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By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By M. H. Forester, John D. Cooner

ALTHOUGH the unmined anthracite will last for approximately 150 years, most of the thicker and cleaner coal beds have been almost entirely first-mined and pretty well robbed, leaving much of the present and future production to come from thin and dirtier beds. Herewith is a section of one of the dirty beds being mined in the Wyoming region [ ] This section shows that 45.8 per cent of the bed is made up of impurities and that the 45 in. of coal in the bed is in five benches, the thickest of which is 19 in. In some localities of the anthracite region there are 14 beds of minable coal. Orderly and proper mining of the coal makes it necessary to rob or second-mine--almost all beds have already been first-mined-in sequence from the top downward. Therefore the robbing of the few remaining portions of the thicker and cleaner beds is in many instances being held up by the mining of the overlying thin and dirtier coal beds. Impurities Impurities consist of fire clay, slate, rock, and bone. The latter, which is black, contains 40 to 60 per cent carbon and often resembles good coal. In some beds there are also bands of "blue" coal, which, as the name implies,

Jan 1, 1950

By W. O. Philbrook, C. W. McCoy

The reduction of chromous oxide from lime silica alumina slags by carbon-saturated iron behaves as a first-order process having a rate of 0.001 grams Cr min 1 cm 2 (pct Cr ) , substantially independent of slag composition and temperature over an important range for iron smelting. The equilibrium ratio (pct Cr)/[pct Crl is below 0.04 for slags having lime-silica ratios above 0.6. MANY studies have been conducted on chromium in slag-metal systems under oxidized conditions. The Purpose of these investigations has been twofold; namely, (1) to determine those conditions which lead to greater chromium recovery in electric-furnace and open-hearth practice, and (2) to determine the nature of oxide inclusions and de-

Jan 1, 1959

By W. C. Hagel, H. J. Beattie

Variations in the secondary phase reactions of six nickel-and cobalt-base alloys were determined as a function of solu-tioning from 1700" to 2200°F and aging at 1200" to 1800° F for times up to 1000 hr. Room-temperature impact energies and hardnesses were also measured. Precipitation hardening of these alloys results mainly from the grain-interior formation of ? '; M23C6 appears principally as grazn-boundary cells which can be eliminated by intermediate high-temperature aging treatments. Cellular precipitation of ?' occurs up to 1500°F in cobalt-nickel alloys devoid of chromium, where precipitation by this mode can be attributed to a large degree of lattice disvegistery. THE usefulness of nickel- and cobalt-base alloys is dependent on balancing the strength and ductility provided by the solid-solution matrix, dislocation-type subboundaries, grain-boundary phases and genera1 precipitation within individual grains. Since equilibrium relationships for complex austenitic alloys are not easily fixed, a satisfactory balance

Jan 1, 1960

By Alfred E. Hunt

Tars paper is suggested by the appointment on the part of the American Societies of Mechanical and of Civil Engineers of committees upon the subjects of " Standard Tests and Methods of Testing," and " Uniform Methods of Tests of Material used in Metallic Structures," respectively, and by a study of the report of one of these committees, and other papers. Moreover, the writer has had frequent occasion to hear the complahts of tnanufacturers who furnish structural material subject to specifications, that in the tests prescribed, the number of tests required, and the methods of making

Jan 1, 1892

By Harry C. Swanson

TRANSPORTING concrete from mixer to forms has always been a problem. Twenty-five years ago this task was generally accomplished by means of wheelbarrow or concrete buggy. On large dam jobs, as the number of these projects increased, the gantry crane or highline came into use. Today several methods of handling concrete are employed on smaller surface construction jobs, for example, transit-mix trucks or dumpcrete trucks, which have crawler cranes with buckets for placing concrete into forms. In 1944, during early stages of developing Mather mine A shaft, several large underground concrete jobs were necessary. At this time the Cleveland-Cliffs Iron Co, purchased the first pump-crete machine, introduced by the Chain Belt Co. of Milwaukee. The machine was used to pour approximately 200 cu yd of concrete for a dam, or bulkhead, located 400 ft from the shaft. Concrete was mixed on surface, lowered down the shaft 1000 ft in a 2-cu yd bucket hung under one skip, spouted into the bowl of the pumpcrete machine from the bucket, and pumped directly into the forms. Since the day of the first pipeline concrete in 1944 to the present time, other equipment and other methods have been developed to permit transportation of concrete by pipeline through vertical and horizontal distances totaling 1 mile from mixer to forms. Much of the efficiency in present handling of underground concrete can be credited to the Bethlehem Cornwall mines, where concrete was transported through 6-in. pipe for great distances down an inclined shaft and along levels into forms.' During initial development of Mather mine B shaft, with concrete work under way on two or more levels at one time, the pneumatic concrete placer, Fig. 1, was selected as best adapted for underground concrete transportation. The 3/4-cu yd pneumatic placer is a small machine readily moved from one location in the mine to another. It can be equipped with two sets of mine car wheels, which will permit moving on regular mine tracks. It is therefore possible to send concrete through the pipe at great velocity; the pipeline is clean after each shot except for the film of cement adhering to the inside. With the proper slump in the concrete, it is possible to shoot concrete 2000 ft with this machine, using the mine supply of compressed air at 95 psi. This equipment was first used at Mather mine B shaft to concrete slusher drifts, Figs. 2 and 3, and finger raises located about 2000 ft from the shaft. In several instances there were bends into crosscuts and up vertical distances into the forms. For the first pours two placers were used. The first was located near the shaft where the concrete could be spouted into it from a 2-cu yd concrete bucket on the cage. The second was set on the side of the drift at a point approximately 1500 ft from the shaft. The concrete was shot directly into the second placer from the first unit and from the second machine directly into the forms. After completion of several pours with the two machines, a trial pour with only one placer located at the shaft proved that the second placer could be eliminated. Since then all pours have been successfully completed with only one placer underground. As production of iron ore from the mine increased and the development program expanded, use of the cage for handling mine supplies and concrete became a major problem. This brought about the first attempt at shooting concrete vertically down the shaft for 2600 ft. A 6-in. pipeline with victaulic couplings installed during shaft sinking was used for the trial. One placer was set on surface 250 ft from the collar of the shaft so concrete could be spouted directly into it from the mixer. This machine shot the concrete 250 ft horizontally on surface to the shaft, 2600 ft vertically down the shaft, and 100 ft horizontally into the second placer located near the rib of the shaft station or plat. The second machine shot the batch into the forms, about 2000 ft. Total distance horizontally and vertically was 4800 ft. The entire time cycle for a ¾-cu yd batch of concrete from the mixer on surface to the forms underground totaled about 5 min. During the past two years the two-placer method from the mixer on surface to the forms underground has proved a very efficient means of transporting underground concrete. Advantages of using pipeline concrete are as follows: 1—Interference with normal mining operation is eliminated. When the cage, skips, mine cars, or mine openings are used for transporting concrete and materials used for making concrete, mine operation suffers in one way or another.

Jan 1, 1955

By E. J. Ripling

A NY mechanism proposed to explain hydrogen embrittlement in titanium and its alloys must, of course, be consistent with the experimental data that characterize this embrittlement. Unfortunately, however, the mechanical behavior of hydrogen-bearing titanium, at least a-ß titanium, has not been unequivocally defined. Lenning, Craighead, and Jaffee have clearly shown that hydrogen cmbrittles a-titanium by elevating its transition temperature, probably as the result of the formation of titanium hydrides. Therefore, in these alloys, hydrogen acts like at least one other interstitial contaminant, namely, nitrogen.&apos; On the other hand, ß-titanium has been shown by these same investigators to tolerate very large amounts of hydrogen without suffering severe mechanical damage.2 Mixing these two phases, however, to form the most important class of commercial alloys, the a-ß alloys, again results in severe hydrogen embrittlement, although the mechanism by which the embrittlement is produced is not of the same type as that which causes brittleness in a alloys. Ductility damage due to hydrogen increases as the strain rate is reduced in a-ß alloys, while embrittlement in a alloys increases as the strain rate is increased, since the latter is a transition temperature behavior. Steel, like the a-ß alloys, becomes more hydrogen sensitive at slow strain rates, suggesting that the mechanism producing the embrittlement in these two metals is similar. Brown and Baldwin&apos; described the hydrogen-produced ductility depression in steel as a function of testing temperature and strain rate by defining the slope of the two surfaces that produced the depression in a three dimensional chart, Fig. 1. One of these surfaces was given by the equations (de/de)4 > 0 (de/dT) < 0 [1] while the other was defined by the pair of equations Surfaces of the type given by Eq. 1 are suggested in two ways. One is an embrittlement mechanism wherein the diffusion rate of hydrogen is competitive with the rate at which the material is being deformed, as suggested by the planar pressure theory of Zapffe and his co-workers.&apos; The other is the diffusion controlled extension of Orowan&apos;s theory on delayed fracture in glass by Petch and Stables.&apos;&apos; Surfaces of the type given by Eq. 2 are also compatible with a mechanism of pressure build up in voids, according to de Kazinczy,&apos; since the solubility of hydrogen in the metal increases with testing temperature so that as the temperature is raised, the pressure in the voids is reduced. Kotfila and Erbin recently presented some data on the dependence of ductility on testing temperature and strain rate for the a-ß 3 pet Mn complex alloy at four different hydrogen levels.H Although data were presented for only three testing temperatures at three different strain rates, their results indicated that surfaces of the types defined in Eqs. 1 and 2 are produced in the alloy when the hydrogen level is sufficiently high—200 and 300 ppm—Fig. 2. Jaffee and his co-workers presented data on a number of different a-ß alloys which indicated the existence of surfaces of the type described by Eq. 2, but the ductility recovery at low temperatures as given by Eq. 1 was not found." In an attempt to aid in crystallizing this description of the ductility dependence of hydrogen-bearing a-ß alloys, tests were conducted by the author on a-ß titanium 140A with three different hydrogen contents. The tensile properties of two as-received rods and one vacuum annealed rod* were obtained over a range of testing temperatures and strain rates as shown in Figs. 3 and 4. Hydrogen analyses were made by the Battelle Memorial Institute on four pieces of the rod whose properties are shown as solid circles in Fig. 4. The hydrogen content of these pieces, taken at widely spaced intervals within the rod, were 280, 270, 289, and 270 ppm, indicating that the hydrogen content within a single as-received rod was quite uniform. One of the broken test pieces whose properties are shown in Fig. 3 as solid circles was also analyzed, and found to have a hydrogen content of 310 ppm. The analyses obtained on two of the vacuum annealed specimens were 92 and 170 ppm.

Jan 1, 1957

By E. W. Gieseke

Coal preparation men today are confronted with problems brought about by changing feed characteristics. The size consist of the coal going to preparation plants has been getting finer and finer. In order to handle these sizes economically, operators are turning to Notation. American Cyanamid Co., in an effort to enable coal flotation plants to produce efficiently at maximum quality and capacity, wnducted experiments which demonstrated that synthetic flocculants are useful for increasing the capacity of coal and refuse filters and for clarifying coal and refuse slurries, and a wetting agent is beneficial in reducing the moisture content of filter cake. Coal preparation men are today confronted with problems brought about by the changing coal markets, changing feed characteristics, and ever increasing labor and supply costs. Small mines are finding it difficult to exist, and the larger mines are rapidly converting to fully mechanized and automated operation to survive. The size consist of the coal going to preparation plants has been getting finer and finer, and the problems facing the preparation plant personnel are growing larger and larger. Facilities can be provided to handle this plant feed in new plants, but the problems are generally not so simple in existing plants where equipment must often be used to perform tasks far beyond its rated capacity. In addition, various state conservation departments, water commission boards, and other Federal and state agencies are endeavoring to eliminate stream pollution. These problems, and many more not mentioned, have been forced on the preparation engineer for reasons of economy and the public interest. In the matter of stream pollution, a determined effort is being made by the coal industry to cooperate with the Federal, state, and local agencies. Economists predict it will be necessary to produce 600 million to 700 million tons of coal by 1970. Bear in mind that the greater proportion of this increased tonnage will have to be processed in existing plants, and you get an idea as to the problems facing the preparation engineer. Methods presently in use for preparing fine coal do an acceptable job down to 48 to 100 mesh. A very large percentage of the - 48 or -100 mesh fraction of the tonnage of coal produced now is being sent to settling ponds or sold at a low figure for reason of quality. This has caused operators to turn to flotation. Building settling ponds and impounding fines is a costly and, at times, impossible method of handling these sizes. Recently a number of flotation plants have been installed to beneficiate material finer than 48 mesh, and these plants have demonstrated that flotation can be successful and increase the plant realization. Coal is a low cost commodity and processes for its beneficiation must be low in cost. Flotation is such a process. It is easily adapted to handling fine coal, requires very little supervision when properly installed, and is economical to operate. Flotation separates coal from refuse and fine clay. For reagents, several combinations are used. Some

Jan 1, 1962

The fate of generations yet unborn lies in man&apos;s hands. Shall it be prosperity, a high standard of living, and the development of spiritual values; or ruin, misery, and a reversion to jungle law? World affairs move in high gear, at high tension, in many directions. Each nation fears the other fellow- races, crosses the white line on curves, skids, takes its half in the center; and the devil take the hindmost. For one, the United States is on the horns of dilemma; it must insure a flow of raw materials of industry and world-wide markets in order that the American people may maintain high standards of living, but the commitments of the United States cannot be fulfilled without trimming present standards of comfort and convenience back to the level of perhaps a quarter of a century ago. A way must be found to retreat without anarchy at home as well as abroad. Everything is relative and all things change, and change is the essence of civilization. It is now clear that man has not kept pace with changes of all kinds, some of them overnight, during the past 50 years. Conventionality has led to stagnation; man now seeks learning of all kinds at an accelerated pace, but men should not be educated beyond their native intelligence for they must be able to apply their education. There must be a resolute action now on 10 great challenges in regard to conservation of human and ma-

Jan 1, 1950

By J. A. Elias, A. J. Heckler

A simplified method is described for the prepauatior~ of comnposite samples for determination of one quadrant of an X-ray pole figure of a sheet material by the Schulz reflection method. Other special conzposite sampling methods were used to investigate specific areas of the pole figures. Plotting nets for these sampling plans were drawn by a computer. Step-scanning techniques were used to obtain detailed information about specific regions of a pole figure. Satisfactory pole figures were obtained for large-grained (0.5 to 1 in. diam) sheet materials. COMPOSITE sampling techniques for preparing one quadrant of an X-ray pole figure have been reported by a number of authors.&apos;-5 All of these methods are similar in that they use a composite sample prepared by stacking and holding together coupons cut from a sheet material. The schulze reflection technique is applicable to the composite sample so that only minor corrections are needed for defocusing and absorption effects. Also, a relatively large area of a sheet is sampled through the use of multiple cross sectional pieces. In general, sampling methods necessary to obtain a composite-type specimen have been formidable enough to discourage their use in routine pole figure determinations. This paper presents a versatile sampling technique which is simpler than those previously described along with an accurate method for obtaining stereographic plotting nets for any orientation of a composite specimen surface. A step-scanning technique is used to obtain more quantitative determinations of specific regions in pole figures, and the composite technique is satisfactorily applied to determine pole figures of very large grained sheet materials. REVIEW OF PREVIOUS TECHNIQUES Mueller and ~nott&apos; first proposed a technique for obtaining one complete quadrant of an X-ray pole figure by using a sheet sample and six different composite samples in which the individual coupons were aligned and held together by two types of jigs. Data from the seven different samples were overlapped to obtain a single quadrant. ~eieran~ and Lopata and ~ula~ obtained a complete quadrant of a pole figure from a single sample prepared by forming a cube from coupons cut from a sheet. These coupons were bonded together using an epoxy cement, and a cut was made at 54.7 deg to the normal, transverse, and rolling directions of the sheet, Fig. I. The normal direction of the cut face projects into one quadrant of a stereographic projection at equal angles to the three principal orthogonal reference directions mentioned above. X-ray reflection data obtained along a spiral path in physical space could then be plotted on a stereographic net offset 54.7 deg from the normal, as shown in Fig. 2. A rotation about an axis representing the surface normal is designated as a, and a rotation about an axis lying in the plane of the surface is 4. From Fig. 2 it is apparent that a tilting angle of no more than 55 deg @ is necessary to obtain the complete quadrant. ~eber~ devised an improved sampling technique by cutting coupons 45 deg to the rolling direction of a sheet, stacking and bonding these with an epoxy cement at an angle of 54.7 deg to a reference plane, and finally grinding and lapping a flat specimen surface parallel to this plane. An important consideration of this technique and that of Lopata and ~ula~ is variation in the diffracting power of the specimen surface due to the bonding medium. While any composite-type sample will have some such variation due to boundaries between coupons, the problem can be minimized by elimination of the bonding medium and by avoiding prolonged etching times which could lead to significant inter lame llar attack of the coupon faces. EXPERIMENTAL TECHNIQUE We were working concurrently though independently on a technique similar to ~eber&apos;s,&apos; but which does not

Jan 1, 1968

By W. C. Browning

The influence of the hydroxyl factor is more damaging to formations penetrated and causes greater consumption of drilling mud additives than previously realized. This hydroxyl effect on clays is essentially independent of the cations present in the drilling fluid and thus differs from the base exchange reactions that have preoccupied mud chemistry with sodium and calcium bentonite concepts for nearly two decades. The new organic polyelectrolyte-con-ditioned muds haw made it possible to use materials other than sodium hydroxide to maintain the alkalinity of such muds. The properties of silicates, as indicated by their dissociation characteristics and buffering action, are such that they can control he pH and alkalinity of drilling muds at the desired level and, at the same time, minimize undesirable hydroxyl effects associated with sodium hydroxide. This use of silicate compounds is different and distinct from prior applications of silicates as deflocculants or shale preservers. Laboratory and field data presented in this report show that silicate compositions can be utilized to adjust the alkalinity of drilling muds and, at the same time, minimize hydmxyl-promoted clay cleavage. INTRODUCTION Studies for improving the efficiency of rotary drilling techniques must consider the chemistry of drilling fluids and of the formations being penetrated. The chemical aspects of drilling must be studied in conjunction with and in relation to the mechanical factors if, for example, penetration rates are to be optimized. Drilling fluid technology has been largely influenced by chemical reactions of the montmorillonite (bentonite) clay minerals. Most of the literature of mud chemistry concerns the properties of bentonite. Clays of the kaolin or illite type, which are nonswelling, are not generally regarded as sources of drilling mud problems. If these nonswelling shale clays are considered, they are commonly regarded as inert solids. Particularly noteworthy is the fact that the relation of surface and colloid chemistry to massive shale bodies has received only scant attention from drilling technologists. Clay studies reported in the drilling mud literature have dealt, for the most part, with the properties of clays in a finely divided state, and often in very dilute suspensions. Yet frequently during drilling, shale problems not related to the rheology of clay suspensions develop in massive non-bentonitic shale sections of zero or near zero permeability. This paper is concerned with surface chemical reactions that can influence the behavior of these non-bentonite clay masses in such a manner as to adversely affect drilling operations. Browning and Perricone1,2 have pointed out that some of the most troublesome shales to drill, such as the Atoka, contain no montmorillonites. They also pointed out that mud problems can frequently be mitigated by reduction of clay cleavage achieved by using drilling fluids with a minimum of available hydroxyl ions. If pronounced clay cleavage occurs during drilling, the borehole may soften, increasing the possibility of sloughing. In addition, the resulting increased incorporation of high-surface-area clay solids into the mud system can reduce penetration rates and necessitate greater chemical treatment. This increase of shale, of colloidal or near-colloidal dimensions, into the drilling mud is due to clay aggregate cleavage and not to base exchange or swelling reactions, such as occur with bentonites. Searle and Grimshaw3 point out the difference between cleavage or slaking reactions of nonswelling clays (such as illite and kaolinite) and the swelling of bentonite. They further state that the speed of slaking is increased in alkaline water. Eitel1 cites Salmang and Becker, who recognized that clay surface reactions impart plasticity and workability to clay masses. Their results clearly show that all liquids which contain hydroxyl groups in their molecules favor the workability of clays. The ancient technique of aging clays in the moist condition to increase their "workability" is evidence that these clay cleavage phenomena are of considerable importance. The same hydration cleavage that occurs during the aging of nonswelling clays for ceramic use also acts to break up cuttings and soften the borehole during drilling operations. The mechanism of cleavage of the crystalline aggregates of illitic, kaolinitic and other nonswelling clays; and the chemical means of controlling this cleavage are therefore of considerable significance to the drilling mud chemistry. Inasmuch as there is little reference in the drilling mud literature to the cleavage reactions of nonswelling clays, the structure of these clays and certain properties that relate to the mechanism of clay cleavage will be reviewed briefly. STRUCTURE OF NONSWELLING CLAYS Clays such as kaolinite, illite and montmorillonite are compmed of alternate layers of (1) silicon-oxygen tetra-

Jan 1, 1965

By H. W. Kropholler, L. A. Cramer, E. T. Woodburn, J. C. A. Greene

A generalized mathematical structure is proposed whereby internal species mass flows within a flotation network are defined uniquely by a matrix of enhancement factors. An element of the enhancement factor matrix is defined as the ratio of the mass flow of that species leaving a given cell in the concentrate to the species mass flow leaving the same cell in the tailings. To predict the enhancement factors, knowledge of flotation kinetics effects is required. Recently experimental data has become available relating to the performance of industrial flotation circuits which indicate that the discrete or discrete-distributed kinetic schemes are capable of reasonably effective simulations. These simulations show the importance of including froth effects. The prediction of performance of networks from small-scale batch tests on flotation streams shows that the model for the froth phase used in the simulations does not scale-up well and that aeration effects are also difficult to predict. The network analysis should be useful in differential flotation of complex ores and it is disappointing-in this context that little information on the kinetics of activation and depression is available.

Jan 1, 1976

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman&apos;s results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman&apos;s demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman&apos;s experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman&apos;s experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman&apos;s experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman&apos;s Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author&apos;s reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By Louise Barton Freeman, Coleman D. Hunter

The total production of oil in Kentucky during the year 1943 reached 7,010,776 bbl., which is more than at any time since 1930. Of this total, 5,287,659 bbl. was produced from the counties west of the Cincinnati arch, 692,359 bbl. from the 18 new pools opened during the year, and 3,260,765 from the Smith Mills pool, which was discovered in August of 1942. This is an important increase in western Kentucky in spite of the low price of crude, and demonstrates effectively the desire of the industry to cooperate in meeting the increased demands made by the war. Western Kentucky Two deep tests were drilled in the Kentucky portion of the Mississippi Embayment this year. Both were drilled to test the St. Peter. One well, drilled in Marshall County by the Adams Oil and Gas Co., did not encounter any St. Peter sandstone but drilled 650 ft. of formation below the position of the St. Peter and above the true Knox dolomite. The other well, in Ballard County, was reported to have tested the St. Peter and to have been temporarily abandoned at 3069 ft. At this depth the well probably was stopped in about the same formation as the Marshall County well. No accurate information is available on the Ballard County well. Several new producing areas were added to the list of fields in the western Kentucky coal basin, in Daviess, Henderson, McLean, Ohio, Union and Webster Counties. The Smith Mills pool was enlarged and production was found in the McClosky (Ste. Genevieve) in addition to the Cypress sandstone from which much of the earlier production had been obtained. There was some interest during the year in testing the Devonian and Silurian formations in the area south and east of the western Kentucky coal basin. In the fall of 1943, a 15 to 20-bbl. well was drilled in Allen County and two more wells are now being drilled. The production was obtained from within a few feet of the base of the Chattanooga black shale, probably in the upper Silurian. One well in Simpson County was drilled completely through the Silurian section before it was abandoned. Several wells were drilled in Logan, Todd and Christian Counties to test the Devonian where it is thinned by removal of the upper formations before deposition of the Chattanooga shale. None of these wells was successful but several other locations are now being tested. The Silurian thins in like manner on the eastern flank of the coal basin as the crest of the Cincinnati arch is approached, and it is along this thinning edge that such fields as the LeGrande, Logsdon Valley, Magnolia, Bowling Green and the Barren County pools were developed. A number of wells were drilled around these old pools in an effort to extend them, some of which were successful. The wells listed this year in Larue, Hardin, Barren, Hart and Warren Counties were drilled in the search for other such fields.

Jan 1, 1944

By Louise Barton Freeman, Coleman D. Hunter

The total production of oil in Kentucky during the year 1943 reached 7,010,776 bbl., which is more than at any time since 1930. Of this total, 5,287,659 bbl. was produced from the counties west of the Cincinnati arch, 692,359 bbl. from the 18 new pools opened during the year, and 3,260,765 from the Smith Mills pool, which was discovered in August of 1942. This is an important increase in western Kentucky in spite of the low price of crude, and demonstrates effectively the desire of the industry to cooperate in meeting the increased demands made by the war. Western Kentucky Two deep tests were drilled in the Kentucky portion of the Mississippi Embayment this year. Both were drilled to test the St. Peter. One well, drilled in Marshall County by the Adams Oil and Gas Co., did not encounter any St. Peter sandstone but drilled 650 ft. of formation below the position of the St. Peter and above the true Knox dolomite. The other well, in Ballard County, was reported to have tested the St. Peter and to have been temporarily abandoned at 3069 ft. At this depth the well probably was stopped in about the same formation as the Marshall County well. No accurate information is available on the Ballard County well. Several new producing areas were added to the list of fields in the western Kentucky coal basin, in Daviess, Henderson, McLean, Ohio, Union and Webster Counties. The Smith Mills pool was enlarged and production was found in the McClosky (Ste. Genevieve) in addition to the Cypress sandstone from which much of the earlier production had been obtained. There was some interest during the year in testing the Devonian and Silurian formations in the area south and east of the western Kentucky coal basin. In the fall of 1943, a 15 to 20-bbl. well was drilled in Allen County and two more wells are now being drilled. The production was obtained from within a few feet of the base of the Chattanooga black shale, probably in the upper Silurian. One well in Simpson County was drilled completely through the Silurian section before it was abandoned. Several wells were drilled in Logan, Todd and Christian Counties to test the Devonian where it is thinned by removal of the upper formations before deposition of the Chattanooga shale. None of these wells was successful but several other locations are now being tested. The Silurian thins in like manner on the eastern flank of the coal basin as the crest of the Cincinnati arch is approached, and it is along this thinning edge that such fields as the LeGrande, Logsdon Valley, Magnolia, Bowling Green and the Barren County pools were developed. A number of wells were drilled around these old pools in an effort to extend them, some of which were successful. The wells listed this year in Larue, Hardin, Barren, Hart and Warren Counties were drilled in the search for other such fields.

Jan 1, 1944

By V. N. Burnhart

After eight years of testing and development, the E. J. Longyear Co. has adapted the wire- line core barrel to small diameter drillholes. Field performance indicates that the apparatus for the BX hole will be an important supplement to the conventional techniques used in the diamond core drilling industry. Higher core recovery, faster drilling progress, and reduced diamond costs will provide substantial savings to the user of coring equipment. The wire-line principle is not new, having been successfully applied to the large-diameter holes of the petroleum industry. But scaling the practices of core recovery in oil well drilling down to the small BX hole presented a number of problems. The technique, difficult even for large holes, was complicated by the exacting limitations of the small diameter in which durable and foolproof mechanisms would be required to operate. Since the maximum benefits could be realized from this sys- tem in holes 1000 ft and deeper or in holes in badly fractured ground, the drill string would have to be able to withstand heavy stresses. Most vital to the success of the idea was the development of a positive latching mechanism to assure proper positioning of the inner tube of the core barrel when the tube is dropped into place. Lastly, little was to be gained from the wire-line method without diamond bits that would give optimum penetration rates and a long service life in the drillhole.

Jun 1, 1955

By R. A. Marriot

The steam-generating plant at the Garfield smelter of The American Smelting and Refining Co. consists of two divisions in which the boilers are classed as direct-fired or waste-heat. The direct-fired boiler plant consists of eight 330-boiler hp. type K-19 and S-I 7 Stirling boilers located in the boiler room adjacent to the power house, and two 330-boiler hp. Stirling type K-19 boilers in the reverberatory building, which formerly were connected to a reverberatory furnace but now are arranged for direct firing. All direct-fired boilers are now fired with natural gas. The waste-heat boiler plant consists of all units connected to reverberatory furnaces, and receiving heat from the exit gases therefrom. In this classification there are two 490-boiler hp. Erie City vertical water-tube boilers, and six 330-boiler hp. type K-19 Stirling water-tube waste-heat boilers. Each furnace has boilers arranged in battery setting. The boilers are directly in front of the furnace and connection is made through a short uptake and flue (Fig. 1). The Stirling boiler settings rest on concrete foundations at ground level, with the furnace uptake and flue at a low elevation. The Erie boilers are carried on steelwork some 15 ft. above ground level, and stand against the face of the uptake with no connecting flue. The constructional requirements of a larger furnace dictated this type of setting.

Jan 1, 1934

By M. R. Geer, J. D. Davis, H. F. Yancey

ALTHOUGH the mechanical cleaning of coal is carried out at plants on the surface, preparation is actually begun at the face in the mine. Here the character of the coal and the amount, character, and distribution of the impurities within the bed may be seen. Blasting methods, dust-allaying procedures, location of mining cut with respect to bands of impurity, and the practice of discarding segregated impurities underground, all have an important bearing on the successful operation of surface cleaning units. The most important single characteristic of both coal and its associated impurities from the standpoint of cleaning is specific gravity. Other characteristics related in one way or another to the preparation of coal are rank, petrographic composition, structure and hardness, and friability. These and still other coal properties are discussed in the first section of this chapter and impurity characteristics in the second. COAL CHARACTERISTICS RELATED TO PREPARATION Rank As a result of work done over a period of several years by committees of the American Society for Testing Materials and the American Standards Association, standard specifications are now available showing the classification of coals according to rank and quality of grade. The term "rank" expresses the degree to which the original coal-forming material has been changed by metamorphism through successive stages from peat to anthracite. Table 1 shows the classification of coals according to rank as devised by the committees of the organizations mentioned. The basic scheme of classification for the higher-rank coals is according to fixed carbon content, calculated to the dry, mineral-matter-free basis. Groups of lower rank are divided

Jan 1, 1950

By K. L. Clark, Nicholas Kowall

MAXIMUM furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. WORK OF OTHER INVESTIGATORS In 1938, Burns, Moore and Archer published a curve7 that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the range found in constructional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only 0.20 per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E. 43xx steels. His procedure consisted of chill-casting a test bar that was large enough to give a surface that could be prepared for Brinell indentations. The test piece was quenched immediately after solidification was complete and hardness readings were taken, so that the carbon content could be read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. EXPERIMENTAL WORK Although Kern&apos;s work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By David A. Thomas, John F. Peck

Sam Leber (General Electric Refractory Metals Laboratory)—I think that the authors should differentiate between the curved grains obtained by swaging and the crumpled grains produced by drawing. This can be seen most easily in the transverse sections of Fig. 2d, and is also apparent in Fig. 2c. This difference in structure indicates that the mode of deformation shou1d affect the texture, since the cylindrical texture should be maintained or even increased by the curved grains developed by swaging. Drawing, on the other hand, crumples the grains. This should convert the cylindrical texture into a normal fiber texture. This has been substantiated by a comparison of tungsten wires fabricated by similar drawing and swaging schedules. Although cylindrical textures have been detected in drawn iron wires, they were weak in comparison to tungsten wires which included swaging as part of the fabrication process. It should also be noted that large curved surfaces developed by swaging are concentric with the surface. The postulated (100) surface of these crystals would be confirmed by a (100) cylindrical texture, as was observed in tungsten. The preservalion of the (100) cylindrical texture by swaging would maintain the <100> direction in the radial position required for easy flow. This might provide a partial explanation for the decreased rate of work hardening observed in the swaged wire. J. F. Peck and D. A. Thomas (authors&apos; reply) — The authors appreciate Dr. Leber&apos;s comments on the differences in textures, microstructures, and properties of swaged and drawn wires. The evidence of the prominence and persistence of the cylindrical texture in swaged bee wires seems quite consistent with our microstructural observations and interpretations. We are presently engaged in further work to correlate the development of texture and micro-structure in drawn bee metals.

Jan 1, 1962