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Low metal prices prevailing at the beginning of 1950 stimulated the search for improved mining methods. More experience was gained during the year with such new developments as the jackleg drill, millisecond delays as applied underground, trackless mining, and Diesel powered equipment. One of the outstanding innovations in mining practice was the starting of the Round Mountain "dry land gold dredging operation." The Government is now inviting the mining industry to open up every available source of new metal supply and this circumstance will undoubtedly speed the development of new machines. New methods will also result but it is doubtful if economic efficiency will be at its peak.

Jan 2, 1951

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

By K. Tanaka, J. D. Mote, J. E. Dorn

It) an attempt to ulLcoce.lP the operative strain-rate-contl-olliy: dislocation nieclzanistns, specially oviented sizgle clystals of the intel-nzediate 1zexagonal phase containing Ag plus 33 at. pct A1 were tested in tension over a wide range of temperatures. Slip was observed to take place by the {0001} <1120> {l100} mechani fracture took place across the(i100) plane and winning occurred by the (i01Z) ?lechanisn. Basal slip exhibited a strong yield point over the -alzge from 77 to 450°K, the upper ,esolved shear st]-ess having the exceptionally high value of 10,500 psi over this entire ?-a?zge of tenzpei,atuves. The critical 9-esolved shear stress for prismatic slip decreased f7-om 48,000 psi at 4.3"K to 23,000 psi at 170°K (Region 1) follozcirg zt:lzich it decl>eased sloz&ly to 21,500 psi at 475°K (Res&apos;on II); from 475" to 575°K (Regioz III), the c7-itical esolced shear stress dec&apos;-eased precipitously to 2000 psi; and from 575" to 750°K (Region IV) it decreased less afi&apos;dly to a low value of about 500 psi. Pvistintic slip in Region I was pobably controlled by the tliel-nally activated riecharzisui of nucleation and g,-ozcth of kinks in dislocations lying in Peierls potential troughs. In Region II for prismatic slip the critical 1-esolved shear stress was slzocn to be deteemined by sh0l.t-range 01-dering, Overall the forgiorz fo basal slip, 7.c.lre1-e a Strong yield-point phenorlienu ia7as observed, the critical vesolved slzea?-stress was shoztn to be determined by n conibirzation 0-f Szizuki locking and short-range-order Izavderzizg, The precipitous decrease in the critical resolved shear stress with increase in ter,/pe7-atrir-e over Region HI was tentatively ascribed to a decrease in the degree of slort-)ange 07-del;iqq (0)- clusteing) and also the effect of fluctuations the degree of o?der, It is at pgreser2t zrtzce)taitz as to 1t1hethe1- these or other possi1)le effects are also ,esponsible. fo- the data obsel-ved 172 Region IV. 1NTEREST in inter metallic compounds stems not only from their role in dispersion hardening of polyphase alloy ystems but equally from their potentialities for high strength, hardness, and stability not only at atmospheric temperatures but especially at elevated temperatures. As summarized in a re- cent symposium of the Electrochemical Society on "Mechanical Properties of Inter metallic Compound", most of the experimental evidence regarding the mechanical behavior of intermetallic compounds centers about the effect of temperature on the hardness and ductility of polycrystalline specimens. The available data reveal that the plastic behavior of intermetallic compounds might be rationalized in terms of the usual dislocation mechanisms appropriate to a solid solutions providing the additional complexities arising from crystal structure, long-range ordering, short-range ordering, and defect lattices are taken into consideration. It is apparent, however, in terms of the history on a solid solutions, that a complete detailed mechanistic rationalization of dislocation processes may not be possible until the deformation processes are studied in single crystals of intermetallic compounds. The present paper contains a preliminary report on the plastic behavior of single crystals of the hexagonal Ag-A1 intermetallic phase over a wide range of temperatures. The results confirm the thesis that single crystal data provide a most effective method of identifying operative dislocation mechanisms in intermetallic compounds. EXPERIMENTAL TECHNIQUES Several factors prompted the selection of the hexagonal Ag-A1 intermetallic phase for this preliminar investigation on the plastic properties of single crystals of intermetallic compounds: 1) This phase has a wide solubility range5 which would permit future investigations on the effect of composition and axial ratios on slip mechanisms. 2) Although it undoubtedly exhibits short-range ordering (or clustering) this intermetallic phase is free from complexities arising from long-range ordering.6 3) Since the atomic radii of aluminum and silver are practically identical, the possible complications due to Cottrell locking are minimized. 4)Whereas the dislocations on the basal planes are expected to dissociate into Shockley partials and are thus susceptible to Suzuki locking, those on the prismatic planes probably remain complete. 5) The axial ratio, being 1.61, is almost ideal, suggesting that short-range ordering may be almost spherically symmetrical. The present investigation was conducted exclusively with the hexagonal Ag-A1 alloy containing 33 at. pct Al. Preliminary investigations revealed that this alloy undergoes basal slip by the (0001)

Jan 1, 1962

By B. C. Allen

The interface energies of chronzium, molybdenunz. hugsten, and their solid-solution alloys Cv-35Re, MO-33Re, and UJ-25Re were studied at 0.6 to 1.0 of the absolllte liquidus ter)zpe,vature using fiz&apos;e )izethods. Liquid surface tension, yv , was deter mined clsing the pendant-drop and drop-weight methods. Results are, respectizlely, 1700, 2370, and 2480 +100 dynes per ct for the rhernium -containing alloys and essentially the same as tlwse reported for liquid chro)riln, trolybdenum, and tungsten. Average solid slrjace energy, rsv< xias ))zeasured using tlre fiber-extetlsion method. The ratio of ysS, the acerage high-angle grain-boundary energy, to ySV cclas jolnd fronz grain-bolzdary grooue angles fort)zed at the surface in an inert atrfizosphere. Absolllte iute?:face energies were deterawined using ?nultip/rase equilibria involzing suitable liquids of known surface tension (tin, silver). Interpretation of the experimented results in view of pvobable tenzperatzcre, orientation, and purity effects giz,e the follouling approximations in ergs per sq ctn: ysv (i2lo. Mo-33Re) - 2100, ySS (Mo, Mo-33Re) - 800, rr (defornzation twins in MO-33Re at 1200"C) - 800. ysV (Cr. Cr-35Re) - 2400. YSS (CY, Cr-35Re) - 1000. Probably Ylv- YSV- 2500 for tungsten and W-25Re, giving yss (It&apos;, W-25Re) - 900. The interface energies of solid and liqid ch?&apos;omiu?.z, nolybdenu?rr, and tungsten are not geatly aff&apos;ected by rhenium and therefore are not a ttlajor factor in the ductili zing rhenium effect in Croup VI-A metals. THE interface energies of the refractory Group VI-A metals, chromium, molybdenum, and tungsten, are not well-established. The objective of this investigation was to study the liquid surface tension, solid surface energy, and grain-boundary energy of these metals and compare them to those found for the bcc solid-solution alloys, Cr-35e,&apos; 0-33e,&apos; and -25e. Five techniques were used to measure interface energies in high-purity polycrystal rod, wire, and sheet at 0.6 to 1.0 of the absolute liquidus temperature. The alloys were chosen to see if there was any connection between interface-energy behavior and the ductilizing rhenium effecL4j5 EXPERIMENTAL WORK Materials. A description of the materials used is presented in Table I. Chromium rod was prepared by arc melting iodide process crystals supplied by Chromallo Cor., hot extruding, and warm swaging to 0.63-cm-diam rod.6 The sheet was prepared by rolling as-extruded rod to 95 pct reduction in area from a hydrogen furnace at 800" to 900°C and surface grinding off 0.02 cm from each face. Cr-35Re rod was prepared by arc melting sintered rhenium powder and iodide chromium crystals, warm rod rolling to 50 pct reduction in area in cans, and swaging to 60 pct reduction in area at 1100" to 1200°C. Some of the rod was warm-rolled to sheet and then surface-ground. Portions of swaged chromium and Cr-35Re were further reduced by swaging and drawing to 0.013-cm-diam wire by the General Electric Co. Mo-33Re and W-25Re rod, sheet, and wire were provided by Chase Brass and Copper Co. The molybdenum sheet consisted of two lots, both essentially the same except for the carbon content. Liquid Surface Tension. The liquid surface tension of Cr-35Re, Mo-33Re, and W-25Re was measured by a combination of pendant-drop and drop-weight methods using techniques already decribed." Following out-gassing, molten drops were formed on the ends of centerless-ground Mo-33Re and W-25Re rods by electron bombardment at 5 x 106 mm. Similar drops were formed on outgassed Cr-35Re rods by induction heating under 1 atm of 99.995 pct Ar. Solid Surface Energy. Solid surface energy was measured by conducting microcreep experiments on molybdenum, Mo-33Re, chromium, and Cr-35Re wires at 2350°, 2306, 1550°, and 180O°C, respectively. In preparation, gage marks -2.5 cm apart and -0.001 cm deep were circumferentially scribed on the wire with a razor blade. Weights of the wire material were then attached. Five to seven reasonably straight wires were hung in a container made out of the wire material. The free end was placed through a small hole in the removable top and secured by bending a small portion 90 deg. The containers not only tended to provide vapor-solid equilibrium for the wires but also protected them from gaseous impurities. They were nominally 2.5 cm in diam by 5 cm high and were made from extruded chromium rod, Cr-35Re arc casting, molybdenum bar stock, or welded Mo-33Re sheet. After deg re as ing, the assembly was outgassed at a relatively low temperature to 2 x 10"5 mm and then recrystallized 2 to 8 hr at the creep temperature in a rhenium-element resistance furnace. The static argon atmosphere was gettered by tantalum radiation shielding. Specimen temperature was measured optically to 25"C using calibration with known melting points and blackbody conditions. The wires generally developed a stable bamboo-type structure according to Fig, l(b), (c), and (d) and retained their gage marks [upper portion of Fig. l(d)]. One or two of the weights were clipped off to provide a low load for the creep anneal. To minimize the possibility of bending or breakage, the wires remained attached to the top of the annealing container which was held to keep the wires vertical. The distance between gage marks was

Jan 1, 1967

By G. W. Toop

In a recent publication,31 Darken has derived an equation to describe thermodynamic behavior in ternary metallic solutions with compositions near pure component 1: Eq. [I] is understood to be a general equation, consistent with the ternary Gibbs-Duhem equation, which is proposed as a logical formalism in view of observed behavior in some binary metallic solutions31&apos;32 rich In Eq. and am are constants obtainable from the 1-2 and 1-3 binaries. The parameter 023 may be determined from measurements on the ternary The purpose of this discussion is to compare Eq. [I) or [3] with other ternary formulations involving binary terms, within the regions of validity of Eqs. [I], [2], and [3]. First, the ternary point is considered to be at the intersection of two composition paths, one with constant N1 and another with constant N2/N3 as shown in Fig. 10. The terms in Eq. [3] may be related to the binary points shown by multiplying the first term on the right-hand side of Eq. [3] by N2 (1) /l -N1, the second term by the third term by and the fourth term by each multiplier being unity: It should be noted here that no suggestion has been made that either the binary or the ternary systems form regular solutions. However, Eq. [5] and hence Eq. [3] shows that the contribution made to the ternary excess free energy from the 1-2 and 1-3 binaries has the same form as for a regular ternary system.1 Before considering the term a23 for the above case, a second geometrical relationship is examined with the ternary point at the intersect ion of three composition paths with constant N1/N2, N2/N3, and Nl/N3, respectively, as shown in Fig. 11. For this geometry, ternary values of NZ and N3 in terms of the binary values shown may be substituted into Eq. [I]. Then by making use of identities of the form Eq. [6] contains terms that are similar to those in a ternary regular solution formulation34 based on the geometry shown in Fig. 11. Although at finite concentrations, unless the 1-2 and 1-3 binaries form

Jan 1, 1968

By A. Kenneth Schellinger, O. Cutler Shepard

Overgrinding, Or the breaking of ore particles into sizes smaller than required for liberation, is a first-magnitude problem in grinding for concentration processes. The conventional ball mill-classifier circuit used in commercial grinding produces mineral particles that are all ground to pass an upper size limit, while the proportion of very fine sizes, or slimes, is uncon rolled. Calculations based on measurements made in commercial plants which were grinding ore for flotation concentration indicate that about go pct of the energy used in grinding is consumed in useless overgrinding.1 In addition to accounting for the consumption of a large amount of energy, over-grinding is detrimental to the flotation process. Overground slime coats larger partitles and inhibits selective action by the flotation reagents on particles which by themselves could be separated very well. A further difficulty is that extremely finely ground minerals do not respond satisfactorily to flotation-collecting reagents, and both selection and recovery decrease markedly with particles finer than 5 to 10 microns.2 conventional classifier-ball mill circuits inherently tend to overgrind the valuable minerals more than the gangue minerals because most valuable minerals are of higher density and are softer and more friable than the gangue minerals. The rem- edy to this situation would seem to be a separating mechanism which would separate free valuable mineral particles regardless of size and density considerations and a mechanism which would operate in the grinding mill so that valuable mineral grains would be removed from the grinding machine as soon as they are freed. A consideration of these ideas led the authors to the conception of a simultaneous grinding and flotation mechanism. So far as the authors are aware, such a machine has never been tried, even on a laboratory scale. Development oF Apparatus and Experimental Method Apparatus development went through several stages before a really workable machine was devised. Work was started with a large cast-iron mortar 7½ in. in diameter and 8 in- deep. A cast-iron disk Was mounted on the end of a vertical shaft SO that it fitted loosely into the bottom of the mortar. On top of the disk four radial cleats ¼ in. high were bolted to agitate the ball charge as the disk, or impeller, rotated. The vertical shaft was driven at 100 rpm by a mechanism improvised from an old coffee-mill type of grinder. A hole was drilled into the bottom of the mortar through which compressed air was introduced for frothing. In operation, more charges of Ore which had been crushed to pass an 8-mesh screen were placed in the bowl along with water and suitable reagents. The impeller was then started and the compressed air turned On so that the ore was ground while being exposed to air bubbles. Mineralized froth was

Jan 1, 1949

By James T. B. Ives

The map exhibited* as an example of my method of construct ing geological strata-maps is essentially an educational appliance. The method, however, is available for the production of maps of comparatively small areas, which, I am confident, will be found of great practical value to mining engineers. Before stating how the method may be so applied I will briefly describe the map exhibited, as the easiest way of making my meaning clear. Almost any region might be taken. This map represents the eastern half of the United States; and the geology is that of the map issued by the Geological Survey, and revised and extended subsequently by Professor Hitchcock for your Institute. I use ten cards, of the colors used in the geological map, each having the geog raphy of the area printed upon it; and I superimpose these in the order in which the colors occur in the index to the map. I next cut away a portion of each card, excepting the lowest, leaving only so much of each as represents the exposure of the formation of that color plus all those which overlie it. When that is done, the whole, looked at from a distance, appears to be an ordinary geological map. Looked at more closely, however, the formations are seen to overlie one another, as in nature. The cards are covered with glass in a frame, which, hinged at the bottom edge, can be let down. The cards are then found to be all hinged in the same manner, and they, too, may be lowered, one after the-other. I am told by teachers of geology of great experience and the highest reputation that by this appliance they will be assisted in im parting to students the first facts and principles of geological sci ence. Having let down the whole series of cards, until that repre senting the Archaean is seen underlying all the rest, the teacher will gradually rebuild it. The Cambrian will thus be laid down upon the Archaean before the eyes of the class, the Silurian upon that,

Jan 1, 1888

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-&apos;. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-&apos;, respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.&apos;&apos;~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By H. E. Rorschach

Activity in Oklahoma oil fields made 1937 one of the best years since 1926. During the year, 3454 wells were completed, an increase of about 25 per cent over the year 1936. Purchasers reports filed with the Corporation Commission of the State of Oklahoma showed a total of 221,842,-788 bbl. of oil purchased from leases in 1937, an increase of about 10 per cent over 1936. The assembly of a complete table of all of the oil fields in Oklahoma has not yet been achieved. Many of the early records of operators and pipe-line companies are incomplete. Table 1 includes all of the new fields, and this year there has been added work done covering pools discovered in previous years, so that most of the important fields in the state of Oklahoma are included therein. The outstanding development of the year was the discovery of the producing horizon classified as the Wilcox in western Payne County by the Mid-Continent Petroleum Corporation on a unitized block in sec. 18, Tp. 18 N., R. 2 E. This block is operated hy the Mid-Continent and owned in conjunction with the Carter Oil Co., Transwestern Oil Co. and Sinclair-Prairie Oil Co. Another important development of the year was the extension of the deep zone in the old Fox-Milroy area of Carter and Stephens Counties. Some of the other discoveries made during the year 1937 are South Cromwell, discovered by Sinclair-Prairie Oil Co.; Cromwell extension of the Fitts pool in Pontotoc County; discovery of the Langston area in Logan County; discovery of the Sporn area in Lincoln County by Skelly Oil Co. and the discovery of the North Wellston area in Lincoln County by Standard Oil & Gas Co. Table 2 shows the new oil areas discovered in Oklahoma during the year 1937 and areas that were discovered in 1936 but developed in 1937. Fox-Milroy Area.—Three wells were completed to the deep producing zone during the year. One of the wells completed in the early part of the year uas the Carter Oil Company&apos;s No. 1 Harley in sec. 24, Tp. 2 S., R. 4 W., 3 1/2 miles northwest of the original discovery well, the Ruth

Jan 1, 1938

By E. Miller, J. M. Eldridge, K. L. Komarek

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.&apos;2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"&apos;12 were made to join the inner and outer titanium

Jan 1, 1968

By N. F. Schulz, H. A. Lex, J. D. Zetterstrom

A green ball of iron ore faces many perils from the time it is formed until it finally emerges from the pelletizing furnace as a hardened pellet. For instance, if the rate of heat transfer into a ball is sufficient to produce vapor from either the free or combined water more rapidly than it can escape at a tolerable pressure, the ball may split, spall, or even explode, a failure commonly known as decrepitation. To avoid such failures, one must either limit the rate of heat transfer during the drying and preheating stages, at the expense of production rates, or improve the decrepitation resistance of the green balls. The latter remedy may often be accomplished through changes in ore preparation, balling procedures, or the judicious use of binders or other additives. INTRODUCTION Pelletization has become established as an especially desirable method for the agglomeration of fine taconite concentrates and it promises to be equally satisfactory for improving the physical structures of certain natural ores. A high-quality pelletized iron ore consists of uniformly sized spheres, usually about 1/2-in. diam, which are strong enough to resist abrasion and breakage during handling and which reduce well without disintegration in the blast furnace. The unfired agglomerates, "green balls", are subject to several destructive effects that must be avoided or minimized if a high-quality product is to be obtained by pelletization. Among these are abrasion and impact deformation or breakage during handling of the wet green balls, deformation and breakage by compressive forces in the bed of ore in the pel-letizing furnace, decrepitation during drying and preheating, wind erosion, and radial cracking at firing temperatures. Moisture condensation from the warm saturated gases downstream from the drying zone on wet, cool balls may cause bed collapse if it becomes excessive. Decrepitation is defined as the sudden disintegration of green balls, usually with an audible pop, that occurs when they are heated too rapidly during the drying or preheating stages of the pelletization process. The extent of ball disintegration may vary from merely splitting off a small fragment to almost total disintegration into the original ore particles making up the ball. Such ball destruction results in a decreased yield of pellets, and the fragments, which also tend to interfere by obstructing the gas flow through the bed, must eventually be screened from the fired product and recycled. The closely related type of ball failure that sometimes occurs during the high temperature firing stage, resulting in radial cracks without fragmentation, was not considered to be decrepitation for the purpose of this investigation. Failure by decrepitation is not usually a serious problem in the pelletization of taconite concentrates. The problem is significant, however, in the pelletization of some natural ores, especially those containing hydrous iron oxides. In some instances, economicd production rates cannot be maintained if the drying and preheating rates are slowed down enough to avoid decrepitation. OBJECTIVES This investigation was undertaken to: (1) Develop a practical laboratory means for quantitatively measuring the tendency for green balls to decrepitate in iron ore pelletizing furnaces, and (2) Investigate the causes and cures of ball decrepitation. MATERIALS Two iron ores were used in the work reported here: a taconite concentrate at 90% minus 325 mesh, containing 65.0% Fe, 8.4% SiO2, and no loss-on-ignition; and a crude oxidized ore at 54% minus 325 mesh, containing 59.1% Fe, 3.6% SiO2, 1.1% A12O3, and 9.5% loss-on-ignition. For a special test of effect of particle size distribution on decrepitation, two other

Jan 1, 1967

By D. J. McAdam

In a series of papers the author and associates have discussed the influence of temperature on the tensile properties of metals.11-18 These papers present much information about the influence of temperature and the stress system on the conventional indices of mechanical properties, with special attention to the fracture stress. A recent study of the data, however, has revealed much additional information about the influence of temperature on the fundamental factors involved in the flow of metals. The present paper presents results of this study. Attention will be confined almost entirely to results derived from tension tests of unnotched cylindrical specimens at strain rates a little slower than those used in ordinary tension tests. According to a concept first presented by Ludwik and elaborated in recent papers by others,8,9,22,23 the mechanical state of a metal depends on the total plastic strain, but not on the temperature during straining, provided that the only structural changes are those essential to plastic deformation. In the summer of 1948, however, the author made the previously mentioned study of results of a general investigation by the author and associates and reached the conclusion that the mechanical state depends not only on the total strain, but also on the temperature during the straining. A number of diagrams were then prepared. These conclusions were presented without diagrams in a discussion last October of a paper by Dorn, Goldberg and Tietz.2 The metals used in the investigation on which this paper is based were Monel and oxygen-free copper. The Monel was supplied by the International Nickel Co. through the courtesy of Dr. W. A. Mudge. The copper was supplied by the Scomet Engineering Co. through the courtesy of Dr. Sidney Rolle. The data to be presented are based on results of tests at temperatures ranging between 165 and — 188°C. Description of the apparatus and methods of test are given in previous papers.1011&apos;1"2 The present paper is the first part of the general discussion of the influence to temperature on the stress-strain-energy relationship for metals. The next paper will deal with metals that are subject to structural changes other than those induced solely by plastic deformation. Influence of Temperature and Plastic Strain on the Flow Stress of Monel and Copper For a study of the influence of temperature on the stress-strain relationship, flow-stress curves obtained with annealed metals at various temperatures will be compared with curves obtained with the same metals after cold drawing or cold rolling at room temperature. Diagrams thus obtained with Monel and copper are shown in Fig 1 to 8. Fig 1 to 7 show the variation of the flow stress with temperature and plastic strain; Fig 8 is a diagram of a different type, derived from Fig 4 to 7. In Fig 1 to 7 strain is expressed in terms of A0/A, in which A0, and A represent the initial and current areas of cross-section. Since values of Ao/A are represented on a logarithmic scale, abscissas are proportional to true strains; moreover, the true strains representing prior plastic deformation and those representing subsequent strain during a tension test are directly additive. Fig 1 shows flow-stress curves obtained with annealed Monel. Five of the curves are based on results of tension tests. Between yield and the maximum load, the flow was under longitudinal tensile stress; between the maximum load and fracture, the local contraction induced transverse radial tensile stress. The portions of curves designated F, therefore, represent flow with increasing radial stress ratio, the ratio of the transverse stress S3 to the longitudinal stress Si. Curve Fo is based on the ultimate stresses of specimens taken from bars that had been cold drawn various amounts.17 Since the tensile stress at the maximum load is unidirectional, curve Fo represents the course that a flow-stress curve would take if the stress during an entire tension test could be kept unidirectional. The flow-stress curve F obtained at room temperature (Fig 1) has been established accurately by numerous measurements of the diameter of the specimen during the extension from yield to fracture.17 At the time of the experiments, however, no apparatus was available for measuring the diameter during tension tests at low temperatures. Nevertheless, curves have been established to represent with sufficient accuracy the flow at low temperatures. Each flow-stress curve must be tangent to a curve U, which starts at a point representing the ultimate stress of annealed metal. Since the ultimate stress is based on the area of

Jan 1, 1950

By W. F. Chiao

Ultrasonic attenuation, a, measurements in the frequency range of 5 to 55 mc per sec have been studied to determine their quantitative relationship with the following three variables of mixed microstructures in steels: 1) the volume percent, XF, of polygonal fer-rite in mixed structures of martensite and polygonal ferrite in Fe-Mo-B alloys: 2) volume percent, XA, of retained austenite plus martensite aggregates in high-carbon steel; and 3) substructural differences between 100 pct bainitic ferrite structures formed at various temperatures. The quantitative relationship obtained in the first two conditions by plotting a us the known structural parameters can be expressed, respectively, as: where al, a 2 and C1, Cz are constants. In the third condition the nature of the attenuation depends on the state of dislocations generated at the transformation temperatures and also on the alloy composition. From these measured results, the mechanism of ultrasonic attenuation caused by these mixed microstructures can also be studied. MUCH interest has recently been shown in the application of ultrasonic attenuation and wave velocity measurements to the study of the microstructural characteristics of steels. The general aims of most of the investigations in this field can be grouped into two categories: one is to study the mechanisms of ultrasonic losses caused by the characteristic phases in the microstructure of steel,&apos;&apos;&apos; and the other is to develop nondestructive test methods and applications for quality control.~&apos; 4 Apparently no work has been done on the evaluation of ultrasonic attenuation meas -urements as a means of quantitative determination of a given phase in the microstructure of a steel. It is well-established that the decomposition of austenite results in four main microstructural constituents—polygonal ferrite, pearlite, bainite, and martensite—and that each phase has different mechanical properties. Thus, when a steel consists of mixed microstructures, the mechanical properties can often be related to a quantitative measure of the volume percent of each phase present. This study relates ultrasonic attenuation measurements to: 1) the volume percent of polygonal ferrite in mixtures of martensite and polygonal ferrite in Fe-Mo-B alloys; 2) the substructural differences between 100 pct bainitic ferrite structures formed at various temperatures; and 3) the vol- ume percent of austenite in austenite plus martensite aggregates in a high-carbon steel. The choice of the specimen materials was based on the laboratory stocks which were suitable to produce the required mixed microstructures for this study. EXPERIMENTAL PROCEDURES Materials and Heat Treatment. Polygonal Ferrite Plus Martensite Structures. This mixture of phases was produced in a vacuum-melted Fe-Mo-B alloy. The alloy was hammer-forged at 1900" ~ to a -f-in.-sq bar. By isothermally heat treating the alloy at 1300° F for various times and then water quenching, variations in the amount of polygonal (or proeutectoid) ferrite can be controlled in a microstructure in which the balance of the material is martensite. In the present work, four different times of isothermal transformation were adopted; after heat treatment, the four specimens were machined for ultrasonic measurements. The compositions, heat treatments, and dimensions of the four specimens are listed in Table I. 100 pct Bainite Structures Formed at Different Temperatures. It has been well-established by Irvine et al.= that the presence of molybdenum and boron in ferrous alloys can retard the formation of polygonal proeutectoid ferrite and expose the bainitic transformation bay, so that a more acicular or bainitic ferrite can be obtained over a wide range of cooling rates. Their investigation6 also showed that the mechanical properties of fully bainitic steels are usually closely dependent on the substructural characteristics of the steels. For studying the substructural characteristics in completely bainitic structures, six Fe-Ni-Mo alloys, of which five were free from carbon addition and one with 0.055 pct C addition, were selected so that a wide range of hardness values for 100 pct bainitic ferrite structures could be produced by normalizing at 1900" F followed by air cooling. The different bainitic transformation temperatures were recorded during air cooling. All of the alloys were vacuum-melted and then forged at 1900" F to square bars. Data on the six specimens of these structure series are summarized in Table 11. Austenite Plus Martensite Structures. The high-carbon steel used to study austenite plus martensite structures was vacuum-melted and then forged into Q-in.-sq bar. The series of mixed structures of austenite plus martensite was produced by quenching the specimens from the austenitizing temperature to room temperature and then refrigerating them at various temperatures within the range of martensite transformation to produce different amounts of retained austenite. Data on the four specimens of this series are listed in Table 111. Quantitative Analysis of the Microstructures. The microstructures containing martensite plus polygonal ferrite were analyzed by the point-counting technique.

Jan 1, 1969

By A. R. Jr. Amos

LOG washers have been used for many years in the washing of clay iron ores, phosphate rock and manganese ores, but not until the past 15 years have they been employed to any extent in the preparation of aggregate materials and fluxing stone. For a machine of such importance where tenacious clay or soft rock must be eliminated, there are few data generally available. The purpose of this paper is to set forth the results obtained from several operations, together with a few suggestions for planning a specific installation. Where the material to be washed out consists of loose surface soil, silt, or small amounts of quickly soluble clay, there is little competition with other forms of washers, because greater power and maintenance are required for the operation of log washers, but where the foreign matter is a stiff clay, such as occurs with high-calcium limestones and in marginal gravel deposits, the ability of other kinds of washers to eliminate com-pletely the hard clay balls is at least uncertain. Then the log washer comes into its own field, for with the breaking and churning action of the logs it will clean out the toughest clay. Even with material from the hydraulic dredge, if it contains tough clay, the log washer is desirable unless the gravel is subjected to a costly soaking and rehandling process. Recently there has been a considerable development in other types of machines to accomplish these results but it is not within the scope of this paper to make comparisons between competitive types, but to present the best obtainable data on log washers only. From the primitive design that gave it its name, a long log hewn from a tree, with paddles forged to shape from strap iron and attached by lag screws, the log washer has gradually been developed to the present all-steel type. As now manufactured, the log washer consists essentially of two built-up logs on which are mounted a series of paddles, carried by shafts fitted at the ends of the logs on bearings fastened outside the enclosing steel box, or trough, which is set at an angle of about 5° to 10° and into which the material is fed. Stuffing boxes at the places where the shafts pass through the box at the lower end are equipped with water-

Jan 1, 1936

By A. R. Jr. Amos

LOG washers have been used for many years in the washing of clay iron ores, phosphate rock and manganese ores, but not until the past 15 years have they been employed to any extent in the preparation of aggregate materials and fluxing stone. For a machine of such importance where tenacious clay or soft rock must be eliminated, there are few data generally available. The purpose of this paper is to set forth the results obtained from several operations, together with a few suggestions for planning a specific installation. Where the material to be washed out consists of loose surface soil, silt, or small amounts of quickly soluble clay, there is little competition with other forms of washers, because greater power and maintenance are required for the operation of log washers, but where the foreign matter is a stiff clay, such as occurs with high-calcium limestones and in marginal gravel deposits, the ability of other kinds of washers to eliminate com-pletely the hard clay balls is at least uncertain. Then the log washer comes into its own field, for with the breaking and churning action of the logs it will clean out the toughest clay. Even with material from the hydraulic dredge, if it contains tough clay, the log washer is desirable unless the gravel is subjected to a costly soaking and rehandling process. Recently there has been a considerable development in other types of machines to accomplish these results but it is not within the scope of this paper to make comparisons between competitive types, but to present the best obtainable data on log washers only. From the primitive design that gave it its name, a long log hewn from a tree, with paddles forged to shape from strap iron and attached by lag screws, the log washer has gradually been developed to the present all-steel type. As now manufactured, the log washer consists essentially of two built-up logs on which are mounted a series of paddles, carried by shafts fitted at the ends of the logs on bearings fastened outside the enclosing steel box, or trough, which is set at an angle of about 5° to 10° and into which the material is fed. Stuffing boxes at the places where the shafts pass through the box at the lower end are equipped with water-

Jan 1, 1936

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,&apos; but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks&apos; and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.&apos;y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.&apos; In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.&apos; These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964

By Frank M. Brooks

Endeavoring to meet the requirements of more oil created by the war effort, the oil industry of Kansas in 1944 maintained a level of exploratory and development work well above the average of previous years. During the year, 1866 test wells were drilled, of which 838 were completed as new oil wells, 89 as new gas wells and 939 as dry holes. These figures compare with 895 new oil wells, 32 new gas wells and 834 dry holes for a total of 1761 tests in 1943. Thus, there was a marked decrease in the number of new oil wells, and an increase in the new gas wells and dry holes. The total daily initial potential of production discovered by the successful wells amounted to 494,689 bbl. of oil as compared with 736,297 bbl. in 1943. The increase in unsuccessful tests and decrease in the daily initial potential of production has caused considerable comment and speculation among the oil operators of the state. This tends to confirm the fact that each year it is becoming harder to find the remaining oil fields. The total number of wildcats drilled in Kansas was 651 in 1944, including the so-called "extension wildcats" (more than 1/2 to I mile from known production). Of this number, 410 are classified as "rank wildcats," being more than one mile from production. The total of 651 compares with the total of 577 for 1943, showing an increase in wildcat drilling of 74 test wells: Of these tests, 81 were successful in finding new oil fields or substafitially extending known areas of production, and 20 either found new gas pools or extended old ones. The ratio of dry holes to producing wells among the "rank" wildcats was approximately 10 to I (372 dry and 38 successful). This compares with a ratio of 10 to I in 1943, 11 to I in 1942, and 6 to I in 1941. A compilation of the results obtained by 34 active companies, including all of the major companies, reveals that their efforts accounted for 286 rank wildcat wells, of which-37 found oil or gas, making a dry-hole percentage of 87. Approximately 55 per cent of all, tests (pool and wildcat) were failures. Thc Kansas Nomenclature Committee of the Kansas Geological Society named and classified 43 new oil fields and 8 new gas fields during the year. The discovery wells of the new oil fields had a total initial potential of 18,358 bbl. for a per well average or&apos; 427 bbl. The average initial potential per well in 1942 and 1943 was 894 and 419 bbl., respectively. With nearly all wells producing at their economic capacity, the total production for Kansas during 1944 totaled 101,896,704 bbl., which compares with total runs of 107,709,679 bbl. in 1943. Production of natural gas during 1944 reached a new high record of 135 billion cubic feet. This compares with 122 billion cubic feet for 1943, and 98 1/2 billion cubic feet for 1942. The large Hugoton field of Southwestern Kansas accounted for about half of the total gas produced. Highlights OF the Year Although 51 new fields were found in the state during 1944, it is apparent that the

Jan 1, 1945

By J. Larsen-Badse

The resistance to dry sliding abrasion us been measured for some hardened and tempered carbon steels. The wear resistance, defined as the reciprocal of the volume loss per unit sliding distance, is found to vary linearly with the hardness of the abraded surface. The data fit two lines, one, of high slope, for the pure metals and for the annealed steels and another, of smaller slope, for the hardened and tempered carbon steels. A relationship is developed showing the alwasion resistance to be proportional to the hardness of the material and to en, where n is the exponent of work hardening. The values of n and of the hardness FOR most materials a high resistance to abrasion is generally associated with a high value of indentation hardness. Brine11 even used the abrasion resistance as a measure of hardness in an attempt at expanding the hardness range covered by his indentation-hardness test.&apos; When comparing different types of materials there is, however, only a very general relation between abrasion resistance and hardness. Sample brittleness seems to contribute to the deviation from a direct relationship. In general, increased brittle- are those relating to the heavily deformed abraded surface. However, for materials having n constant or varying m a regular manner over a wide range of strailts, the wear resistance will also be a linear function of the bulk hardness of the material. For tempered steels containing a dispersion of cementite in ferrite the increase in wear resistance due to the dispersion is found to be a linear function of the volume fraction of Fe3C and of the reciprocal of the mean free ferrite path. This indicates indirectly that the yielding of this material, when it is already heavily deformed, follows the Orowan criterion. ness leads to decreased abrasion resistance.&apos; When comparing materials in the same group, e.g., the metals, the spread is less. Kruschov found that the abrasion resistance of pure metals and of annealed steels is directly proportional to the hardness of the metal. For hardened and tempered steels he obtained another linear relationship, one of smaller slope and intersecting the line for the pure metals at the location of the data for the annealed steels. He also found that the abrasion resistance of cold-worked metals is independent of the degree of cold working. This shows, as he concluded, that the process of abrasion work hardens the metal in the surface region to a very high degree.

Jan 1, 1967

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."&apos; The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall&apos; reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel&apos;&apos; structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,&apos; whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By John C. Cook

Long-wave short-pulse radar has been shown capable of exploring to distances of several hundred feet through massive, dry rock salt. Exploration distances of 30 to 60 ft through bituminous coal and massive limestone, respectively, have also been demonstrated with low-power experimental radar equipment in underground mines. Working ranges up to 250 ft in limestone and coal are considered feasible. Radar reflections should be produced by all large electrically contrasting objects such as fault gouge masses, wet shattered ground, metallic mineralization, adjacent mine workings (dry or flooded), and abandoned drill holes. It is believed that radar can locate such obstacles in advance of underground mining through all massive rocks of low free-water content, including many igneous and metamorphic rocks. Three years of studies and experiments in radar exploration through rocks are reported.

Jan 1, 1974