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By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

By Edmund M. Warner

Any city dweller who has walked alone along a remote mine passageway has to be impressed by the eerie silence-the total absence of noise except for one's own breathing and scuffing of boots on the bottom. An underpound mine can have tremendous contrasts, from complete silence to the ear piercing clatter of percussion drills working in the mine roof. Noise in underground mining machines is both useful and detrimental. Without characteristic noises that are recognizable to miners, operators would have a more difficult job operating their machines. Noise serves as a warning of approaching machinery, and changes in noise give indication that breakdowns may occur. But excessive noise is a health hazard. In recognition of this fact, our congress included noise exposure as a part of the "Coal Mine Health and Safety Act of 1969." As [Fig. 1] indicates, allowable noise exposure is established by specifying a time duration permitted at different noise levels. This is the well known "Walsh-Healey" criteria which govern noise exposure in many industries. In most industries noise exposure is not a constant value. Noise emitted from coal mining machinery varies widely, and therefore interpretation of compliance is not a simple matter. Time, environment, instrumentation and machine productivity, as well as the designed machine characteristics affect the results. It is the purpose of this paper to present the underground coal face machinery noise problem from a manufacturer's point of view. Manufacturers are very much aware of their responsibility to alleviate the noise problem. Not infrequently, orders are received from coal operators that a given new machine must comply with "The Coal Mine Health & Safety Act" noise regulations. Such a request is indicative of the misunderstanding which exists with machine users, while indicating their desire to comply with the law. Obviously, if all machinery could be designed and used at some arbitrary low noise level, it would be possible to simplify the regulations. However, there still remains the pervasive problem of existing machines. Extensive investigation to create practical retrofit kits for existing machines, to substantially reduce noise have been only marginally successful. Certain machine mechanisms are inherent noise makers. The only really good solution is to substitute a quieter mechanism. Such overall new designs have been undertaken, and several examples are mentioned later in this paper. Before describing machine noise problems, it is necessary to define noise values. Noise levels are measured in decibels. The designation "DBA" is decibels measured on the "A" scale, or one in which the frequency sensitivity of the instrumentation is about the same as the human ear. The numbers are often misinterpreted because it is a logarithmic, rather than an arithmetic scale. In comprehending the numbers, it should be remembered that any increase of 3 dB doubles the sound power. In practical terms this means that two noises of equal power at the same distance away increases a dB reading by three. Consider [Fig. 2] showing a simplified case of a worker on a machine subject to

Jan 1, 1980

By D. Perry, G. W. Binkley, G. K. Dumbauld, F. A. Brooks

A new cementing technique has been developed which is particularly applicable to permanent-type well completion operations. The technique makes use of the accelerating effect of calcium chloride on setting time and strength development of cement cake deposited in squeeze cementing. An unique feature is that the accelerator is applied after the unaccelera-ted cement slurry has been squeezed and the excess has been reversed from the well. Laboratory data on the accelerating effect of calcium chloride applied to the fi1ter cakes of three low-water-loss cementing compositions demorzstrate that the procedure results in relatively rapid development of strength and impermeability of the cement cake. Simulated squeeze-ceinenting tests made in the laboratory likewise corroborated the practicality of the procedure. The laboratory tests showed that a newly developed oil-emulsion cemerzting composition is more susceptible to acceleration of set than are modified cements containing high percentages of bentonite. The acceleration procedure has been used successfully in field operations. INTRODUCTION Nature of Problem In squeeze-cementing operations, a substantial amount of time is consumed in waiting on the cement to develop strength after it has been squeezed into the well. Frequently, an interval of 18 to 24 hours or longer is required for the development of strength sufficient to prevent failure of the cement during subsequent operations in the well. Reduction of this waiting-on-cement time offers appreciable savings both in time and in money. A particular type of squeeze-cementing operation to which an increasing amount of attention has been given is encountered in permanent-type well completion operations wherein perforations are to be squeezed off1. In this procedure, it is customary to pump the cement slurry down the tubing and out into the perforated section through a retractable extension pipe. Squeeze pressure is then applied, which forces the cement slurry into the perforations and causes the build up of a compact filter cake of cement within the perforations. The excess slurry remaining in the hole is then removed by reverse circulation. The extension pipe is then retracted, and, if a new interval is to be perforated, a perforating gun is run through the tubing. The newly perforated interval may then be tested by swabbing. In such operations, it has been customary to allow approximately 20 hours or so for hardening of the cement squeezed into the perforations. This time interval is usually measured from the time that the cement is reversed out of the hole to the time that subsequent swabbing is started. If the cement has not developed strength at the commencement of swabbing, the pressure differential caused by swabbing results in failure of the squeeze job. At the time that the work described in this report was initiated, particular consideration was given to the reduction of waiting-on-cement time in squeeze cementing by the permanent-type completion technique. Consequently, much of the experimental work was directed to this specific objective, though the process which was developed for acceleration of strength development has possible application in other than permanent-type completion operations. Method of Attack Although quick-setting cements

Jan 1, 1957

By Robert F. Love

Deep under the hills of southwestern Wyoming lies a nonmetallic mineral deposit of incredible dimensions and value. This nearly pure, horizontal bed of the mineral trona, a sodium sesquicarbonate (Na2HC0,.NaHC08.H20), is found in the Green River formation some 1500 ft below surface. It is believed that evaporation of an ancient saline lake left this sodium carbonate as the evaporite and mysteriously left practically no sodium chloride, which is the common constituent of an evaporated saline lake. The trona bed averages 10 ft in thickness and extends over an area of several hundred square miles. In 1938 a geologist with the U. S. Geological Survey identified the trona in the core from a former oil exploration drillhole. By so doing, he initiated the developments of a chemical industry of impressive growth in the area, an industry on the threshold of further and much more spectacular growth. A drilling program by the Union Pacific Rd. and Intermountain Chemical Co. in the early 1940's succeeded in blocking out mineable reserves of several hundred million tons. Development of the deposit started in 1946 with the sinking of a 12-ft diam, concrete-lined shaft 1500 ft deep-followed by construction of a small pilot calcining plant. Actual mining of the trona started in 1947 and continued on a limited scale until 1953, when the $15 million surface facilities were completed, along with the second shaft and other expanded underground facilities. Since April 1953 the mine has been producing more than half a million tons per year, from which the refining plant has produced more than 300,000 tons per year of high quality soda ash.

Dec 1, 1956

By W. E. Curran

For years the geographical isolation of the Southern iron-ore district from the great producing centers in the North and East enabled it to meet its conditions and solve its own problems without regard to the practices and policies of other districts, but during the past few years distances have been shortened, practices and wages are being standardized, .and these changing conditions have brought new problems to the South.

Jan 1, 1937

By John S. Rinehart, Norman Ahlquist

The model which Birkimer has developed to explain the increase in fracture strength of brittle, rock-like materials with increasing rate of loading may have some applicability. It should be noted that since his analysis presupposes elastic behavior he could equally well express his result as an increase of stress to fracture with increasing strain rate, a fact which is well known. Certainly his experimental results do not contradict his strain rate to the one third power law. On the other hand, we do feel that the data are insufficient and inadequate to establish the relation- ship definitely. 'In metals, the whole fracture picture is greatly complicated by concomitant plastic flow and, in rocks, by the presence of macroscopic flaws and inhomogeneties. Both lead to uncertainties as to the state of stress during the fracture process. He quotes in support of his theory Rinehartfs results on rock in which the latter found that under impulsive loading by explosives, rocks appear to be many times stronger than under static loading. We suspect that the observed increase has little specific relevance to the theory which Birkimer puts forward. Rinehart's measurements were made by spalling rocks using a sawtooth shaped stress wave of known intensity and duration. The rise time of such a pulse is essentially zero, certainly less than 0.1 microseconds, so that it is not possible to apply Birkimerfs theory quantitatively. We favor attributing the increase in fracture strength to two factors. First, the action takes place very quickly in an exceedingly thin region so that statistically the probability is small of encountering one or more of the large flaws that contribute so significantly to the reduction of strength of most rocks under tension. It is also conceivable that the compressive wave that has just passed by the region of fracture has strengthened the rock by collapsing some of the larger flaws. Second, the state of stress obtaining at the time of fracture is not all that existing when the

Jan 1, 1971

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa.*.. *May: '71.. 1 3 2. Bethlehem, Pa Aug. '71.. 1 10 3. Troy, N. I X Nov. '71.. 1 13 4. Philadelphia, Pa Feb. '72.. 1 17 5. New York, N. Y.*.... May, '72.. 1 20 6. Pittsburgh, Pa Oct., '72.. 1 . 25 7. Boston, Mass Feb., '73 1 28 8. Philadelphia, Pa.*.... May, '73 2 3 9. Easton, Pa Oct., '73 2 7 10. New York, N. Y Feb., '74.. 2 11] [ ]

Jan 1, 1925

By Lysle E. Shaffer

TEACHING engineering students how to write and speak effectively -is one of the greatest problems facing the technical schools today. No phase of engineering education has received more criticism, and rightly so, for the criticism is justified. Year after year we continue to graduate men that are indifferent to the use of a tool they will need every day of their lives. Our young engineers cannot write a clear, concise report, and their business letters are a disgrace to the profession that takes pride in precision. The problem is not new. The remark ascribed to Sir James Barrie, that "The man of science appears to be the only man who has something to say, just now-and the only man who does not know how to say it" is as uncomfortably true today as it was thirty years ago. The records of meetings of engineering educators and the transactions of the engineering societies show that the inability of the engineer to communicate his ideas has been discussed for years. Engineering educators, prodded by industry, have recognized that the problem exists, but they have not solved it. Instead they continue to expose the student to composition and rhetoric, hustle him through English and American literature, and then blame his high school because he does not know enough English grammar to write a clear sentence. We must face the fact that the graduate is not going to reflect on the high school, but on his college. If the high school has shirked the job, the responsibility for correction rests on the faculty of the professional school.

Jan 1, 1948

By J. A. Berger, G. W. Wiener

Several transition metal nitrides have been prepared and their saturation magnetization determined. On the basis of an atomic model of ferromagnetism involving a consideration of nearest neighbor interactions and the assumption that all atomic moments of the metal point in the same direction, it appears that the nitrogen interacts with d-shell of the transition metal in such a way as to reduce the magnetic moment. THERE is a large class of materials having metallic properties which are formed by a combination of hydrogen, boron, carbon, oxygen, or nitrogen with the transition metals. Several attempts have been made to establish the type of metal-nonmetal bonding in these interstitial alloys because it is believed that many of the physical properties of these materials are determined by the characteristics of this bond. Several of these alloys are ferromagnetic, and thus a powerful method is available for investigating the structures in a direct manner by measuring the saturation magnetization. The latter is a fundamental property of ferromagnetic metals and alloys which depends primarily on the electron distribution surrounding the atom. For the first row of transition metals, this refers specifically to the 3 d-shell. Since bonding involves the electronic configuration between atoms, there is reason to suppose that a relationship exists between ferromagnetism and bond type. In the case of the interstitial structures studied in this work, bonding will refer to the distribution of electrons between the transition metal and the nonmetal. Since these alloys have metallic properties, it is further proposed that any bonding interactions will involve the outer p-shell of the interstitial element and the incomplete d-shell of the transition metal. If this is the case, then the relationship between ferromagnetism and metal-non-metal bonding is established qualitatively. In order to investigate the subject quantitatively, certain transition metal nitrides were chosen because they have simple crystal structures, are ordered alloys, and are ferromagnetic. They also have sufficiently high saturation magnetization to be of technical interest. Currently there are two major theories of ferromagnetism, each of which has been applied to the interpretation of the saturation magnetization in terms of atomic structure. They are usually referred to as the band theory and the atomic theory. The former has found widespread application to the study of pure metals and certain solid-solution allays. However, it has not been applied to the interstitial structures or ordered alloys because it does not interpret the properties directly in terms of the crystal structure. The atomic theory on the other hand is especially suited to the study of interstitial structures because it permits an interpretation of ferromagnetic phenomena in terms of the crystal geometry. As has been pointed out previously, the nitrides have simple ordered crystal structures and, therefore, the choice of the atomic theory for the interpretation of the data is a natural one. One of the prime difficulties with the atomistic theory is that its mathematical justification is much more difficult, and for this reason its general acceptance will depend to a large extent on the value it has in explaining and predicting the results of experiment. Before the presentation of the theoretical basis for understanding the metal-nonmetal bond, it is useful to review the ideas existing prior to this work. Four different interpretations have been given to the metal-nonmetal bond. These are summarized as follows: 1—acceptance of electrons by the nonmetal from the incomplete d-shell of the transition metal, 2—transfer of electrons from the nonmetal to the incomplete shell of the transition metal, 3—no exchange of electrons between the two atoms, and 4— a resonating type of bond involving the p electrons of the interstitial atom giving rise to half bonds. Zener'-4 in a recent series of papers has proposed a new theory of ferromagnetism and has developed an explanation of the observed saturation magnetization of iron nitride (Fe,N) using the concept that nitrogen accepts electrons from the 3d-shell of iron. Jack," on the basis of atom size considerations in iron carbonitrides, has proposed that nitrogen transfers or donates electrons to the inner 3d-shell. He found that the effective size of the carbon atom was less than that of nitrogen and thus suggested that the interstitial atoms give up electrons. Kiessling" has studied the borides of several transition metal atoms and proposed that boron loses one p electron to the transition metal. He postulated that the additional electron added to the metal lattice compensates for the loss in metallic properties which results from the increased metal-metal atom separation. GuillaudT3" has proposed similar arguments from some recent magnetic studies he had made on manganese nitride. However, he did not base his conclusions on a quantitative argument. Pauling," in a recent paper, discussed electron transfer in in-termetallic compounds. He classified nitrogen as a hyperelectronic atom which can increase its valence by giving up electrons. He classified the transition metals as buffer atoms which are capable of either accepting or giving UP an electron. He pointed out that two factors are operating which promote electron transfer because they lead to increased stability. The first is an increase in the number of bonds, and the second is a decrease in the electric charges on the atoms. These ideas when applied to the interstitial nitrides would indicate a viewpoint favoring electron transfer by nitrogen to the transition metal. Hagg7s arguments in favor of no exchange are adequately summarized by Wells." Implicitly, Hagg

Jan 1, 1956

NEW MEMBERS The following list comprises the names of those persons who became members during the period Apr. 10 to May 10, 1914: Members ADAMS, HENRY H., JR., Merchant, Henry H. Adams & Co., and Colonial Iron Co., 149 Broadway, New York, N.Y. ADAMS, LELAND D., Mine Mgr., Supt., East Canada Smelting Co.,Weedon, Quebec, Canada. AGUILERA, EUGENIO, Chief Engr. Mining & Foresting Dept. of Santiago, Santiago de Cuba, Cuba. ALFORD, NEWELL GILDER; Min. Engr., Asst. Chief Engr., St. Bernard Mining Co,. Earlington, KY.

Jan 6, 1914

By R. N. Singh, A. S. Atkins

One of the most difficult problems associated with modern mechanised longwall mining is the lack of system flexibility to deal with local changes in geology, seam thickness and the face design parameters. As a consequence of system rigidity and the quest for increasing the coal face performance, the percentage extraction in the U.K. is currently below 52%. The paper outlines the current guidelines used in face design which permit coal to be left in situ for various purposes and discusses the strata control implications in extracting subsequent panels in the same and adjacent coal seams. The paper examines the application of strata mechanics to the design of longwall layouts for maximizing .the percentage of coal extraction. Remedial measures include optimizing pillar dimensions, reduction in roof coal left for support purposes by improving the use of available powered support technology and application of thick seam mining methods including sub-level caving and techniques of extracting coal from odd shaped pillars. Case studies are described where coal extraction has been maximized by adopting a new single heading retreat mining system; a shallow seam partial extraction system utilizing, existing heading machines and minimisin8 coal sterilization in pillars by replacing longwall access roadways by goaf scour.

Jan 1, 1984

By B. E. Cornish

Most technical and statistical data published on pyrophyllite relating to production figures, uses, markets and sales, have in the past traditionally linked the mineral with talc and soapstone. This is due to several common superficial physical properties resulting in substitute uses and applications. However, these minerals are not similar in chemical composition and do not generally occur in a similar geological environment. Pyrophyllite now stands on its own in the marketplace-particularly in ceramic applications-due to the combination of excellent heat shock and creep resistance properties of the mineral. The increase in pyrophyllite use in the field of ceramics indicates the continuing realization of these marked unique properties. Several new fields of ceramic applications, previously the preserve of high-alumina materials, have been developed on the intrinsic properties of pyrophyllite. Pyrophyllite is an aluminum silicate with the molecular formula of AI2O34SiO2H2O. It would be more appropriate to group pyrophyllite with such materials as kyanite, diaspore, andalusite, and certain high-alumina clays in relation to its general applications (Stuckey, 1928). These materials all have good beat shock resistance properties at high temperatures and are widely used for the manufacture of refractories. For those reasons they are interchangeable in some applications. Pyrophyllite also has many uses in nonceramic applications, the most important to date being as a substitute for talc in fillers. The major pyrophyllite mining operations are located in the US, Japan, Korea, Canada, and Australia, where the mineral is widely used as a raw material for general ceramic, mineral filler, and dilutant applications. Commercial Applications Pyrophyllite was first used in the last century for lining stoves and fireplaces, and also in the carving and polishing of ornamental objects. The rise in industrial demand for new products and applications resulted in the introduction of pyrophyllite as an alternative, mainly for talc and soapstone. Industrial filler applications followed for paint, paper, cosmetics, rubber, pesticides, crayons and pencils, and bleaching soap. The first use of pyrophyllite in ceramic applications was prior to World War II, in the manufacture of ceramic cladding tiles in the US. This was followed by the production of kiln furniture refractories and whiteware when pyrophyllite was offered by suppliers in North Carolina as an alternative to some local clays. The largest tonnages of pyrophyllite used today are in refractory linings in steel ladles in Japan, as seen in Table 1. The consumption of pyrophyllite in Japan is second only to clay and chamotte among refractory raw materials used. Recently this technology has been adopted in Australia. Japanese and Australian practice has resulted in appreciable technical and economic benefits, particularly when pyrophyllite is used in combination with zircon. The potential growth for this application is substantial if US and European steelmakers follow. Investigation and research into the properties of pyrophyllite determined the following main advantages of pyrophyllite-based ceramics: high corrosion resistance for molten iron, steel, and slags; good heat shock resistance; good indices of deformation under load and hot creep resistance (refractories); and increase in mechanical strength of whiteware products promoted by a better distribution of mullite in finished products (also obtained at lower firing temperatures than normally required in production of triaxial ceramics). White cement

Jan 1, 1983

Jan 1, 1911

Jan 1, 1912

Jan 1, 1909

By Sandip K. Mukherjee, Anthony W. Laurito, Madan M. Singh, Jon C. Volkwein

In the past, little attention has been paid to the costs of ventilation, since it seldom represented a significant portion of the total mining cost. However, in recent years adverse mining conditions and increases in power charges have caused ventilation costs to rise. The federal regulations have set minimum standards for volumetric airflow rates in underground coal mines. As a mine develops, the air volume and pressure requirements increase. There are several methods by which the quantity of airflow to the mine and working faces can be increased. Some of the methods include (1) increasing main fan output or replacing the main fan by a new higher capacity fan, (2) reducing leakage across stoppings and overcasts, (3) adding a new ventilation shaft or borehole, (4) reducing resistance to airflow by reducing the resistance factor of the individual airways, increasing the number of airways (especially the parallel airways), or re- arranging the air courses by using the available entries, and (5) using auxiliary ventilation systems. This paper addresses the cost-benefit analysis of several of these alternatives as applied to a large operating coal mine located in southern Illinois. Pressure and quantity surveys were conducted under-ground, and measurements were taken at the main exhaust fans on the surface. The existing ventilation network was modeled by using the Penn State ventilation simulator. The input data included the configuration of branches, resistance of each branch (including a component for shock losses), and changes in pressure and volume. The results of the simulation were compared with the survey data to check the merits and accuracy of the model network. The net- work was designed to take into account shafts, major entries, overcasts, regulators, gob areas, working faces, and major leakage paths. The model network served as the basis for the cost analyses of networks designed for increased airflow. The applicable alternatives for increasing airflow were simulated. Performance data obtained from these simulation runs were utilized to conduct the cost-effectiveness analysis. The costs for each f the alternatives included capital, operating and maintenance costs. These costs were expressed as annual costs in terms of dollars per cfm of circulating air, taking into account the economic life associated with each of the alternatives. The benefits were expressed as increased airflow quantity in the critical sections. The result of these analyses show that for the short-range plans evaluated, the most cost-effective way of increasing airflow at this mine would be to reduce leakage through stoppings and overcasts.

Jan 1, 1982

By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors' results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24'n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,'' specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-' amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-' amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors' reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald's experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald's colleagues cannot be operative at this temperature. A detailed discussion of the general' inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By Pol Duwez, Paul Pietrokowsky

Titanium and vanadium form a complete series of solid solutions at temperatures above 885°C. Below 885°C, vanadium is slightly soluble in a titanium (about 1.5 pct V at 650°C) and a two-phase a plus ß region extends to 18.5 pct V at 650°C. The alloys up to 15.0 pct V transform into a supersaturated a solid solution upon rapid cooling from the ß phase. Above 15 pct V the ß phase may be retained. The temperature at which the ß to a' martensite-type transformation takes place decreases steadily from 850°C for 0.5 pct V to 325°C for 12.7 pct V. IN the transition series of the periodic table, the six elements that have a body-centered cubic structure at all temperatures, namely chromium, vanadium, molybdenum, columbium, tungsten, and tantalum, fulfill the conditions required for the existence of complete series of solid solutions with the high temperature (ß) form of titanium. Up to the present time, complete solubility at temperatures above the a to ß transformation of titanium has been observed in the systems Ti-MO,1,2 Ti-Cb,2 Ti-W,³ and Ti-Ta.³ The two remaining elements, vanadium and chromium, have atomic diameters which are not as near that of titanium as the atomic diameters of the four other elements. Both are smaller than titanium and the difference, expressed in percentage of the titanium atomic diameter, is 12.3 pct for chromium and 8.2 pct for vanadium. On this basis, the least favorable conditions for solid-solution formation are therefore encountered in the Ti-Cr system. The early work on the Ti-Cr system4 revealed that up to about 1100°C the solubility of chromium in ß titanium is limited, and an intermetallic phase exists near the stoichiometric composition TiCr2. It was found later' that a continuous series of solid solutions extends across the diagram at higher temperatures, and TiCr2 forms by solid state reaction. It became apparent therefore that complete solubility would also be present in the Ti-V system. The present investigation confirms this possibility. The iodide-refined titanium used in this investigation was purchased from the New Jersey Zinc Co., New York. According to the manufacturer, a typical analysis of this product is 0.0065 pct Mn, 0.0022 pct Fe, 0.0015 pct Cu, and 0.0042 pct Pb. The Vickers hardness number (10 kg load) of the crystalline bar varies between 55 and 80. The vanadium metal was purchased from the Westinghouse Electric Corp., Lamp Div., Bloomfield, N. J. The purity of this metal is probably above 99 pct V. The oxygen content must have been quite low, since a bar about 1/4 in. square could be cold rolled into a ribbon 0.020 in. thick. To prepare the various alloys on the titanium-rich side of the diagram, the titanium rod was machined into cups 1 cm in diam and about 1.5 cm high. Pieces of vanadium, of the proper weight, were cut from the square bars and placed within the cups prior to melting. On the vanadium-rich end of the diagram, single pieces of the metals, in the proper weight pro-

Jan 1, 1953

By P. E. Landolt

MILITARY necessities and economic scarcities, occasioned by the first and second World Wars, led to the search for substitute materials and new products to meet the demands of advancing technology accelerated by research development. Among others, lithium came to attention. Its chemistry had been studied for a long period, but its general use was quite restricted due to limited known sources of raw material. In World War I, Germany used lithium metallurgically for two principal purposes: 1-hardened lead alloy, B-Metal, for railway bearings as a substitute for lead-tin-antimony alloys; and 2-light strong aluminum alloys, Scleron, in which zinc was largely substituted for copper.

Jan 12, 1951

By AIME

BILL BREWSTER was a natural for the steel business. His family lived at Iron Mountain, Mich., when Bill was born on June 14, 1889, so that he had iron in his blood. Always he has looked toward the finished product, rather than the raw material, so that it was a fore-gone conclusion that he should work toward the steel end of the business. After preparing for college at Hotch-kiss Academy he entered the Sheffield Scientific School of Yale University from which he graduated in 1910 with the degree of Bachelor of Philosophy. No reunion of his class would be complete without Bill Brewster. Unlike many of us who try several jobs before settling down, Bill shot straight for the mark. After a summer's work at Iron Mountain, making sure of his background in the production of the raw iron ore, he entered the employ of Wisconsin Steel Works of the International Harvester Co. in September 1910 and has been there ever since. It wasn't much of a job to start with, just a laborer in the billet dock department, but soon there was an opening in the blast-furnace department, where he started as superintendent's clerk in December 1910.

Jan 1, 1946