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By R. T. Webber, B. B. Owen

THE vapor phase deposition of molybdenum and tungsten from the hexacarbonyls has been thoroughly investigated by Lander and Germer1 and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2.3 could be similarly deposited, but did not investigate this metal extensively. Recently,4 conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. APPARATUS AND TECHNIQUE The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T2 and T3 containing crystals of the carbonyl. T2 is kept in a constant temperature bath (not shown), while T3 is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Ss, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by S5 is used to determine the volume included by S4, S6, Se, S10, the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: I, the specimen temperature, from room temperature to about 1000°C, 2, the carbonyl vapor pressure, from 40 to 220 microns, and 3, the hydrogen flow. In several runs, 0.8 to 1.8 pct of hydrogen sulfide was introduced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1948

By HAROLD VINTON COES

MANAGEMENT has been tersely defined as getting things done through the efforts of other people; but before we proceed further, let us distinguish between administration, management, and organization. Oliver Sheldon in his book, "The Philosophy of Management," offers the following definitions: Administration is the function in industry concerned in the determination of the corporate policy, the co-ordination of finance, production, and distribution, the settlement of the compass of the organization, and the ultimate control of the executive.

Jan 1, 1943

By Robert P. Burrows

In preparing this paper the object has been to set forth facts relating to illumination problems, which, judging from the results realized in the iron and steel and other industries somewhat similar to mining, will tend toward furthering safety, production, and contentment of employees, as well as economy of operation in mines. By applying the principles of illumination with the assistance of modern appliances, the full benefits in efficiency may be derived from improvements already made in other details of mine operation. The lighting of a typical coal mine may be*divided into four distinct parts: 1, The lighting of the buildings about the top; 2, the lighting of the working faces; 3, general illumination at the bottom; and 4, special applications of lighting. The lighting of buildings about the top may be treated in the same manner as that of any other industrial plant, for we have a boiler room, an engine and generator room, a forge, a machine shop, and a hoist room. These can be well and efficiently lighted by the use of 100-watt tungsten-filament multiple lamps with proper reflectors so spaced and suspended that a power consumption of from ¼ watt per square foot in the boiler room to 1 watt per square foot in the machine shop is obtained. The methods that apply to this kind of lighting have been ably treated by a number of authors,' and for this reason a detailed discussion is unnecessary. The lighting of the working faces is usually done by means of portable lamps, of which there are four types in use: The oil torch, the acetylene Iamp, and the oil and the electric safety lamps. The different types have been fully described in numerous papers and articles and will not be covered here, although a few figures on the cost of operation will no doubt be

Jan 1, 1916

By Wilbert G. McBride

Two Also 3 1/2-ton motor trucks were used by Young Bros. while operating at the Mammoth Collins mine at Shultz, Ariz. One was equipped with an oil tank holding 1,075 gal. and was used for the transportation of "tops." The other was fitted with a stake body and used to carry machinery, wood, rails, pipe and all classes of miscellaneous supplies. The bodies were made of oak with maple flooring and were attached to the frame of the chassis by U-bolts, to avoid drilling the main members of the frame. Most of the hauling was done from Tucson, a distance of 47 1/2 miles. During the first 3 months, part of the road was in very bad condition and the tire cost was excessive. After this part was repaired the road was in fair condition, but never good. There were no excessive grades or bad sand, but wagon ruts, too narrow for the truck wheels and of a different gage, caused heavy tire loss; while chuck holes, sharp curves and stones, both imbedded and loose, were objectionable features. During wet weather the trucks could not get sufficient traction to climb some of the hills and were likely to stick in the mud in certain places, so that no attempt was made to run them unless they were on the' road when the rain started. This lost time amounted to about 5 per cent. of the total, but, whenever possible, it was utilized in making minor repairs. The price of gasoline was from 17 to 21 c. per gal. Rubber tires were used throughout. Drivers were said $4.50 to $5 per shift, and a return trip to Tucson was counted as two shifts even when made in one day. Drivers were provided with a room in Tucson and were paid for a11 time lost due to causes beyond their control. Trucks were loaded one way only. Speedometers were placed on both trucks but the excessive vibration soon caused them to fail. For this reason, and because no account was taken of the distance covered in picking up a miscellaneous load or in other minor ways, the mileage given is under the actual distance traveled. Some of the weights had to be estimated, but care was taken to have the number of ton-miles low rather than high, to avoid underestimating the costs. The cost of hauling from Tucson to the mines was $12 per ton

Jan 1, 1917

By Ellsworth Daggett

Jan 1, 1879

By D. E. Stephenson. Discussion by R. G. K. Morrison, L. Obert

R. G. K. Morrison (Chairman, Dept. of Mining Engineering and Applied Geophysics, McGill University, Montreal, Que., Canada) - The discing of drill core has been a recognized pressure phenomenon for many years but only recently has an interest been taken in the mechanism involved. The work of Jaeger and Cook is referred to in the text. The authors have now advanced the study to establish, within certain loading limitations, a direct relationship between axial and radial stress at failure. This is an important contribution. In mines generally, where pressure conditions result in the spalling of openings, the faces of drifts and crosscuts, on scaling, usually show a concavity with respect to the opening very similar to the face of the drill hole after the separation of the stub. The same holds for shaft sinks. This suggests a similarity between the mechanism of the discing of core and that of the spalling of an opening, under pressure, to develop a more stable outline. The latter, commonly regarded as shear, is the most conspicuous type of failure observed in

Jan 1, 1967

By Earl H. Miller, Henry H. Bruhn

COMMERCIAL beds of sylvite ore were discovered by the Snowden & McSweeney Co. while drilling a wildcat oil well some 25 miles northeast of Carlsbad, N. NI., in 1925. After a preliminary core drilling program the U. S. Potash Co. sank a 1060-ft shaft within 4 miles of the original discovery. This shaft was in an isolated location in a sand desert area with only the roughest of dirt roads connecting it with the neigh- boring town of Carlsbad some 21 ½ miles west.

Jan 6, 1954

By J. P. Carson

The works of the Tula Iron Company are in the Republic of Mexico, State of Jalisco, twenty-eight leagues southwest of Guadalajara, ten leagues northwest of the town of Sayula, through which passes the projected line of the Mexican National Railroad. Its geographical position would be about: latitude, 20' 10' N., longitude, 40 35' w. of Mexico City. The surrounding country is a rolling plateau, 6000 feet above the sea, enjoying the most magnificent climate in the world, the average temperature being about '70'. The works were commenced in 1850 by a company with very small capital, having not the least idea of the undertaking. They soon fell into the hands of the money-lenders, and after changing

Jan 1, 1879

By Paul M. Tyler

MILITARY power stems from industrial power and industrial power in turn depends predominantly upon an ample and assured supply of mineral raw materials. It thus becomes the duty of mineral economists to collate the vast array of data and logical deductions in order to reach an unemotional judgment as to the ability of the Soviet economy to withstand the strain of prolonged military action on the modern scale. Russian publications, reports: and official speeches have been laboriously screened and analyzed. Since these are the sources of information for the lower echelons of the Soviet industrial organization itself, they carry factual data that can be pieced together to show the present-day pattern. Apparent contradictions and obvious distortions or omissions can often be rationalized on the basis of observations made by foreign engineers and consultants during the 1930'5 and by checking against the technical literature published before even so-called technical articles were riddled by bombastic and presumptuous claims.

Jan 6, 1951

By S. W. Miller

Most of the steel welding done at the present time is in material containing not over 0.3 per cent. carbon, and the tests here described were in similar material. These tests are not as yet completed but it is hoped that more results and more reasons for the conclusions may be presented at the meeting in February. From the time the author found the peculiar structure in electric welds referred to in a previous paper,' that is, needles or plates in the grains and similar material, in larger spots, at the grain boundaries, he has felt that these plates which may be iron nitride and probably contain some carbon, were at least partly responsible for the brittleness of electric welds. He has found but few traces of similar lines in oxyacetylene welds until the last 2 mo., he has since found large numbers under certain conditions. In the top of these welds, they are quite numerous. In the body of heavy oxyacetylene welds, they appear at times, but not nearly to the extent that they do in electric welds; the author has never seen them in the body of welds in material less than % in. (19 mm.) thick. They are shown in Fig. 82. The reason they were not noticed before is undoubtedly due to the fact that in making tests of welded pieces the weld was always ground off level with the plate, and as this structure only appears in the top 1/16 in (1-5 mm.) of the weld, they were removed by the grinding or machining; also, welds 3/4 in. thick had not been examined. It did not appear, in making bending tests, that this structure had much influence on the strength of oxyacetylene welds; while electric welds are noticeably brittle. Further, oxyacetylene welds made with certain special materials were exceedingly brittle even after the tops of the welds were removed; this was true in cases where there was no sign of the plates whatever and where the welds were remarkably free from oxide and the other usual defects. It appeared, therefore, that this brittleness did not depend on any variable that had been noticed so far, and it was decided to find where the rupture occurred in various kinds of welds made

Jan 1, 1920

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE ST. Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 12, 1918

By Roman Y. Poderny, Vladimir V. Rjevskii

In the USSR, the Moscow Institute of Radio Electronics tronics and Mining Electro-Mechanics (MIRGEM) has started what it hopes will become a nationwide movement to educate mining students in the precise specialties that industry has come to require. Courses for mining engineers, the MIRGEM faculty proposes, should dovetail as exactly as possible with specific jobs available in the mining profession. Acting upon this thesis, MIRGEM revised its own curriculum in 1962 and has since presented an over-all plan for Soviet mining education before two mining school conferences as well as the Ministry of Higher Education and a number of major Soviet industrial ministries. The plan was universally approved with some suggested revisions. SOVIET MINING EDUCATION TODAY At present, mining education in the Soviet Union covers the exploitation of solid minerals and raw materials, including coal as well as ferrous and nonferrous metals. The extraction, storage, and refining of oil and gas is treated as a separate discipline. In all, there are 33 Soviet universities and institutes that train mining engineers for careers in the industrial, research and educational fields.

Jan 9, 1966

By Theron Wasson

The year 1942 in Michigan was devoted largely to the development of fields discovered in 1941 but was also characterized by a great increase in prospecting for new productive horizons below the Dundee limestone. Some new fields were discovered but as yet these have shown few signs of being of major importance. Michigan's total production for 1942, of 21,754,000 bbl. of oil, as reported by the U. S. Bureau of Mines, was second only to the record year of 1939 when 22,799,000 bbl. of oil were produced. All important fields were prorated throughout the year, and it is obvious that without proration a new all-time high would have been established for the state this year. From 1925 to the end of 1942, Michigan has produced annually the following amounts of oil: Year Barrels Source 1925 4,000 1926 94,000 1927 435,000 1928 592,000 1929 4,641,000 1929 Michigan Geological Survey 1930 3,928,000 3,785,000 1932 6,925,000 1933 7,942,000 1934 0,603,000 1935 15,776,000 U.S. Bur. Mines, 1937 1936 11,928,000 U.S. Bur. Mines, 1938 1937 16,628,000 U.S. Bur. Mines, 1939 1938 19,211,000 U.S. Bur. Mines, 1938 1939 22,799,000 1940 19,764,000 1941 16,361,000 1942 21,754,000 Total 183,170,000 This tabulation shows the steady growth of the industry in Michigan since the first discovery of oil in 1925. Maes A map of the oil and gas fields of Michigan in 1941, published in the report for 1942, shows the main producing areas and should be referred to if information in regard to their location is desired.* The main producing zones were shown in the columnar section in the same publication. Development in Fields Reed City Field.—During 1942 the Reed City field, which ended 1941 with 112 producing oil wells, added 70 new producers to bring the total at the end of the year to 182 wells and 4700 proven acres. A south extension of the field developed during the year was in large part responsible for the increase. Approximately 9,000,000 bbl. of oil was produced from the field during the year, bringing the total accumulated production to the end of the year to roughly 11,750,000 barrels. Headquarters Field.—The Headquarters field, which started the year with ro producing oil wells, ended the year with 41 wells aid 1240 proven acres. Approximately 2,300,000 bbl. of oil was produced in 1942. Kawkawlin Field.—Although not a 1941 discovery, the Kawkawlin field has been actively developed on the 40-acre spacing plan during the last year, 42 producers having been completed, bringing the total number of wells at the end of the year to 77. Nearly 500,000 bbl. of oil was produced during the year.

Jan 1, 1943

By Theron Wasson

The year 1942 in Michigan was devoted largely to the development of fields discovered in 1941 but was also characterized by a great increase in prospecting for new productive horizons below the Dundee limestone. Some new fields were discovered but as yet these have shown few signs of being of major importance. Michigan's total production for 1942, of 21,754,000 bbl. of oil, as reported by the U. S. Bureau of Mines, was second only to the record year of 1939 when 22,799,000 bbl. of oil were produced. All important fields were prorated throughout the year, and it is obvious that without proration a new all-time high would have been established for the state this year. From 1925 to the end of 1942, Michigan has produced annually the following amounts of oil: Year Barrels Source 1925 4,000 1926 94,000 1927 435,000 1928 592,000 1929 4,641,000 1929 Michigan Geological Survey 1930 3,928,000 3,785,000 1932 6,925,000 1933 7,942,000 1934 0,603,000 1935 15,776,000 U.S. Bur. Mines, 1937 1936 11,928,000 U.S. Bur. Mines, 1938 1937 16,628,000 U.S. Bur. Mines, 1939 1938 19,211,000 U.S. Bur. Mines, 1938 1939 22,799,000 1940 19,764,000 1941 16,361,000 1942 21,754,000 Total 183,170,000 This tabulation shows the steady growth of the industry in Michigan since the first discovery of oil in 1925. Maes A map of the oil and gas fields of Michigan in 1941, published in the report for 1942, shows the main producing areas and should be referred to if information in regard to their location is desired.* The main producing zones were shown in the columnar section in the same publication. Development in Fields Reed City Field.—During 1942 the Reed City field, which ended 1941 with 112 producing oil wells, added 70 new producers to bring the total at the end of the year to 182 wells and 4700 proven acres. A south extension of the field developed during the year was in large part responsible for the increase. Approximately 9,000,000 bbl. of oil was produced from the field during the year, bringing the total accumulated production to the end of the year to roughly 11,750,000 barrels. Headquarters Field.—The Headquarters field, which started the year with ro producing oil wells, ended the year with 41 wells aid 1240 proven acres. Approximately 2,300,000 bbl. of oil was produced in 1942. Kawkawlin Field.—Although not a 1941 discovery, the Kawkawlin field has been actively developed on the 40-acre spacing plan during the last year, 42 producers having been completed, bringing the total number of wells at the end of the year to 77. Nearly 500,000 bbl. of oil was produced during the year.

Jan 1, 1943

By Leo F. Reinartz

This is the fourth and final installment of Leo Reinartz' summation of the steelmaking industry over the first one hundred years. ALTHOUGH basic open-hearth steel has been in the limelight for many years, it has had to share some of its glory with two lesser but nevertheless important rivals, one 50 years old and one a rejuvenated process. Electric steel Electric-steel manufacture began in a humble way in the United States in 1906, when the first heat was tapped from a 3-ton Heroult electric furnace at the Halcomb Steel Co., Syracuse, N. Y. During the intervening years, it has completely eliminated the crucible process. For many years electric melting furnaces were located predominantly in relatively small, nonintegrated plants, making all kinds of high-grade alloy steels. Most of these furnaces, with capacities ranging from 5 to 20 tons, had basic bottoms. During and after World War II, many large basic electric furnaces, some up to 200 tons in capacity, were installed in integrated plants to make commodity steels. There were several reasons for building electric furnaces. Capital investment per annual ton of capacity was low and furnaces could be installed quickly. Since these furnaces used mostly scrap iron in the charge, no extra expensive coke- and blast-furnace capacity had to be added. The perfection of the top-charging design, and the development of large transformers and furnaces, made possible tons per hour as high as from modern 350-ton. open-hearth furnaces. Electric furnaces have high availability and repair costs are low. The process is flexible. Alloy and plain carbon steels of high quality can be made. Where power costs are low, the operating cost can

Jan 1, 1961

THIS chapter and the one following deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the simplification of the first two ' laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the "heat balance" of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced, and we assume that the cause lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities of flow distribution, air leakage, etc., present in any real, open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained- by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot-metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million B.t.u. per net ton. of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million B.t.u., and the sensible heat in the preheated air at the port ends is 117 million B.t.u. so that the total heat input at the ports is 477 million B.t.u. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million B.t.u., but 120 million of this is supplied by the heat in the hot metal and by various heat--evolving reactions in the bath, so that only 75 million B.t.u. need be supplied to the bath by the flame.

Jan 1, 1944

By Robert Anderson

ROUGHLY, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term; it connotes the contraction in volume of a metal or alloy on passing from the liquid to the solid state. Pattern-makers' shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of, sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring tempera-tures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment and technical knowledge of men experienced in the production of castings.

Jan 10, 1921

By R.J. Anderson

Roughly, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term and refers to the contractio~l in volume of a metal or alloy on passing from the liquid to the solid state. Patternmaker's shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring temperatures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment, and technical knowledge of men experienced in the production of castings.

Jan 1, 1923

By R. J. Anderson

Roughly, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term and refers to the contractio~l in volume of a metal or alloy on passing from the liquid to the solid state. Patternmaker's shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring temperatures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment, and technical knowledge of men experienced in the production of castings.

Jan 1, 1923

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964