminum-copper.l,2,3,4 Working with silver-rich copper alloy, Cohen5 secured some very interesting Rockwell F hardness changes of from 1-5 Rockwell points between the first peak and valley. Fink and Smith borrowed one of Cohen's specimens and, following his heat treatment and quenching practice to the letter, secured6 very different results in which only one peak was obtained and in which the hardness level at the aging lime of Cohen's first peak was 20 Rockwell F points higher. Fink and Van Horn7 encountered serious deviations in age-hardening high purity aluminum-zinc alloys. They stated that "the discrepancies were larger than might be expected from possible experimental errors in the Brinell readings." Geisler, Barrett and Mehl8 likewise encountered anomalous hardening results in aluminum-silver alloys, securing quite different age-hardening curves from two identical specimens. They stated that "the treatments of these samples had been the same, so that the different behaviors could be attributed only to accidental variations in the quenching practice."

Jan 1, 1950

By M. Baeyertr

Since 1915 many papers and books have covered industrial applications of X-rays from various angles. Two of the more recent are a paper by Fink and Archer, which describes in detail the technique of radiography, and a paper by Clark2, which embraces the whole field of X-ray metallogmphy. This paper, therefore, is confined to work of the X-ray Laboratory of the Western Electric Co., which naturally divides into two categories: radiography and diffraction patterns of various types. Radiography Radiography is the field in which the application of X-rays has had most general appeal among the industries which produce or use metals and alloys. Equipment permitting the examination of heavy sections of metals less permeable than aluminum or other light alloys requires apparatus capable of generating hard X-rays over a considerable period of time. The equipment used in the work presented in this paper is practically identical with that described by Fink and Archer in their paper on radiography in industry and is easily capable of penetrating 1/8 in. of lead. Radiography is used in two major groups of problems: (1) in the development of cquipment and tools and (2) in studies of materials. So far there has been no instance in which the use of radiography for routine inspection is justified. This is partly due to the fact that the manufacture of telephone apparatus involves the production of many identical parts by standardized procedures and equipment that has had development and trial before being put on a regular production basis. It is during this stage of development of equipment and tools that radiography has been used to particular advantage.

Jan 1, 1931

By B. L. Averba

THE determination of retained austenite by X-ray diffraction uses the following relationship:"" Pa = constant . RVaA (8) [1] where: P is the diffracted power from phase a; R, the calculated intensity factor; A, the absorption correction; 8, the diffraction angle; and Va, the irradiated volume of phase a For a flat sample making a glancing angle + with the incident beam the absorption correction is calculated as: * 1 sin (28 - 4) A .= 1 [2] µ sin, (28 — 4) + sin 4 where µ is the linear absorption coefficient. Beu3 has proposed that the computed absorption correction be combined with the constant and that the experimental observation of the absorption correction used in the original method be eliminated. This procedure is permissible only if: 1—There is no preferred orientation in the sample, and 2—The geometric requirements have been met precisely. If these conditions are not met the validity of the determination is questionable. Unfortunately the necessary conditions must be tested experimentally for each determination, and this is done most easily by observing whether the apparent absorption has the form of Eq. 2. In practice it may be convenient to plot P/R vs the parameter sin (2? — )[sin (28 — +) + sin +] to obtain straight lines for the ap- parent absorption correction. Deviations from straight lines indicate either that the sample has not been positioned correctly or that the relative intensities are incorrect. Geiger counter spectrometer methods also have been used successfully for retained austenite determinations. In the usual spectrometer arrangement the sample makes equal angles with the incident and diffracted beams (8 = ); thus the absorption correction is simply 1/2µ and independent of 8. The retained austenite is then easily calculated from integrated intensity measurements on austenite and martensite lines. If the austenite content is not too low and if excessive fluorescence is not encountered it is possible to use filtered radiation and a recording spectrometer. The integrated intensities are then proportional to the areas of the diffraction peaks. For lower austenite contents the following technique was used: A bent quartz monochromator and a Geiger counter spectrometer are employed. The monochromatic radiation is focused on the front slit, and the counter slit is made broad enough to include the entire line. A series of readings are taken in the vicinity of the diffraction peak. The highest reading includes the diffraction line plus background. The background is obtained from the average of several readings on each side of the peak. The integrated intensity is obtained by subtraction. CrK, and FeKa have been used for such determinations. This technique has been found to be as sensitive and as accurate as the photographic methods. In the spectrometer methods the ratio austenite/ martensite may be obtained from readings on austenite and martensite lines and the application of Eq. 1. It is also possible to use external standards and to obtain the austenite contents from measurements on the austenite lines alone. The small correction for carbides then becomes unnecessary. The best standards are probably samples with known

Jan 1, 1954

By Arthur Smith

THE Verde mining district is in Yavapai County, in north-central Arizona. Jerome, the principal town, has a population of 6000 and the two important mines of the district-the United Verde and the United Verde Extension-lie almost within its limits. Perched high on the southwest side of the Verde valley, at elevations of 4800 and 5500 ft. (1463 and 1676 m.) respectively, both mines have long tunnels from their lower levels through which the ore is hauled to the smelters. Clarkdale, the smelter town for the United Verde mines, lies in the Verde valley 4.1 miles (6.5 km.) distant in an air line from Jerome and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel and Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 miles long and has a compensated grade of 4 per cent. At Clarkdale it connects with the Verde valley branch of the Santa Fe railroad. Clemenceau, the smelter town for the United Verde Extension mine, lies 3.5 miles (5.8 km.) in a southeasterly direction from Clarkdale, at an elevation of 3420 ft. It is connected to the Verde Valley branch of the Santa Fe railroad at Clarkdale by the Arizona Extension R. R., . a subsidiary of the United Verde Extension Mining Co. The portal of the haulage tunnel, at an elevation of 3757.5 ft., is also connected with the smelter town by 4 miles of standard-gage track belonging to? the same company. In the vicinity of Jerome, the great southern escarpment of the Arizona plateau forms the northeast side of the Verde valley. The general level of this escarpment, or "rim" as it is called, is about 4000 ft. above the Verde River. A corresponding elevation is reached only by the highest peaks of the Black Hills, which bound the valley to the southwest. Two lava-capped mesas, known as "Mingus" and "Wood chute mountains," form the culmination of the Black Hills. That part of the Old Black Hills mining district which lies between their crests and the Verde River is now known as the Jerome, or Verde, mining district. If the . smelter towns are not included, a strip about 7 miles long by 3 miles (11 by 5 km.) wide, embraces practically all of the properties belonging to the Jerome district. This strip lies parallel to and along the side of the Verde valley from First View, 2 miles northwest from Jerome, to the vicinity of Allen Springs, at the south end of Mingus mountain and all within the boundaries of the Prescott national forest reserve.

Jan 3, 1924

By A. B. Kinzel

ALTHOUGH vanadium is an important constituent of almost every brand of high-speed steel manufactured today, little is known as to its role in this series of alloys. The now standard 18 per cent tungsten and 4 per cent chromium constituents were the result of developments and improvements before 1903. In that year, vanadium was added to the steel by Dr. J. A. Mathews. This proved to be an outstanding con-tribution, so that the standard high-speed steel of today is generally referred to as the 18-4-1 type-18 per cent W, 4 per cent Cr and 1 per cent V. Various modifications have been attempted, since then, but with the exception of the introduction of cobalt, no striking improvements have occurred. Vanadium has been increased to 2 per cent in many of the common brands, and at least one brand contains 5 per cent V in addition to the usual tungsten and chromium. The carbon has been gradually increased so that it is not uncommon to find 0.80 per cent in the standard grade, although the carbon in the 5 per cent vanadium steel mentioned above is approximately 1 per cent, and even 1.2 per cent has been made experimentally. The role of vanadium has never been well understood, and although vanadium has been increased to 2.5 and even 5 per cent in certain high speed steels, it has not been generally established that the higher vanadium contents 'result in superior cutting properties. However, in all of the investigations, of which the writers are aware, the interrelation of the vanadium and carbon contents was not considered as a prime factor. The carbon content was held at 1.2 per cent or less-generally at the usual 0.65 to 0.75 per cent.

Jan 1, 1932

By Kenneth Robertson

THERE is probably less known of this subject than of any other connected with the metallurgy of iron. In all the books that treat of this matter, there ore given analyses of slags, their chemical formulae, the loss of iron, etc. ; but few, if any, give the character of the iron mode at the time; none give analyses and physical characteristics of the ores and limestones used, and they present merely isolated examples from various furnaces, and consequently one is more frequently puzzled than enlightened after reading them. During two years I have had occasion to analyze the slags and many of the pig-irons from two furnaces, and for this article I hove made analyses of all the different grades of pig mode by them. A

Jan 1, 1873

By Guy R. B. Elliott

If chemical mining is to work, it is extremely important to watch heat balances. Some reactions with coal give off heat and others absorb heat. The reactions of coal with oxygen or air give off heat, but the reactions of coal with steam or with carbon dioxide absorb heat. By balancing the proportions of the two types of reactions, the energy of the coal can be almost completely recovered and environmental damage is minimized. The chemical reactions are listed in Table 1 in the usual form with subscripts (s) and (g) indicating solid or gaseous materials. In reaction 1, solid corbon, C(s), reacts with gaseous oxygen, O2(g), to produce gaseous carbon dioxide, CO2 (g). H means enthalpy or available heat in the material; F is free energy, and it measures whether the reaction can go at all, and if so, how much.

Jan 9, 1973

By W. Laird

For years, the coal industry has been confronted with face ventilation problems, ignitions, dust, and their effect on productivity. To improve face ventilation, minimize face ignitions, and control dust in the face areas, studies have been conducted over the past 30 odd years by coal companies, federal government research programs and others. These studies included brattice curtains, water spray nozzles, water pressures, highly efficient water filtration systems, auxiliary fans, differ fans, various dust collection systems and the recently developed "Spray Fan" ventilation system. This system consists of spray banks strategically placed on continuous miners to ventilate immediate face area.

Jan 1, 1984

By Cuppam Dasarathy

THE object of this note is to report briefly certain results of investigations on the Fe-In phase diagram. BISRA-high purity H-iron and 99.9 pct pure indium were used to prepare the alloys. The experimental techniques consisted of thermal analysis, optical metallography, and X-ray diffraction. A phase diagram based on the present results as well as those reported earlier by the author' is shown in Fig. 1. It is seen that the liquidus points fall on a smooth line which meets the monotectic isotherm at 1470°C. The liquidus extends up to 3.4 at. pct In. The phase boundary separating the two liquidus L1 and L2 is shown dotted. The experimental solidus meets the monotectic isotherm at -0.9 at. pct In. The 6/6 + L2 boundary drops steeply to the 6 + La/y + L2 boundary at -1350°C. In this region, it is impossible to detect satisfactory thermal arrests because of the steep phase boundary. The present diagram shows that indium lowers the temperature of the d/y transforma-tion and raises the temperature of the y/a transfor-mation. The y +d region is found to be very narrow. Indium gives rise to a restricted y field when alloyed with iron. The width of this field is between 0.4 and 0.5 at. pct In. Details of the alloys containing 40 and 50 at. pct In have already been reported by the author' and the transformation temperatures of these alloys are included in Fig. 1. It appeared from optical metallography and X-ray diffraction that the room temperature solubility of indium in a iron is less than 0.28 at. pct since alloys of 0.28 at. pct In and above, slow cooled to room temperature, contained dark etching second phase particles situated both in the matrix and grain boundaries of the a-grains, see Figs. 2 and 3. These particles were identified to be unalloyed indium by X-ray diffraction. The lattice parameter of the a phase reached a maximum of 2.8672A at the indium level of -0.28 at. pct. The present diagram, Fig. 1, is in substantial agreement with that of Stadelmaier and Fiedler' except for certain differences in detail. For example, they found the monotectic composition and temperature to be 7.0 at. pct In and 1443oC, respectively, while the present work indicates them to be 3.4 at. pct In and 1470°C. The 6 + L2/y + L2 transformation is indicated in the present work to occur at -1350°C, whereas Stadelmaier and Fiedler find this to occur at -1320°C. They also claim that the width of the y field is 0.2 at. pct In while the present work shows the width to be between 0.4 and 0.5 at. pct In. 1) Indium, when alloyed with iron, gives rise to a restricted y field, the width being >0.5 at. pct In.

Jan 1, 1970

By R. R. Webster, H. T. Clark

I. A. Sirel—I would like to ask Mr. Sims what would the preferred hot metal analysis be as far as manganese and silicon are concerned if you used specially made iron for this process instead of basic iron. C. E. Sims (authors' reply)—A preferred composition would contain somewhat less silicon than the basic pig iron used in these experiments. High silicon requires a large lime addition. Lime must be added in sufficient quantity to neutralize the silica formed and to leave an excess for dephosphorization. Manganese presents almost no problem in operation. It is almost completely oxidized and, in burning, develops considerable heat. The evidence indicates, however, that, in continuous commercial operation, there will be an excess of heat produced, and the bath will need to be cooled in some manner as by the addition of scrap or by utilizing the energy for the direct reduction of ore. There do not seem to be any serious limitations on composition of pig iron. One heat was made with an iron containing 2.27 pct silicon and the phosphorus finished at 0.007 pct. In another, the iron contained 0.45 pct phosphorus which was lowered to 0.019 pct. This indicates considerable leeway in composition. D. R. Loughrey—We are all very much interested in the recent discovery of very large deposits of iron ore both in Labrador and in Venezuela. I would like to ask Mr. Sims if the iron ore at either or both of these places is such that it would lend itself to the manufacture of iron suitable for use in the turbohearth. C. E. Sims-—According to my information, those ores are not essentially different from ores now used in this country for making basic pig. They should, therefore, be adaptable to this process. D. I. Brown—You have spoken about the leeway, or spread in analysis of the various irons you can use in the vessel. I would like to have you tell us, if you can, about the different kinds of steels which can be made in such a vessel. The turbohearth process, or it might more aptly be called pneumatic openhearth, is a little different from that used in most Bessemer shops and in the one in which I worked. If we had a blow in the air over 10 min, the boss was in the pulpit in a hurry

Jan 1, 1951

By Tracy L. Atherton

The mapping of slant-hole oil fields is complicated by the fact that relationships between wells are subject to variations in three dimensions and are not readily adaptable to representation on a plane surface. Formalized perspectives usually expand into an undecipherable maze of lines and peg models with the necessary supporting dividers serve only to awe the beholder with their perplexity. The usual compromise arrived at is a plotting of the projection of the courses of all of the wells in the field onto a horizontal plane (Fig. I). These complicated plots, when used in conjunction with the individual vertical projections of the wells, heretofore have been the most practical foundation for the study of general field problems. This method has many shortcomings, however, which arc not found in the recently developed straight-hole equivalent projec-tion method. The new method supplies a series of maps similar to the type now in common use in straight-hole fields. It is remarkably simple to use and supplies a ready check on clearances between wells. Perhaps the method can best be understood if the steps that led to its development are described. Common practice of oil-well surveyors is to supply the owner with a tabling of the survey and a plan view plotted against the true meridian. If a vertical projection is plotted, it is usually plotted separately and shows vertical depths against the projection of the stations along a section line joining the top and bottom of the hole on the plan view. A more practical method would be to plot the section line of the plan parallel to the abscissa of the vertical projection (Fig. 2). If this is done, any line parallel to the "base line1' will pass through the points on each projection that represent a single point in the hole. Another very useful graph, which the well surveyor could provide, would be plotting of vertical depths against measured depths. Fig. 3 illustrates the next step facilitated by this form of plotting. The lines designated "well A" represent the proposed course of a hole to be drilled. Superimposed on the drawing, in its proper relative position, is the plan view and a portion of the vertical projection of a present producer, well B." From an inspection of the plan view we arrive at the correct conclusion that the only indicated possibility of collision is at the point of crossing of the wells on the plan view. Referring to the vertical projection, note that the vertical depths of stations on B, in the vicinity of the crossing, are plotted on the same plane of projection as A. The clearance is the indicated distance between the two vertical sections measured along the parallel to the "base line," which passes through the point of intersection of the plan view. Repeat this process for the other wells crossing the proposed course of A on the plan view and you have a preliminary check of clearance for the proposed course. A similar comparison of crossings on the vertical projections of all >

Jan 1, 1941

Jan 1, 1931

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.''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 worke1s3'4 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 Robert Glass Cleland

THE THIRD and most important item on the Phelps Dodge agenda for the development of new ore supplies involved the site of the company's initial venture into Arizona, the old mining camp of Morenci. By the purchase of the Arizona Copper Company's holdings in 1921, Phelps Dodge had obtained control of virtually the entire Morenci district, including town, public utilities, and, above all, the huge mineralized area that had once been divided between numerous competing companies. Because of this rigid concentration of ownership in the hands of one organization, Phelps Dodge was able to plan and successfully carry out a program of greater magnitude than any Arizona mining company had previously under- taken. The immense deposit of low-grade ore, usually referred to as the Clay Orebody, had been known to the mining companies of Morenci for many years. Pioneer exploratory work, both by the Arizona Copper Company and later by Phelps Dodge, revealed that the deposit, mostly of light-gray porphyry rock, lay under a hard capping from two hundred to five hundred feet thick. An intensive drilling

Jan 1, 1952