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By C. E. Murphey

C. E. Murphey, Jr., has presented a relevant, simplified comparison of drill string response when drilling with and without bumper subs. His point that drilling without bumper subs gives conditions further from resonance is valid. Thus, drilling from a floating vessel without bumper subs is undoubtedly feasible, especially when the heave motions of the drilling vessel are small. When these heave motions become large, an evaluation of the magnitude of the change of bit weight is a requirement for a realistic comparison between using and not using bumper subs. As Murphey states, this evaluation should include the effects of damping and presence of drill collars. The analysis would be similar to that presented in our Appendix, but is far beyond the scope of this Reply. ***

By Eduardo Martinez Baca

Although Mexico has always been justly considered by the whole world essentially a mining country, this reputation is due principally to the richness of the deposits which have been worked. In reality, the majority of the States have been little

Jan 1, 1902

By G. W. Thompson

G. W. THOMPSON,* Brooklyn, N. Y.-This subject has two aspects, neither of-which can be ignored: these are the economic aspect and the technical aspect. Under ordinary conditions, economic law will take care of the conservation of tin. Under present conditions it seems desirable that economic law should still be permitted to operate as far as is practicable. It is true that this law operates rather slowly, and that under war conditions it cannot be depended upon to give our Government the supply it immediately needs. There should, therefore, be a designation of the essential industries by the Government, and tin should be supplied for those needs, letting the non-essential industries take what is left. At the same time, information ought to be forthcoming as to how tin can be conserved; with tin selling at 80 c. per pound, more or less, it is to the interest of every consumer to get the best information he can as to how he can save tin. Economic law would properly punish those who do not study their own interests in this way. I deprecate, therefore, any centralized socialistic effort toward avoiding penalties through failure to observe and obey economic law. In saying this, however, I am not unmindful that it is desirable for our Government to take such control of the tin situation as may be necessary to the prosecution of the war, practically regardless of the effect of such action upon individual industry, which should studiously seek to adjust itself to the new condition. The Government should promulgate such technical information as it can collect, showing how tin can be conserved, and should urge upon every consumer the exercise of his common sense in self-protection. There is very little danger of any one attempting to hoard or corner tin, in the present state of the market. Most consumers will be glad to live from hand to mouth, covering their sales by purchases, or vice versa. As to the technical aspects: Tin and tin alloys are used to give certain practical and also certain artistic results. The practical factors are those involved in proper adhesion, continuity of surface, protection, the right degree of hardness, proper working qualities, etc. The artistic results are those that appeal purely to the eye or to our cultivated sense of what is desirable. There is no doubt that a great deal of tin could be saved if there were not a demand for certain pleasing effects. How can this saving be brought about? The users of tin hearing alloys are not the only ones involved in this question. The manufacturers of solder and babbitt have for a long time sought to give certain appearances to their fabricated bars and ingots in order to make them more salable. The user of a solder is very apt to judge of its working qualities by the appearance of the bar; the same thing is true with regard to babbitts. Under ordinary conditions, manufacturers are justified in trying to

Jan 12, 1918

By James P. Munroe

Appalling as has been the loss of life in the last 51 months, there is one slight compensation: no longer will there be in the world a cripple, in the old meaning of the term. Men handicapped by wounds or disease, there will be, unfortunately, and in numbers beyond what the world has known since the wars of Napoleon; but neither they nor the industries from which they were called off to war will be "crippled" in the sense in which both would have been had mankind not learned the lesson of conservation and come to understand that the most important field for such conservation is not in the forests and the mines but among men and women. From the beginning of the Great War, France, Great Britain, Belgium and most of the other Allies have studied the problem of restoring the soldiers and sailors injured through war to physical and economic efficiency; and from their experiences, especially from that of Canada, the United States has learned much. Consequently, our task of preparing for the return of our disabled men has been easier and, in some ways, more comprehensive than theirs. Complex as are the details of the machinery which the United States has set in motion to take care of the men injured by wounds or disease, the plan itself is simple. Taught by European experience, the Surgeon-General of the Army and the Bureau of Medicine and Surgery of the Navy have provided, on both sides of the Atlantic, every known surgical and medical facility for restoring the injured or diseased man to a physical condition as nearly normal as possible. While in the hospital in Prance or England, on the transport coming to America, and in the hospital here, the disabled man is incited in every way to believe in his future efficieney, to want to be a normal worker, to desire to retake his place in that society of workers from which he went, temporarily, to do the greater work of preserving civilization. Furthermore, since purposeful occupation is now regarded as an essential form of treatment with most men in the hospital, especially in the convalescing stage, many of these men will have been actually started on the road to earning before they are discharged from the army surgeon's care.

Jan 1, 1919

By L. A. Delano

DURING 1916, the St. Joseph Lead Co. milled 2,505,670 tons of ore. This is a daily operating average of 7855 tons. The economic concentration of such a large tonnage necessarily requires a plant equipped with modern machinery and operated efficiently. The milling process used in producing this output has been a gradual development through the long period of years that the company has been in existence. HISTORICAL SUMMARY OF MILLING PRACTICE Ore was first mined at Bonne Terre, Mo., in 1864. The early milling practice was crude. It consisted of breaking the ore into small pieces by hand, pulverizing in a Blake crusher and a pair of Cornish rolls to approximately minus 6 mm., and jigging in the old-fashioned hand jigs. Only the coarse heavy galena was saved, the gangue being shoveled off and discarded. The output for the first year under this method was only 240 tons of pig lead. The first mill of the company was a combination of extensions and additions built from time to time as the mines developed. It was a museum of early mulling machinery, such as jigs, percussion tables, huddles, dolly tubs, log washers, etc., following no definite flow sheet. The chats, or tailings, were hauled to waste dumps by mule and ox teams, as much as 500 tons per day being moved in this manner, until a railroad was built in 1880. This mill was burned in 1883, at which time the annual output had reached approximately 7300 tons of pig lead. A new mill of 500 tons capacity was designed and built by C. B. Parsons. This mill has been admirably described by H. S. Monroe.1 The ore was crushed in Blake crushers, Cornish rolls, through 6-mm. screens, and treated by jigs of the Parsons type, percussion tables and log washers, or trunking machines, for cleaning the galena. The middlings were recrushed in rolls and treated on Harz jigs. The mill was operated without change, except later installing Gates crushers and en-

Jan 9, 1917

By J. A. Herbst, D. W. Fuerstenau

The effect of mill speed and ball load on the dry ball milling of dolomite is examined in the context of the batch grinding model. Observed changes in the parameters of the model are interpreted, as far as possible, in terms of the mechanics of particle motion in the mill. A parameter estimation scheme previously proposed by the authors is shown to provide the basis for a successful simulation of grinding behavior over a wide range of mill speeds and ball loads. Finally, a combination of experimental and simulated results is used to determine the optimum mill speedball load for closed circuit grinding in this mill-material system.

Jan 1, 1973

By George R. Mansfield

Interest in the reserves of phosphate rock in the United States and their proper conservation has recently been aroused by hearings held in different parts of the country by the "Joint Committee to investigate the adequacy and use of phosphate resources of the United States." This committee was appointed within a few days after a Presidential message to Congress on the same subject, dated May 20, 1938, and began to function almost immediately. Hearings were held in Washington, D. C., Pocatello, Ida., Wilson Dam, Ala., Knoxville, Tenn., and Lakeland, Fla. The resulting testimony, when published, comprised a volume of 1182 pages.l At the earlier hearings held in Washington and Idaho the seeming disparity between the great reserves of the West and the smaller reserves in the East led to some suggestions as to the desirability of curtailing or even prohibiting the exportation of phosphate rock so that eastern producers, becoming alarmed, cooperated in making available for the use of the committee information hitherto closely guarded. This information has provided an opportunity for new studies by official agencies, for a restatement of the reserves of Florida and Tennessee, and for some modification of figures for the Western States. The writer, representing the Federal Geological Survey, was given free access to the Florida material and has prepared for publication a report,² some features of which are summarized in this paper. The Tennessee material was studied by Dr. G. I. Whitlatch,³ of the Tennessee Division of Geology. Prof. J. Stewart Williams,* of the Utah State Agricultural College at Logan, has published a recent study of the phosphate resources of Utah and the writer has given some further study to reserves of western phosphate from the viewpoint of including material of lower grade than that hitherto considered. Technologic advances in the phosphate industry must be credited with a large share in the expansion of reserves by making available for

Jan 1, 1942

By F. Louis Grammer

The iron industry has been so markedly the cynosure of all eyes, that a sense of weariness has overtaken many on-lookers, and a new wonder is desired. While the commercial phase of the iron industry has necessarily engrossed the public attention and probably is the more worthy of record, still the mechanical and metallurgical phases have recorded conspicuous advances and merit attention. In order to appreciate the present condition of blast-furnace practice, it is necessary before enumerating the advances made during the past decade to give a brief discussion of the tendencies in the methods of administration as well as the conditions governing supremacy, for these factors have modified the aims of the manager. It might also be well to apologize for a record of the advances made during such a short period as a decade, were it not that, for the individual, time is marked as much by the impressions recorded on the brain as by the jumps of the second hand of a watch. Furthermore, this article is written in order to carry out a project of the late Dr. Egleston, to have a record made each decade. I regret that the data collected by him, and forwarded to me, end with 1896, and therefore do not include the interesting results which followed the introduction of Mesabi ores. The perusal of the notes is melancholy reading, somewhat like the feelings we experience in going through a graveyard. It is a record made up of so many plants, which have ceased to be factors in the iron world, if they are not entirely moribund. Historically, they would be interesting, emphasizing as they do the abnormal and somewhat overestimated importance of furnace lines, taken without proper reference to volume of blast and nature of stock used. I regret, however, that the time at my disposal does not permit of this presentation.

Jan 1, 1905

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By Carl Henrich

A.. S. DWIGHT, New York, N. Y.-Mr. Henrich's paper is rather inconclusive as to the role that alumina really plays in slags. He gives a number of interesting instances of high alumina, with conclusions that he draws from the analyses, in the light of what he knows of the accompanying conditions, but the information given is hardly sufficient to permit intelligent criticism of these conclusions, for it is well known that the slag composition is not the only factor that can produce some of the furnace results favorable or disastrous, as the case may be, which he records. As a matter of fact, most metallurgists who have wrestled with this problem in connection with the smelting of lead and copper ores, usually arrived at some sort of a working hypothesis which met the local conditions fairly well, and then, being busy men, were inclined 'to leave the theoretical question very much as Mr: Henrich leaves it when he says: "A question with which I purpose dealing at some future time." It is unfortunate that in the Golden Age of the smelting industry in the West, when we were all dealing with large tonnages of complex ores, often containing large percentages of alumina in combination with other. refractory elements, the smelting companies were not generally equipped for research as they are today, and much experience that might have been,

Jan 4, 1917

By C. S. Smith

The solubility of tantalum at 1100°C is 0.025 pct in pure copper, 1.2 pct with 20 pct Ni, and 2.7 pct with -30 pct Ni. The solubility decreases with temperature, and the alloys are precipitation hardenable. A 79/20/1 Cu-Ni-Ta alloy reaches maximum hardness after aging at about 750°C and, if cold worked, does not recrystal-lize below that temperature. The alloys have good tensile properties at moderately elevated temperatures and, since they can be hot and cold worked nearly as easily as cupronickel, they are suggested for service at temperatures above the usual limits for copper alloys. MASSIVE tantalum dissolves extremely slowly in copper-rich alloys, and tantalum powder forms refractory surface layers which prevent its solution unless special precautions are taken. After many trials, an 80 pit recovery was consistently obtained by using a mixture of a finely divided tantalum powder with two or three times its volume of potassium tantalum fluoride (K2TaF1,-melting point about 750°C) poured in a slow stream directly on to the surface of the molten copper alloy, so that each particle would remain coated with flux and be immediately and individually wetted by the molten metal. A 50-50 nickel-tantalum alloy has a melting point of about 1400°C and small lumps of it slowly but satisfactorily dissolve in molten copper-nickel alloys as does commerical "ferro-tantalum." The high affinity of tantalum for carbon makes it necessary to avoid carbonaceous crucibles. COPPER-TANTALUM ALLOYS Castings with good shrinkage resulted when 0.1 pct Ta or more was added to copper melted under charcoal and cast in air. Copper in two-pound melts to which 0.1, 0.15, and 0.2 pct Ta had been added retained residual amounts, by analysis, of 0.025, 0.023 and 0.026 pct, respectively. The solubility of tantalum in molten copper at about 1200 °C is therefore about 0.025 pct. The electrical conductivity of these three samples was 100.48, 100.00 and 100.20 pct IACS in the annealed condition, and 98.24, 97.98 and 98.08 in the cold-drawn condition. Wires 0.080 in. in diam withstood from thirteen to nineteen reversed bends after annealing for 30 min in hydrogen at 850°C and the metal was therefore completely deoxidized. The annealing temperature corresponding to 50 pct loss of work hardness in 1 hr in a strip cold rolled 77 pct reduction was 175C, compared to 230°C for equivalent undeoxidized material. It is unusual for a decrease of recrystallization temperature to result from an alloying addition, and the tantalum probably combines with and removes some minor impurity in the original copper that restrained its recrystalliza- tion. No difficulty whatever was encountered in hot or cold rolling or drawing these ingots, and were tantalum not so expensive it would make an excellent deoxidizer for copper. COPPER-NIcKEL-TANTALUM ALLOYS Studies were made of the solubility of tantalum in a large number of copper-rich alloys, but of these significant solubilities were found only in the case of an iron alloy (which, however, separated into two immiscible liquid layers) and alloys of copper and nickel, in which tantalum is freely soluble and which were found to have interesting properties. The latter alloys are the subject of U. S. Patent No. 2,430,306 (1947). They are not at present available commercially. The Ternary Constitution Diagram—The copper-rich corner of the constitution diagram was constructed on the basis of microscopic examination of samples of various composition and treatments. The alloys were hot rolled to 0.25 in. from castings 0.625 in. thick, then annealed for 1 hr at 1000°C, quenched, cold rolled to 0.10 in. and finally annealed for various periods of time at temperatures between 800" and 1100°C in a nonoxidizing atmosphere and quenched. When the solid-solubility limit had been transgressed, particles of a compound believed to be Ni2Ta*were

Jan 1, 1960

Chairman, MRS. JESSE SCOBEY The Foreign War Relief Committee closed its dispensary fund during the past month with a contribution to the American Fund for French Wounded of $1720.51, balance on hand, principal and interest, as a gift from the New York Section of the Woman's Auxiliary for pressing emergency dispensary work in France. The American Fund for French Wounded was authorized to cable this sun at once, in consideration of the fact that their existing dispensaries, including the one established by the New York Section at Briey, were in excellent condition, while their mobile dispensary fund was confronted by the most urgent need for work among the refugees now returning in pitiable condition and in great numbers to certain distressing centers. The committee sewing at Fund headquarters every week has had seven working days, with an enrollment of twenty: The average attendance was ten; largest attendance for any one day, thirteen; smallest attendance, eight. Interest in this activity is growing steadily and it is the intention of the committee to push the work vigorously for the next few weeks.

Jan 3, 1919

By William J., Coulter

IN the early days of Colorado mining, between 1880 and 1900, when Leadville, Kokomo, and Robinson were boom mining camps, the entire area around Climax for a matter of fifteen miles was overrun with prospectors, so the mineralized outcrop at Climax was not unknown. The principal interest in minerals during this period was in gold, silver, and lead, and since the Climax outcrop showed none of these it drew little attention. Geology played an important part in bringing prospectors to the very edge of the Climax deposit. The Mosquito fault, which crosses near the base of Bartlett Mountain, continues as an important geological structure, at least as far as Leadville some twelve miles distant, and at the base of Bartlett Mountain the vertical throw on the fault is estimated to be between 2000 and 5000 ft. The sedimentary beds known to the Leadville district are all present on Bartlett Mountain to the north of the Mosquito fault, which cuts them off abruptly, and exposes the Pre-Cambrian rocks that underlaid them, so the prospectors, who were searching for gold, silver, and lead in the sediments

Jan 1, 1946

By W. E. Hess

At the Vesta mines of Jones & Laughlin Steel Corp. on the Monongahela River, 35 miles south of Pittsburgh, JCM Joy continuous miners and 6-SC shuttle cars are used for pillar extraction in the Pittsburgh seam. The entire output of the mine goes into coke production for blast furnace operation. Because this coal, which has high metallurgical qualities, is close to the place where it is ultimately used and because supplies with these properties are being rapidly depleted, complete recovery is essential wherever possible. With the introduction of the continuous miner into the Vesta mines, therefore, it was necessary to plan a project which would facilitate development and provide for future total recovery. Use of continuous miners under varying conditions has necessitated changes with regard to roof action, method of development, method of pillar attack, and innovations in mining. In the following pages these changes will be discussed.

Jan 2, 1955

Many of those who attended the meeting at Chicago spent the first part of the following week in Pittsburgh, when the Experiment Station of the Bureau of Mines was dedicated and the fourth annual First Aid and Mine Rescue Contests were, held. The Bureau buildings were open for inspection during the three days, Monday, Tuesday, and Wednesday. The dedicatory ceremonies were held in the Bureau of Mines main building, Monday morning, Sept. 29, Mr. T. J. Gillespie, representing the Pittsburgh Chamber of Commerce, presiding. In his address of welcome, Hon. E. V. Babcock, Mayor of Pittsburgh, said: "The reclamation work already done stands out conspicuously beneficial to industry and populace alike all over the United States. It has demonstrated methods of preservation of life and reclaiming of injured persons which are new and greatly beneficial to modern civiliza-tion. The establishment of this institution in Pittsburgh was greatly desired, and now it is here it is greatly appreciated." The response was given by First-Assistant Secretary of the Interior Vogelsang, who represented Secretary Franklin K. Lane. He said that the Bureau of Mines did more during the war for the triumph of American arms than any other institution.

Jan 11, 1919

By Bruce A. Kennedy

If it had not been for the persistent cold wind, the sun blazing out of a cloudless blue sky would have made it one of those warm, idyllic early spring days which attract the socalled "snowbirds" to Northern Mexico for a vacation at this time of year. At a drill site perched on top of a rather exposed mountain we were installing a number of borehole extensometers in diamond drill holes. A Threading Problem For the uninitiated in geotechnical instrumentation, a borehole extensometer is a series of anchors installed at various depths in a borehole, each anchor being independently connected by a tensioned wire to a measuring device set in the collar of the hole. Any movement of the rock at depth is detected by the anchors and transmitted by the wires to the measuring device. Flexible plastic tubing is used as a spacer between the anchors and the measuring wires are run up the inside of the tube. At this particular site we were installing an instrument string nearly 1000 ft in length. Threading wire only 0.041 in. in diam through 1000 ft of plastic pipe is almost as difficult as getting the proverbial camel through the eye of a needle.

Jan 1, 1971

By W. A. Anderson

IN the pressure die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger and a complete shutdown of the equipment. All of the zinc alloys used for pressure die-casting today contain approximately 4 per cent of aluminum, which is more than sufficient to make plunger operation feasible. The clearance between the plunger and its bushing is an important matter. As the space becomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still used in some machines. However, the rate at which the plunger clearance increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new materials more capable of retaining the desired clearance during long periods of use. Today many die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the plunger will operate for a long time, of course. The authors have developed a laboratory apparatus in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clear-ance area.

Jan 1, 1939

New York Meets first Wednesday after first Tuesday of each month. J. E. JOHNSON, JR., Chairman. EDGAR RICHARD, Vice-Chairman. D. M. LIDDELL, Secretary, 7 Wall St., New York, N. Y. C. A. BOHN, Treasurer. JOHN V. N. DORR, LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. R. L. AGASSIZ, Chairman. JAMES G. CARLETON, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Cambridge, Mass., W. E. C. EUSTIS. G. A. PACKARD. Columbia Holds four sessions during year. Annual meeting n September or October. W. H. LINNEY, Chairman. OSCAR LACHMUND, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON, S. SHEDD. Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman. I. F. LAUCKS, Vice-Chairman. CHARLES SIMENSTAD, Secretary-Treasurer, 425 Lyon Bldg., Seattle, Wash. GLENVILLE A. COLLINS, JOHN N. POTT

Jan 7, 1917

By J. T. Norton, H. Blumenthal, S. J. Sindeband

The interstitial phases formed by the transition elements with carbon, nitrogen and boron constitute a unique class of substances which are of considerable technical interest because of their well developed metallic properties and their high hardness and melting points. They are also of interest from the point of view of structure. It was pointed out by Hagg1 some years ago that the principal factor determining these structures was the relative sizes of metal and metalloid atoms. He predicted that if the ratio of the radii of metalloid to metal atoms was less than 0.59, the metal atoms would be arranged in a close-packed fashion of relatively simple type. This prediction has been amply confirmed. It appears, however, that this specification applies most generally to those structures in which the metalloid atoms occupy isolated positions in the lattice and there is no tendency for strong binding between the metalloid atoms themselves. The series of borides of the type MeB2 formed from the transition elements of the fourth (Ti, Zr) and fifth (V, Cb, Ta) groups of the periodic table provide an opportunity to investigate this situation further. If one takes as a basis the radius of 0.87 A for the boron radius and the Goldschmidt values for the metal atoms in 12 coordination, then the radius ratio varies from 0.54 for zirconium to 0.64 for vanadium, which latter is considerably greater than Hagg's limit of 0.59. It was of interest, therefore, to see if these five elements would form borides of the MeB2 type and have simple isomorphous structures. When this investigation was initiated, relatively little information had been published on the structure of this group of borides. McKenna2 reported the preparation of ZrB2 by a carbon reduction process. Its structure was hexagonal and the approximate lattice constants were given as a = 3.15 A, c = 3.53 A. Ehrlich3 reported the structure of TiB2 as being of the C 32 type with a = 3.02, c = 3.21 and c/a = 1.06 A. Recently, Kiessling4 published the results on ZrB2, showing it to be one in which the metal atoms are arranged in a simple hexagonal lattice with the boron atoms in flat sheets, midway between the layers of metal atoms. The structure is C 32 type with a = 3.169, c = 3.530 and an axial ratio =1.11 A. He also states that CbB2 and TaB2 are isomorphous with ZrB2. Preparation of Borides The borides of titanium, zirconium, columbium and tantalum were made by the electrolysis of fused salt baths after the method described by Andrieux.5 The bath, totalling about 6500 g in each case had the following general composition: Metal Oxide + B2O3 + CaO + CaF2. The actual proportions of the ingredients were determined for each individual case. Although Andrieux reports the preparation of vanadium boride by the same electrolytic method, several attempts proved unsuccessful. However, it was possible to prepare VB2 by the carbon reduction method used by McKenna to produce ZrB2. The mixture consisted of V2O5 + 6B2O3 + 11C and the reduction was carried out in an induction heated graphite crucible. This method proved satisfactory for ZrB2 and TiB2 and undoubtedly the others could be made in the same way. The borides, which were all in the form of fine gray metallic crystals from the electrolytic bath or gray powders from the reduction process, were carefully separated from other constituents and analyzed chemically for metal and boron content. The densities of the boride powders were measured using a standard 10 cc pyenometer at 18°C and ethyl benzene proved to be the most satisfactory liquid for this purpose. X Ray Technique The boride crystals, as prepared, were too small for single crystal examination so that powder techniques were employed. Patterns of the finely ground borides were prepared, using the Norelco recording X ray spectrometer. The lines on these patterns were indexed with the aid of Hull-Davy charts and the approximate dimensions

Jan 1, 1950

By F. C. Holden, R. D. Buchheit

In the course of studies made on the Ti-Cu alloy system,' particles identified visually as TiH were encountered unexpectedly in a specimen of high-purity Ti-0.8Cu alloy. The particles did not appear immediately after preparation, but following-storage in a dessicator for several days. Since the alloy had been vacuum annealed to a low hydrogen concentration (19 ppm by vacuum-fusion analysis), the appearance of the TiH particles was suspected as a surface contamination effect. A specimen of a Ti-0.8Cu alloy had been annealed 2 hr at 790°C and water quenched, to produce the single-phase equiaxed a structure. The metallo-graphic sample was ground through 600X paper, rough-polished on a high-speed wheel with a mixture of alumina and chromic acid, awLhish-polished on a slow-speed wheel. Disturbed metal layers were removed from the final surface by alternately etching with a 1 1/2 HF-3 1/2 HNO3-95 H2O solution and polishing on the slow-speed wheel with fine alumina. The final surface was swab-etched with a 1 1/2 HF-3 1/2 HNO3-95 H2O solution, rinsed in tap water, and dried in a stream of filtered air. The micro-structure, shown in Fig. 1, was composed of equiaxed a grains without any trace of second phase. After storage in a dessicator for 3 days, the appearance of small particles in the structure became evident (see Fig. 2). After 7 days of storage, the particles were more distinct, and in some grains, began to appear as elongated particles. The specimen then was etched a second time (without repolishing) to produce the structure shown in Fig. 4. On the basis of micro- structural observation, the line markings were identified as TiH; attempts to obtain diffraction patterns from the surface for positive identification were not successful. That the structure is a surface effect was demonstrated by grinding with 240X paper to remove the surface layer. The surface then was ground, polished, and etched using the procedures described previously. The same observations were made: the freshly prepared surface was devoid of any second phase, whereas the particles again appeared after several days storage. The same effect has been observed in other a-stabilized titanium alloys, including a high-purity Ti-0.20 alloy containing only 16 ppm H by analysis. The effect has not yet been observed in unalloyed titanium, nor does its appearance appear to be consistent with any particular alloy system. From these observations, it is concluded that certain a-titanium alloys are susceptible to the formation of titanium hydride at the surface of metallo-graphic specimens. The hydrogen probably is diffused into the surface from a residual film of etchant decomposition products. Estimates of the hydrogen

Jan 1, 1961