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By Donald M. Hausen

Microscopic evaluation of trace quantities of metalliferous phases in flotation products requires counting large numbers of particles. Particle counts of many thousands may be required for precision, but cannot be obtained practically by conventional microscopic techniques. A less tedious microscopic method for evaluating trace sulfides in mill tailings was developed for the O'okiep Mining Co. in South Africa. Hundreds of thousands of particles were evaluated by this method called "gross-counting." Gross-counting consists of counting microscopic fields rather than point-counting individual particles. Total counts are calculated by multiplying the average number of particles per field by the total number of fields examined over the entire mount. Total gross-counts range from about 20,000 particles for +200 to 100,000 or more for -400 mesh size material in lucite mounts. Sulfides and metallic particles in each field are identified and tallied along with field counts. Totals for each type of metallic particle are divided by the total gross-count to give volume percent which is corrected to weight percent by specific gravity factors.

Jan 1, 1973

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats of Formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 and the heats of solution of tellurium and selenium in liquid bismuth have been measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides have been measured in a constant temperature gradient calorimeter. The thermo-dynamic quantities are interpreted in relation to the stability of the compounds and the nature of the solid-liquid transition. THE selenides and tellurides of several elements of Group VB of the periodic system are of interest because of their electronic properties. The compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 are semi- conductors; they also have gained prominence in the fields of thermoelectricity and photoconductivity. However, little is known about their thermody-namic properties. As part of a research program on the thermo-dynamic properties of intermetallic compounds, the heats of formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 were measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides were measured in a constant temperature gradient calorimeter. The results, in addition to their intrinsic interest as thermodynamic quantities, contribute to an understanding of the stability of the compounds and the nature of the solid-liquid transition. 1) EXPERIMENTAL 1.1) Materials. Samples of the compounds SbzSe3 and Bi2Se3 were prepared by melting the elements in stoichiometric proportions in evacuated Vycor capsules followed by quenchinn in water. They- were then annealed in vacuum for 12 hr at 550°C. A sample of Sb2Te3, consisting mainly of one large grain, supplied by the Lincoln Laboratory,

Jan 1, 1964

By W. S. Ayres

The protractor here to be described embodies several important improvements that have been suggested by the use of other protractors and by observing the errors occurring in practice with them. It is more particularly an improvement

Jan 1, 1896

By E. H. Griswold

The many complexities arising from our present oil pool proration systems emphasize the need for a suitable standard of property rights. Attempts at conservation and unitization agreements have frequently failed because of the lack of such a standard. The necessity of reducing production to consumption has caused umpires, committees, commissions and other governing bodies to allocate the production of flush fields among the respective owners. The methods of allocation vary widely and conservation of underground reserves is frequently neglected or misused. Critical economic conditions increase, rather than modify, competitive methods. In some fields we have irregular and uneconomically close well spacing. Many operators drill unreasonably large holes, take excessive sand penetrations or leave their wells untubed in order to secure higher potential open-flow tests than their offsets. All of these practices result in economic waste and frequently damage to the pool. Regardless of our agreement with the fundamental principles of proration or unitization, both are actual necessities in many of our present economic situations, and we are in urgent need of a suitable standard of rights to facilitate and simplify their operation. The problems pertinent to unit management are simple and of daily use in many partnership enterprises, but the problems of fair and proper division of production under either proration or unitization are, as yet, subject to controversy. The rights of respective owners must be ascertained and standardized before we can eliminate wasteful practices and still preserve constructive competition in our industry. Valuation of Tracts In a recent unitization conference it was found that each participant had a different basis for calculating the relative values of tracts. Some of these assumptions were as follows: 1. Unrestricted open-flow operation to abandonment. 2. Current proration system to abandonment.

Jan 1, 1933

By S. R. Smith, W. M. Voorhis, J. D. Young

The Tennessee Valley Authority (TVA) has conducted investigations to identify the major causes of coal pile inventory adjustments. This paper describes past and current attempts to improve inventory survey accuracy and reduce costly inventory adjustments. The unique interaction between accountants and engineers is also reviewed. Data and results of a recent field test wing downward-looking radar developed by Ohio State University are presented. These show great promise in determining coal pile depth and density, thus improving inventory accuracy. This electromagnetic remote sensing technique, if successful, would provide an optimum technical and economic method of surveying all 12 TVA stockpiles without costly borehole drilling or disrupting stockout and reclaim activity. The effect of changing coal quality to meet environmental standards has made accurate coal pile density measurement more important than ever in reducing the costs of electric power generation from coal.

Jan 1, 1984

By Edgar G. Hill

MUCH has been written and said recently about the methods used and materials and equipment employed in building the long tubes that criss-cross a great part of the [ ] united States, like the pattern of a spider's web. This paper will discuss the fundamentals of design of these lines from the economic as well as the engineering view-point, pointing out the effect of the volumes transported, and the load factor at which they are operated, on the unit costs of transportation, as well as the effects on costs of the character of the fluids the lines are called upon to handle. Generally speaking, crude-oil pipe lines carry oil from the producing fields to the [ ] refineries. Sometimes part of the journey is by pipe line to a coastal point and tank ships are employed for the rest of the trip. The main lines of directional flow of crude oil through pipe lines in the United States are shown on Fig. I, but this, of course, does not always show individual pipe lines. BASIC FORMULA FOR FLOW OF CRUDE OIL The laws governing the flow of crude oil through pipes are well known. The basic

Jan 1, 1942

By J. E. Lawrence

Copper-decorated lattice disorders in silicon have been analyzed by electron transmission microscopy, chemical etching, and P-N junction reverse current measurements before and following different gettering treatments. Lattice disorders acted as the nucleating sites for copper precipitation. Copper precipitates in silicon resist chemical etching, absorb electron beams more than silicon, and cause excess reverse currents. Totally gettered disorders will chemically etch rapidly, be transparent to electron beams at extinction contrast, and not contribute to excess reverse currents. Three different gettering procedures were performed to determine the effectiveness of different EXTRANEOUS metal contamination can alter the minority carrier lifetime and resistivity of bulk silicon as well as cause excessive reverse currents in semiconductor devices. Previous workers have reported such activity for gold,1,2 copper,'-* iron,' and rnanganese.2,5 Gettering is a method employed to render these impurities electrically inactive. However, some property of the junction-degrading metals prevents gettering procedures from being wholly reliable. The comparative effectiveness of gettering with different agents has been the topic of earlier publications.2,3,6-11 Two mechanisms for gettering metallic impurities have been proposed: the distribution coefficient mechanism by Thurmond and Logan7 and the compound formation mechanism by Goetzberger and Shockley.2 Both of these models evolved from data gettering mechanisms. First, phosphorus was allowed to enter a protective SiO2 film but remain away from the Si-SiO2 interface to test the effectiveness of the compound formation gettering mechanism. Second, phosphorus was allowed to enter the backside of silicon wafers to test the effectiveness of the lattice strain gettering mechanism. Finally, nickel was diffused into the backside of silicon wafers to test the effectiveness of the distribution coefficient gettering mechanism. In each case, copper precipitates dissolved as a result of the gettering treatment. Tightly packed precipitates will resist gettering more than loosely packed copper precipitates. acquired by the electrical analyses of gettered semiconductor materials. An electrical analysis, however, cannot identify the fate of the gettered metals. The radiotracer technique has recently been applied to determine the redistribution of metals following different gettering treatments.3,9,10 The spatial resolu tion of the radiotracer technique prevented the analysis of metal precipitates which contribute to the excessive reverse currents of P-N junctions. The gettering processes employed by the earlier workers, almost without exception, allowed the gettering agent to enter the silicon lattice. This procedure makes it quite difficult to differentiate between the distribution coefficient and the compound formation mechanisms. The metallographic analysis of gettered copper precipitates discussed in this work supplements the earlier work by obtaining direct evidence of silicon lattice defects decorated with copper before and following different gettering treatments. The effectiveness of a process which restricts the gettering agent, phosphorus, to a dielectric film and thus away from the silicon lattice is discussed in addition to the ef-

Jan 1, 1969

By Edgar G. Hill

Much has been written and said recently about the methods used and materials and equipment employed in building the long tubes that criss-cross a great part of the United States, like the pattern of a spider's web. This paper will discuss the fundamentals of design of these lines from the economic as well as the engineering viewpoint, pointing out the effect of the volumes transported, and the load factor, on the unit costs of transportation, as well as the effects on costs of the character 01 the fluids the lines are called upon to handle. Generally speaking, crude-oil pipe lines carry oil from the producing fields to the refineries. Sometimes part of the journey is by pipe line to a coastal point and tank ships are employed for the rest of the trip. The main lines of directional flow of crude oil through pipe lines in the United States are shown on Fig. I, but this, of course, does not always show individual pipe lines. Basic Formula for Flow OF Crude Oil The laws governing the flow of crude oil through pipes are well known. The basic

Jan 1, 1942

By Edgar G. Hill

Much has been written and said recently about the methods used and materials and equipment employed in building the long tubes that criss-cross a great part of the United States, like the pattern of a spider's web. This paper will discuss the fundamentals of design of these lines from the economic as well as the engineering viewpoint, pointing out the effect of the volumes transported, and the load factor, on the unit costs of transportation, as well as the effects on costs of the character 01 the fluids the lines are called upon to handle. Generally speaking, crude-oil pipe lines carry oil from the producing fields to the refineries. Sometimes part of the journey is by pipe line to a coastal point and tank ships are employed for the rest of the trip. The main lines of directional flow of crude oil through pipe lines in the United States are shown on Fig. I, but this, of course, does not always show individual pipe lines. Basic Formula for Flow OF Crude Oil The laws governing the flow of crude oil through pipes are well known. The basic

Jan 1, 1942

CONTENTS PAGE Ross, J. M. and WAYLAND, R. G.-Mining Methods at the Homestake. Discussed by Benjamin F. Tillson, R. M. Raymond, I, H. Barkdoll, Arthur Notman 1 EMMEL, RUDOLPH.-Mining Methods in Zaruma District, Ecuador. Discussed by Rudolph Emmel, George A. Packard, Fred Hellmann, R. M. Raymond, Arthur Notman 2 MISHLER, R. T. and BUDROW, L. R.-Methods of Mining and Ore Estimation at Lucky Tiger Mine. Discussed by Fred Hellmann, Benjamin F. Tillson...4 PARK, JOHN FURNESS.-Mining Methods of Jarbidge District. . Discussed by R. S. Lewis : 5 Mining Methods at the Homestake Discussion of the paper of A. J. M. Ross and R. G. WAYLAND, presented at the New York Meeting, February, 1925, and issued, as Paper No. 1408-A, with MINING AND METALLURGY, February, 1925. BENJAMIN F. TILLSON, * Franklin, N. J.--It requires a good deal of timber to operate, especially the caving systems. An important function in mine operations now seems to be forestry and to operate a timber tract in order to insure a supply of timber. By depleting the timber resources of your section, you only increase your costs later when timber must be brought in from the Pacific Coast or the East. Our experience has been that any square-set method of timbering is the most expensive. Timbering for stoping systems, top slicing if you will, although it uses a large volume of time does not require as expensive timbering as the square-set method; also it does not require as long a life for-the timber, so that such wood as birch and maple, which have strength but not long life under the fungus conditions in the mine, may be used. All the drifts in the orebody are thoroughly timbered, and it has required a lot of timber. If we had it to do over, we would spend a lot more money in the development of rock drifts; as a matter of fact, we must ultimately come to that any way.

Jan 6, 1925

By AIME

NEW YORK'S largest hotel, the Pennsylvania, will be filled with mining and oil men and metallurgists the third week of February when some 3000 AIME members, their wives, and guests will gather for the Institute's 1948 Annual Meeting-its 166th general meeting. Except for the usual Sunday afternoon and evening sessions of the Mineral Industry Education Division at the Columbia University Men's Faculty Club, the big assembly will be under one top and members will not this year have to consult compass and map to find their next session. Possibly enervated by the stupendous effort of the Anniversary Celebration last spring and the plethora of highly successful fall meetings, the various committees have been a trifle slow in arranging their social and technical programs, but in mid December as we go to press there is already much to report indicative of substantial fare and high interest. The definite timetable schedule will appear in the February M&M.

Jan 1, 1948

References are in all cases to the earliest known editions. In the few cases where the first edition has been unavailable for consultation, the particular one studied is indicated. English translations are included when known, but not others. [ ]

Jan 1, 1942

By Kandalla Ravindranath, C. C. Patel

Studies of the adsorption of dialkyldithiocarbamates at the surfaces of galena and sphalerite have shown that characteristic contact angles are obtained at galena surfaces in the 7-10 pH range, whereas lower angles are obtained at unactivated sphalerite surfaces even at pH 71 Further, the angles at sphalerite surfaces progressively decrease with increase in pH. However, when sphalerite is activated with cupric sulfate, characteristic contact angles are obtained at pH 7 and beyond. This shows that galena and sphalerite can be selectively floated with dithiocarbamate collectors at pH 7 and beyond. Experimental Materials Ore: The lead-zinc ore for the present study was obtained through the courtesy of the Geological Survey of India from Dariba, Udaipur, Rajasthan, India. The average ore analyzed 15.5% lead, 11.6% zinc, 6.7% iron, 15.6% sulfur and 36.6% acid insolubles. The ore was crushed in a Denver laboratory rod mill and sieved in a Denver automatic sieve shaker to obtain a -200- to +250-mesh (Tyler standard) fraction. This particular size was chosen because it was conducive to good liberation of sulfide minerals, both from one another and from gangue minerals. Collectors: Dimethyl, diethyl, diisopropyl and diisobutyl dithiocarbamates were prepared and purified by the methods described by Klopping and Van der Kerk.2 A freshly prepared 0.03% dithiocarbamate solution in distilled water was used for flotation studies. Frother: A 0.03% solution of pine oil in ethyl alcohol was employed. Activator: 7.3 g of cupric sulfate pentahydrate were dissolved in 1 1 of water and used for the activation of sphalerite. Depressant: 16.0 g of zinc sulfate heptahydrate were dissolved in 1 1 of water and used for the depression of sphalerite.

Jan 1, 1972

By John R. Don

In the South Island of New Zealand an unusually favorable opportunity is offered for the analysis of the older crystalline rocks, underlying the sedimentary rocks which form the "country" of the gold-deposits. The Manipori formation of this island, comprising the greater part of the mountainous district west of lakes Manipori and Te Anau, in Otago, consists of an enormous thickness (estimated by Professor Hutton1 at 160,000 ft.) of crystalline schists, gneiss, syenite, and syenitic gneiss, with associated masses of granite; the whole forming the most picturesque fart of New Zealand. The famous West Coast sounds occur in this formation. No paying auriferous lodes have been discovered in it; and for this reason an examination of the rocks is specially interesting here. Stelzner, Posepny, and others, who have criticised the conclusions of Sandberger, have laid great stress on the fact that all the silicates analyzed by him were taken from the vicinity of orebodies containing those heavy metals which he notes as occurring in the silicates of the country-rock; their contention being that these metals, supposed to occur as silicates in gneiss and other crystalline rocks, were really contained as sulphides, and were therefore impregnations from the neighboring orebodies. The same objection, whatever be its weight, might be urged with equal justice against Mr. Becker's derivation of the mercury and gold of the lodes of the Pacific Coast from' the granite underlying their country-rock. In the case of the

Jan 1, 1913

By H. Habenicht, J. J. Scott

An experimental method is described to compare strain data for rock and rock bolts when exposed to shock waves released by blastings. Static and dynamic strains were measured. Bolt gage response indicated a static decay of the bolt anchorage coupled with a reaction due to blasting vibrations. A distinct loss of bolt tension was indicated during vibrations and this was accompanied by a smaller but steady loss of tension due to static loading. The strain losses were found to relate to the shock source distance and the vibrational amplitude in the rock and bolts. Millions of roof bolts are used each year to stabilize mine openings and prevent their failure. Frequently, bolts become loose and lose their effectiveness as reinforcement to the mine structure. Many attempts have been made to determine the cause of loosening, including observation of the bolt tension or bolt torque through the use of torque wrenches, compression pads, and load cells. Pull tests have been used extensively to determine anchorage characteristics.102 These investigations have shown that even when bolts are loaded below the nominal anchorage capacity of the rock under 'static' conditions they exhibit a decay of load through adjustments and slippage at the bolt anchor. Since bolts are quite often found with the plate hanging loose from the rock surface, this condition suggests that some additional mechanism may have played a part in loosening the anchorage. Vibration from blasting or shock loading have been suggested as one cause in this type of anchorage deterioration. This paper gives the results of an investigation carried on at the University of Missouri at Rolla to determine the influence of shock waves on rock-bolt anchorage stability. ROCK BOLT ANCHORAGE UNDER DYNAMIC LOADING CONDITIONS In this report dynamic loading conditions are defined as conditions under which rock and bolts are exposed to vibrations occurring as a consequence of blasting, machine vibrations, earthquakes, rock bursts, etc. Whatever the location of the shock source, the waves created suffer extensive alterations along their travel paths, depending upon the vibrational properties and geometric parameters of the transmitting media. Together with reflection, refraction and diffraction at material boundaries, waves suffer changes in their nature to form tensile, compressive and shear waves. They become polarized, retracted, accelerated, dispersed, so that the waves incident at a point in the material can be the result of either one or a combination of this wide range of processes. A certain fraction of the wave energy will be lost due to friction, deformation, and material failure at the anchor-rock contact. Thus, the physical nature of wave propagation is such that it inhibits an exact analytical solution. For this reason this investigation should be considered qualitative rather than quantitative even though numerical data have been used as a base. CONCEPT OF THE INVESTIGATION Experiments were designed to find, from a series of rock bolts installed in natural mine rock, whether or not, and to what extent, bolt tensions would be influenced when bolts were exposed repeatedly to shock waves such as those produced by blasting. Electronic instrumentation available in the rock mechanics laboratory of the University of Missouri at Rolla was used to observe wave development in the rock and vibrational reactions in the bolts. EXPERIMENTAL PROCEDURE Fig. 1 illustrates schematically the experimental equipment. Electric resistance wire strain gages were used as sensors for the strain response of the rock and the bolts. Bolts were 5 ft long and 5/8 in. in diam, equipped with two-leaf type expansion shells for 1 3/8 in. boreholes. The bolt gages were mounted by use of Du Pont Household Cement, covered with an epoxy insulation and then enclosed in a copper foil for electronic shielding. For details of placement and the wiring diagram see Fig. 2 and 3. The output of both the rock gages and the bolt gages was fed into cathode ray oscilloscopes from which the vibrational traces could be photographed. A static strain indicator was also used to read the output of all gages.

Jan 1, 1968

By H. T. Green, R. M. Brick

True stress-strain data on alloys of pure iron with up to 2.4 pct Al were obtained in the temperature range +100° to —185°C. Alumi-num was found to reduce yield and flow stresses of iron at low temperatures but to have little or no effect on ductility. The effects of temperature and composition on strain hardening are discussed. SEVERAL independent studies of the behavior of high purity iron binary alloys at low temperatures are now in progress in attempts to evaluate systematically the variables affecting the low temperature brittleness of ferritic steels. This paper reports the results of one such investigation in which the tensile properties of aluminum and aluminum plus silicon ferrites were measured from 100" to —192°C. True stress-natural strain data have been obtained in order to evaluate as many as possible of the parameters which describe the behavior of the materials involved. In comparable studies at the National Physical Laboratory in England, iron and iron alloys of high purity have been produced' and tested at subat-mospheric temperatures.' True stress-natural strain curves were obtained there also. The purest iron contained 0.0025 pct C and 0.001 pct O and N. Even this, as normalized at 950°C following hot rolling, showed little ductility at -196°C. The grain size was ASTM No. 3, and the room-temperature yield strength was 17,800 psi (which seems too high for pure iron). Some of the NPL irons contained considerably more oxygen and demonstrated intergran-ular fracture at —196°C. The authors2 carefully differentiated between intergranular fractures associated with excessive oxygen content and transcrys-talline cleavage with little ductility encountered at —196°C in the purer material. The cleavage stress was half again as great as that associated with inter-granular fracture. Test Material, Preparation, and Procedures Of a number of Fe-A1 alloys produced, eight were considered to be sufficiently pure for testing. Partial chemical analyses (Table I), low observed yield points, and high ductilities indicate these alloys to be comparatively pure for vacuum-melted irons of sizable ingots, 5 Ib or more. To produce the binary Fe-A1 alloys, electrolytic iron was melted in air, cast into slabs, and rolled to strips 0.010 in. thick. These strips, joined into a continuous ribbon and wound into 2 1/2 in. diameter spools, were subjected for four weeks to a moving atmosphere of purified dry hydrogen in a stainless-steel tube at 1050" to 1150°C. Charges of these spools were melted in beryllia crucibles under good vacuums (1 micron), and aluminum (99.97 pct Al) was added to the melts. Compositions of these alloys are recorded in Table I. The ingots were hot forged and then cold rolled at least 65 pct to 3/8 in. rods which were vacuum annealed to the desired grain size, approximately ASTM No. 4, prior to machining into tensile test bars. All tensile specimens had gage sections 1 in. long, with a fillet of 1.5 in. radius to the shoulder. Gage diameters were 0.250 in, except for a few rods where additional cold work required use of a 0.200 in. gage section. After machining, 0.002 in. was removed from the gage diameter using 240, 400, and 600-grit metallo-graphic papers. The final polish with 600 grit left the fine scratches running in the longitudinal direction. By this means, surface metal strained during machining was removed. A few specimens heat treated after machining were similarly reduced 0.004 in. to remove any material affected chemically by the atmosphere during heat treatments, as is discussed in a later section. Tensile tests of the eight alloys at constant temperatures from +100° to —185°C were performed in apparatus which has been described." The essentials include a double-walled insulated metal vessel which contained the liquid heat-transfer medium surrounding the test specimen. A constant temperature was maintained by means of a pyrometer which regulated the pressure of dry air driving liquid air through a copper coil. Temperature variation was less than ±2°C during a specific test. For axial straining, two lengths of case-hardened chain, terminating in simple shackles, loaded the specimen through threaded grips. The lower grip bar passed through a hole in the bottom of the test vessel to which it was joined by a thin-walled

Jan 1, 1955

By T. V. Moore

DURING 1910, crude-oil production in the United States reached a record level averaging about 3.700,000 barrels daily. Export declined sharply while imports increased with the result that large quantities of crude oil were run to storage during the year. Imports consisted largely of residual fuel oil brought in from South America bit because of a shortage of that product in this country and of Mexican crude. The price of petroleum products followed the declining trend of the last three year resulting in serious disparity between crude and product prices. This condition was aggravated in some areas by the increasing production of distillate by recycling operations and by the high tanker rates prevalent in the last two months of the year. As a result two small purchasers found it necessary to reduce crude-oil price in the Corpus Christie area of Texas.

Jan 1, 1941

THE CHAIRMAN (A. F. LUCAS, Washington, D. C.).-The activities of the Petroleum and Gas Committee for the half year have brought gratifying results, as exemplified by 14 technical papers, brim full of novel and attractive issues in which we are all keenly interested. I beg to extend my hearty thanks to all members and authors who have responded to my appeal, and to all those who have endeavored to meet the growing demand which has resulted in the augmented production of this commodity which is so essential for the Nation's welfare, comfort and safety. As you well know, within the last few years, petroleum and its products have been used for numerous and novel purposes, so that we have become accustomed to their use in thousands of activities, and pleasures as well, but we should also note that we have been wasting and misusing these wonderful products, apparently believing that their sources are inexhaustible.

Jan 1, 1918

By R. G. Whittemore, R. Derry

Nickel metal, in powder form, has been produced by pressure reduction, with hydrogen gas, of slurries of nickel hydroxide at temperatures up to 250°C. The nickel hydroxide was obtained by precipitation from nickel chloride and nickel sulphate solutions, using both magnesium oxide and calcium oxide. Rates of reduction and yields were determined as a function of temperature, hydrogen overpressure, seed addition, and the amount of alkali used. The mechanism of reduction of slurries obtained from the sulphate system was studied, and major differences between the sulphate system and the previously examined chloride system investigated. Specifically, in the sulphate system, contra the chloride system, no seeding was necessary, plating and densification were virtually absent and only short induction periods occurred. Grades of product are given and the use of this process in the recovery of nickel from laterites is discussed. The selective reduction of nickel from mixed hydroxide slurries and effluent treatment plant sludge has also been examined.

Jan 1, 1973

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962