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By Paul A. Farrar, Sanford Adler

The Tz-Zr system was reinvestigated using both metallographic and X-ray diffraction techniques. It mas found that titanium and zirconium are soluble in all proportions in both the a and 0 phases. The minimum in the transformation was found at 50 at. pct and 535°C. THE Ti-Zr system has previously been the subject of several investigations.1-6 A study by Hayes et al.5 using magnesium-reduced titanium and zirconium melted in graphite crucibles indicated that the system was a continuous series of solid solutions in both a and 0 phases with a minimum at approximately 545°C and 65 pct* Zr. These conclusions were substantiated by the work of Duwez4 as well as by the limited data of Craighead et al.,3 Fast,2 and deBoer.1 However, a more recent investigation of the titanium-rich region by Ence and Margolin6 indicated that the solubility of zirconium in a, titanium at 500°C is approximately 22 pct with the a + 0 field extending to approximately 47 pct Zr. Therefore in order to resolve this discrepancy the following investigation was initiated. EXPERIMENTAL PROCEDURES The alloys used in this investigation were prepared as 20- to 30-g buttons by nonconsumable electrode melting in a helium atmosphere. The starting materials were Bureau of Mines titanium BHN 71 and Foot Mineral iodide crystal bar zirconium. The titanium was premelted before the alloys were prepared to avoid excessive weight losses in the final melting. The compositions of the alloys prepared were as follows: Ti-12.0, 22.2, 29.0, 39.6, 50.0, 58.0, 72.4, 83.5. and 90.8 pct Zr. Prior to heat treatment the alloys were cold-worked 10 to 20 pct, stopping at the first signs of cracking. Specimens for heat treatment were wrapped in molybdenum sheet and annealed in argon-filled quartz capsules for the following times and temperatures: 750°C-40 days, 675°C-61 days, 600°C—109 days, 575°C-112 days, 550°C-112 days, 525°C—127 days, and 450°C —153 days. Quenching was accomplished by breaking the capsules in an iced-brine solution. The standard techniques used for polishing the specimens involved belt grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch7 or "R" etch 8 Debye-Scherrer X-ray powder photograms were obtained for a number of samples using a 114.6-mm camera and CuK, radiation. Exposure times were from 19 to 23 hr. The powder samples were obtained by filing to 270 mesh size. After filing the samples were wrapped in molybdenum foil capsuled in quartz and reannealed at the temperature of original heat treatments; following the heat treatment the samples were quenched into iced brine without breaking the capsules. RESULTS AND CONCLUSIONS On the basis of the microstructural examinations of the heat-treated samples and of the X-ray diffraction data, the Ti-Zr system shown in Fig. 1 was constructed. The data indicate that a, and 0 titanium form a complete series of solid solutions with a, and ß zirconium. The minimum was found to occur at 65 pct (50 at. pct) Zr and 535°C, in excellent agreement with the earlier investigations,1-5 see Fig. 2. Typical microstructures are shown in Figs. 3 to 7. Figs. 3, 4, and 5 show the 22.2, 39.6, and 50.0 pct Zr alloys after heat treatment at 675°C for 61 days with the 22.2 pct Zr showing equiaxed a, and the 39.6 pct Zr alloy a + transformed ß, while the 50 pct Zr alloy shows only transformed B. Figs. 6 and 7 show the 29.0 and 39.6 pct Zr alloys after heat treatment for 109 days at 600°C. The 29 pct Zr alloy has an equiaxed a structure while the 39.6 pct alloy has a partially recrystallized a+ß structure. X-ray diffraction data obtained from the 50 pct Zr alloys after heat treatment at 525° and 450°C as well as from the as-cold-rolled material showed only those lineos which couid be indexed a: a titanium, good agreement with the previously published values. 2,4,5,9 Chemical analysis* of the 50 pct Zr alloy

Jan 1, 1967

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky's approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky's paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By Alfred E. Hunt

In a paper written for the Boston meeting of February, 1888 (Trans., xvi., 693), on "Some Recent Improvements in OpenHearth Steel Practice," the writer described the reducing agent used by the Carbon Iron Company as "a peculiar graphite from Cranston, near Providence, R. I." Upon an application pending at that time, a patent has since been issued as number 259,795, to Mr. Matthew Graff, for the use of solid carbonaceous matter in the form of coke, charcoal, gas carbon, bituminous or anthracite coal, ground to the size of coarse sand and then coated with a mash of lime, magnesia, clay, or other material of a like character, as an agent to reduce metallic oxides. An amount of this prepared carbonaceous matter equal to from 25 to 30 per cent. of the weight of the ore treated is required to perform the complete reduction. The idea is that the carbonaceous matter is protected against rapid combustion by a suitable coating of some inert material, so that, in effect, its action as a reducing agent will be similar to that of the Cranston graphite previously used, allowing the solid carbon to remain without combustion in intimate mixture with the iron oxide at a temperature sufficiently high to reduce the ore and in some cases to melt the matrix in which the iron is held. In the present practice of the Carbon Iron Company, the use of graphite, except for the formation of bottoms of the reverberatory furnaces in which the reduction is performed, has been entirely abandoned, and " retarded coke," as it is called at the works, has taken its place. Five hundred and fifty pounds of Connellsville coke is ground in a pan to 16-mesh fineness, or is taken in the form of ordinary coke-dust, and made into a hollow basin on the mixingfloor ; and seven bucketfuls of a wash composed of equal parts of lime and fire-clay, mixed in water to the consistency of thin cream,

Jan 1, 1889

By J. O. Mack, J. B. Russell

In recent years, solders containing 20 per cent tin with no bismuth or cadmium have been developed by a few companies, and personnel have been properly instructed in their use. In addition, since the tin shortage, a number of solders containing less than 10 per cent Sn, and some with no tin, are being used in special applications; however, a solder of this type has yet to be developed that is satisfactory for general use. Table i.—Composition Ranges Prescribed for a Commercial Substitute Solder Element Per Cent Tin............................ 18.0-20.0 Bismuth (maximum)a............ 0. 80 Silver.......................... O. 10-1. 25 Bismuth plus silver (minimum).... 0. 85 Antimony (maximum)............ o. 50 copper (maximum),,,,,,,,..,,,, 0. I3 Other elements, each (maximum)6 0.03 Lead........................... balance a When silver is present in excess of I per cent, the Bi content shall be 0.50 per cent or over. b Total not to exceed 0.10 per cent. The Purpose of this investigation was to develop an alloy containing a maximum of 15 per cent tin, with no cadmium or bismuth, having solder properties equivalent to or better than those of substitute solders now specified containing 18 to 20 per cent tin (Table I), or even approaching the properties of the standard 40 to 60 tin-lead solder. The wartime restriction of bismuth and cadmium, elements that have beneficial effects on fluidity, solidification range and strength, makes it increasingly difficult to develop a general-purpose solder containing a maximum of 15 per cent tin. In the course of this investigation, 11 elements were used in various combinations with the basic I5-85 tin-lead alloy. These elements were antimony, silver, copper, indium, thallium, lithium, calcium, barium, potassium, sodium and arsenic. In all, 116 low-tin solders were investigated, with the idea of developing a solder that will give satisfactory working properties, specifically in regard to "wetting" of copper, brass and iron, solidification range, capillarity and shear strength of a soldered joint. The relative importance of these various properties plays an important role in the search for substitute solders, since it is almost impossible to retain all of the desired qualities of a high-tin solder and still make drastic changes in the alloy composition. Because of the expected uses of a general-purpose solder, it is necessary that it have properties, especially in regard to wet-tability, that will enable it to be used on the metals in common use. Basic Considerations The maximum liquidus temperature of a solder is determined by the particular application involved and the temperature that can be obtained by the source of heat. If a soldering iron is used, it must not only

Jan 1, 1945

By Carls Benedicks

It is well known by every one who has had to deal with boiler tubes that these are often seriously affected by a sort of corrosion, occurring as a local pitting, that frequently causes a perforation of the tube in a rather short time. The characteristic appearance of this corrosion is shown in Fig. 1. A very similar corrosion occurs in condenser tubes (Fig. 2).l A study of the microstructure or local chemical composition of the metal (iron 70:30 brass) fails to reveal any cause for this pitting. Of course one might possibly assume the starting point to be some oxide particle, causing an electrolytic local action, but this in no way explains the continued corrosion, progressing even when the assumed oxide particle must have disappeared. By the excellent work done by the Corrosion Research Committee of the Institute of Metals, and communicated, in October, 1923, to the Institution of Engineers and Shipbuilders in Newcastle-on-tyne, stress was laid on the faot that a content of entangled air has a very obnoxious effect. In the following correspondence, Sir George Goodwin stated that "engineers have, for a long time past, regarded air as the big enemy to be fought against in all questions of corrosion'72 and Kenneth Fraser pointed out that the most vital point is "the avoidance or removal of possibly the chief cause of present day corrosion, i. e. entrapped air and gases brought out of solution."3 In their reply, however, the authors state that they had "never for a moment believed that entangled air was responsible for the beginnings of corrosion, and express the opinion that the gradual liberation of air could not account for localized corro~ion."~ On consulting the many textbooks on corrosion, as that

Jan 1, 1925

By R. A. Generes, H. C. H. Darley

Laboratory tests showed that at elevated temperatures a reaction takes place between all metal hydroxides and clay muds, which results in a thickening or solidifying of the mud, the extent of which depends on the nature of the ingredients. Calcium hydroxide gave the strongest solidification whereas barium hydroxide only caused a mild thickening, indicating that the use of barium hydroxide muds instead of lime muds would be a good way of preventing high-temperature solidification. It was found possible to prepare barium mud in the laboratory with caustic soda and a thinner in the same manner as lime muds, and these barium muds had the same or better toleration of high solids content, resistance to salt contamination, and low gel strengths as the corresponding lime muds. Three field trials have been made with barium mud. The principal difficulty encountered was in determining the correct proportions of the tourly treatments required to maintain low gel strengths. A satisfactory systern was finally developed, and low gels were maintained throughout the third test. The wells on which the trials were made were not carried deep enough to test the resistance to solidification adequately, but oven tests at 350°F were made periodically and no tendency to solidification was noted except immediately after severe cernent contamination had introduced excessive amounts of calcium into the system. Although barium hydroxide costs considerably more than lime, the total mud costs were as low, and on the last well significantly lower, than the average cost of lime mud wells drilled in the vicinity. INTRODUCTION The advantages of repressing dispersion and hydra-tion of clay cuttings carried in the mud, particularly when drilling through thick clay formations, are well recognized. This repression is generally achieved by the use of lime, and lime muds have in consequence the desirable characteristics of high toleration of solids, low thixotropy, and good resistance to contamination. They have, however, the disadvantage of high-temperature solidification. This phenomenon has been described in detail by Gray et al, who have shown that it is the result of a chemical reaction between the hydroxides and the clay minerals. The work described in this paper was undertaken to find a substitute for lime which would not cause this solidification. LABORATORY EXPERlMENTS The principal positive requirement for a substitute for lime is that it should repress the hydration and dispersion of clay. It is well known that monovalent cations promote hydration while polyvalent cations repress it. Therefore, a few representative polyvalent salts and hydroxides were tested to determine whether they could be used as substitutes for lime. Their efficiency at repressing hydration and dispersion was measured by means of the clay-volume test. It has been shown elsewhere' that this test is a good measure of degree of dispersion of clay in suspension and that hydration accompanies and correlates with dispersion, so that measuring one measures the other. The test is made by centrifuging a 1:100 mixture of mud and 1-N NaCl and observing the volume of sediment—the greater the volume, the greater the dispersion. The tendency to caux solidification was measured by heating the muds in pressure vessels for 16 hours at 150°F and 370°F. An approximate quantitative

Jan 1, 1957

By Gordon G. Bentle, W. P. Fishel

GREINER, Marsh, and Stoughton1 have reviewed the literature in a monograph on the iron-silicon system. The lack of agreement among the various studies may be due to the difference in the purity of materials in some cases. The results of the X-ray method indicate only a general rather than a specific limit of the y loop. The iron-titanium system was investigated by Roe and Fishel,' whose results are used in determining the iron-silicon-titanium y loop. The literature indicates that no study has been made thus far of the iron-silicon-titanium system in the y loop region. Experimental Procedure The alloys were made from Armco iron, 99.86 pct Si, and 98.5 pct Ti. The titanium contains 1.07 pct Fe. The Armco iron contains 0.01 pct C, 0.005 pct Si, 0.02 pct Mn, 0.006 pct P, 0.01 pct S, and 0.04 pct Cu. A dilatation sample of Armco iron was prepared in the same manner as were the other samples. Several dilatation runs indicated that Ac3 begins at 905°C and ends at 910°C, which compares favorably with the study of Wells, Ackley, and Mehl' employing specially purified iron. All alloys were melted in an induction furnace in Alundum crucibles and were top poured into baked core sand molds. The ingots weighed about 600 g as cast. Dilatation samples of 4 in. by % in. diam were taken from the bottom end of the ingot, from which turnings for analysis were taken. Turnings from each end of two of the samples indicated that the alloys possessed uniform silicon content. A hole was drilled halfway through each end of a 4 in, dilatation sample. A chromel-alumel thermocouple was inserted in each hole and the surrounding metal peened in to hold the thermocouple in place. Fig. 1 represents the dilatation apparatus. The heating unit is an Alundum tube wound with resistance wire; the dilatation tube is a McDanel combustion tube; the push rod is zircon; the dial gage is graduated in 0.0001 in. and was vibrated to prevent sticking. A blank run over the temperature range of interest gave no significant dilatation. The thermocouples were attached to a multiple recording micromax which indicated the temperature at each end of the sample at 35 sec intervals. A Lindberg control unit governed the rate of heating of the furnace, and lowering or raising the

Jan 1, 1957

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,' and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.'.' Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett's No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

By Thomas E. Howard

Recently, the mining community has begun to move toward a more prominent place in the structure of American society. Extensive press coverage of our energy problems during the past year or two has led to an increasing awareness on the part of the public of the vital role that mining must play if today's standard of living is to be maintained. It appears that mining may be emerging from a status generally characterized in the public mind as an esoteric, dirty, man-killing, land- scape-despoiling endeavor, to a new stature that may eventually become as respectable as agriculture. To be sure, we are still being criticized, as has been the lot of miners since the time of Agricola. In fact, the clamor has never been louder. Nevertheless, the public, in increasing numbers, is beginning to know it needs us. But we cannot be complacent. Our improving stature brings along with it increasing responsibility. The mineral industry will be expected to produce mineral raw materials and fuels in ever larger amounts and sell them at reasonable prices, in the face of rising labor costs, decreasing labor availability, chacging labor attitudes, increasingly stringent environmental regulation, stricter health and safety standards, and a deteriorating geo-political climate.

Jan 6, 1975

By G. P. Gladis, R. H. Atkinson

Palladium has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items—at least I00 times as rare as gold. Although both visual and spectro-photometric examination demonstrated that the color of Palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400' to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By G. P. Gladis, R. H. Atkinson

Palladium has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items—at least I00 times as rare as gold. Although both visual and spectro-photometric examination demonstrated that the color of Palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400' to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By S. Weinig, J. Winter

The grain boundary adsorption of solutes as a function of bulk concentration and solution temperature was studied using internal-frictimz techniques. From the variation of the cor-responding energy of activation for the Phenomenon, the inter-actior2 energy between a solute atom and a high-angle boundary was calculated. Interaction energies in the range of 0.3 ev were obtained, and were used to obtain the actual concentration of solute at the grain boundary. In corroboralory creel, studies the direct grain boundary contribution to the total creep strain was measured. It was found that the interface creep varied with the type and magnitude of the solute adsorbed. Subscribing to the theory of their being energetically favorable sites at the grain boundary for solutes of both Positive and negative size deviations, ternaries were investigated in Which solutes of both types were present. A marked increase in the resistance to grain boundary creep was manifested. THE major difficulty which has been encountered in investigations of the grain boundary segregation of solutes has been the lack of a sufficiently sensitive method of measuring the amount of adsorbed solute at the boundary. For the general case of a high-angle boundary, no direct method of measuring the adsorption at the boundary has been found to date. Internal friction has been used in several studies of grain boundary adsorption1-3 and although it is somewhat indirect, it was demonstrated to have the necessary sensitivity. In this investigation the authors have used internal-friction techniques in conjunction with a study of the grain boundary contribution to the total creep strain. As both parts of the investigation were performed on the same specimens it was possible to combine a highly sensitive technique with a somewhat more direct method in order to obtain information about the adsorption phenomenon. From internal-friction studies the rate of increase of the activation energy was observed to be a function of the difference in size between the solute and solvent atoms. It was proposed that if Gibbs' adsorption isotherm is considered, i.e., where r is the excess solute at the boundary, c is the bulk concentration, and ay/ac is the change in grain boundary energy with bulk concentration, then AH b/ac must vary in the same way as ay/ac and therefore In this way a relative measure of the grain boundary adsorption of solutes is directly obtainable from in-ternal-friction studies. If the previous work in the field of grain boundary adsorption of solutes is examined, certain apparent information is desirable if the phenomenon is to be understood. The most important questions that must be asked are as follows: 1) Is the adsorption of solutes at the grain boundary an equilibrium process? 2) Can the Mott model of the grain boundary be used as a basis of setting up an elastic interaction between the grain boundary and solute atoms? 3) Is it possible to obtain an exact measure of the excess solute at the grain boundary as a function of temperature and bulk concentration rather than merely a relative measure of the adsorption 4) Are the conclusions obtained from an indirect method such as internal-friction studies meaningful in considering gross grain boundary effects such as creep? EXPERIMENTAL PROCEDURE The material used in this investigation was Bureau of Mines "superpurity" titanium (79 Bhn—1500 kg

Jan 1, 1960

By W. A. Griffith

Fractional replication of factorial design, a general method for planning experimentation and for analysis of data obtained, is described as applied to a flotation investigation. This method leads to determination of optimum process conditions with minimum experimental effort. Its advantages over simple factorial design are demonstrated. A METHOD for planning experimentation and for analyzing the data secured will be demonstrated. This method, termed fractional replication of factorial design, employs a relatively small number of individual experiments to determine which of a large number of process variables are controlling, to determine which combination of levels of these variables is most likely to produce optimum results, and also to predict what results will be obtained with a particular combination of conditions not already tested. Although the general method is not new, having been developed by Finney in 1945,' the extent to which it can improve the effectiveness of applied research generally has not been recognized by metallurgists. The fractional replication procedure is particularly useful in flotation experimentation and an example from such an investigation will be used in the paper. However, it has equal value in any investigation in which similar experimental difficulties are encountered. In developing a flotation process for a particular mineral separation, the investigator is inevitably confronted with the following difficulties: 1—There are a large number of potentially important process variables. 2—Results of individual experiments are not highly reproducible, due in part to the difficulty in precisely controlling all the variables. 3—Considerable effort is expended in conducting individual experiments. 4—There are practical limits on the number of individual experiments which can be made. In situations of just such a type, modern statistical methods of planning experimentation and analyzing data have their greatest value. Applications of one such technique, called factorial design, to problems of this type have been described by Dorenfeld and others.'-' The simple factorial design is an efficient procedure when the investigator hopes to provide a comprehensive understanding of the effects and interrelationships of a small number of variables over a limited range. In applied research, this is seldom the main objective. Rather, the investigator usually wishes to determine which of the many potentially important variables are in fact controlling, which levels of the controlling variables will provide opti- mum metallurgical results, and what these results will be at optimum conditions. Interest in detailed trends is limited to the controlling variables and to levels in the region of optimum conditions. Simple factorial design has serious deficiencies for such objectives and is not the most efficient method of experimental design. Deficiencies of Factorial Design In a simple factorial design, an experiment must be made at every possible combination of each level of every variable, once these have been chosen and the levels of each to be included have been decided upon. As the number of variables or levels of each increases, the experimental program quickly reaches prohibitive size. For example, an investigation of only four variables, each at four levels, requires 256 individual experiments. Often upon completion of such an extensive program, it is found that one or more of the variables has metallurgically unimportant effects or that a poor estimate has been made as to the appropriate range of levels to be investigated. The result is that only a small proportion of the data obtained falls in the range of real metallurgical interest. Indeed, it frequently can be anticipated that certain combinations of levels of variables will not produce results of interest, but they still must be included so that the essential balance, or orthogonality, of the design will be retained. It may be true that factorial design will provide the greatest amount of information from a given number of experiments, but it does not necessarily follow that it will lead to the desired information with a minimum number of experiments. Much of the information provided may be of little value. Advantages of Fractional Replication The disadvantages of simple factorial design are overcome to a great extent by a modification known as fractional replication. This is a technique for sampling systematically the potential data of a full factorial experiment, that is, the data which would have been obtained if the complete factorially designed program had been completed. Only a fraction of the total array of experiments is made, but the experiments are chosen in such a way that the important advantages of factorial design and the accompanying analysis of variance are retained. The data obtained from the first group of experiments are used to determine which of several variables are controlling and which levels of these variables are most likely to produce the desired result. Unimportant variables and levels of variables then may be

Jan 1, 1956

By John D. Ridge

For mining geologists, the most important trends during 1962 have been the increased concentration of the exploratory activities of American mining companies in the United States and Canada and the greater use of the combined techniques of geology, geophysics and geochemistry in searches over larger areas for wider varieties of metals and minerals. The principal reasons for these changes in approach have been the deterioration of the political-economic climate in many areas of the globe of equal or greater geologic promise and the realization that modern exploration is most efficiently and economically conducted through the use of all available means of detecting ores in areas sufficiently large to raise to a maximum the chances of success. The attitude of certain major U.S. metal-producing companies can be shown by the officially ex- pressed positions of their principal officers. Early in 1962, Clyde E. Weed, Chairman of the Board of Anaconda, remarked that "because of unsettled conditions and disruptive influences in many of the copper-producing areas of the world, it is imperative that domestic copper-producing capacity be improved and made as efficient as possible in order to meet consumer demands at reasonably stable prices." In November, Robert G. Page, President of Phelps Dodge, pointed out that his company is not only concentrating most of its exploratory effort on this continent but is also increasing the number of metals for which it is searching. Frank R. Milliken, President of Kennecott, recently said that "most of our exploration money is going into the northern part of the Western Hemisphere."

Jan 2, 1963

By W. D. Brown

Newell1 has shown that hydrogen is removed from steel in a vacuum at a temperature of 500° to 900° C. within 136 hr. Holm and Thompson2 also state that, especially when the hydrogen is high, the results obtained by extraction at 800°C. agree with those obtained by vacuum fusion. In this laboratory, an apparatus was designed (Oct. 1940) and used wherein the piece of steel was heated at 100°F. in a Torricellian vacuum (Fig. I). This vacuum was produced by raising and lowering a "leveling bottle or bulb" containing mercury. Extensive tests were made with this apparatus. The weakness of the procedure was the possibility of leakage of air into the tube around the rubber stopper at the bottom. The present plan is to raise and lower the mercury by applying vacuum from a mechanical pump, to the top of the tube and then to a bottle of mercury in which the bottom of the tube is immersed. The Apparatus The extraction is made in a Pyrex tube A, I in. i.d. It is drawn down at the top at N and an 8-mm. i.d. tube is welded on it. To this a Pyrex stopcock E, 4-mm. bore, is welded. The tube between N and E is preferably 8 in. long and is graduated in milliliters. The total length of A to the stopcock is 28 inches. Heat is supplied by a split-tube furnace. 0 in. long by 6 in. in diameter, hinged on the side. A short pyrometer couple P is inserted through the walls of the furnace. In use this is standardized by comparison with a standard couple in a I-in. tube, just opposite this short couple. In the I-in. tube A a glass rod R, flattened at one end, supports the sample S and the length of R is so adjusted that the sample is in proper place. (It may float in the mercury.) The tube A is inserted in a large rubber stopper to fit the bottle B and extends nearly to the bottom. It is so placed that the handle of the stopcock faces the operator. In this stopper also is a short tube D bent at right angles for the application of vacuum. Also in this stopper is an 8-mm. tube C reaching nearly to the bottom; this is bent so as to miss the heater and again bent to bring it in line with and as near as possible to the upper and reduced part of tube A. On this tube C is welded a 4-mm.-bore stopcock H. In order that the two tubes may be as near as possible, the handle of stopcock H faces the back, or is the reverse of stopcock E. The total height of II above the bottom is 28 in. As explained later, this is the pressure-measuring tube C. The bottle B is about half full of mercury. The mercury must cover the ends of A and C by about I in. when they are evacuated. By tees T and rubber tubing RT the tubes A, C and D, the latter through the three-way stopcock M, are connected to the vacuum pump. A sheet of asbestos at K prevents the stopcocks E and H from becoming so hot that they leak. A good grade of vacuum lubricant prevents leakage of E and H. In order to measure the pressure of the

Jan 1, 1945

By W. F. Wheeler

In the study of the coals of Illinois now being carried on by the State Geological Survey, an attempt is being made to determine the most satisfactory basis of comparison between different coals. The following discussion is based upon work done for the Survey in the laboratories of the State University and under the general direction of Prof. S. W. Parr. "Pure coal" has been defined by Mr. A. Bementl as ash- and moisture-free coal, and the use of this pure coal" as a basis for comparing different bituminous coals has lately been much discussed among engineers in the middle West. By some the B.t.u. of the pure coal is being used to check calorimetric results, and to calculate the calorific value of different coal-samples from the same seam, for which purposes it is necessary to assume—first, that the composition and calorific value of pure coal from different parts of the same coal-seam are uniform, and, second, that these values remain constant after the coal is mined, both of which assumptions there are reasons to believe are inconsistent with the facts. Certain variables are included in pure coal, as ordinarily defined, and disregard of them may lead to serious error. In any event, where delicate shades of difference are involved, no sure interpretation of results car] be made, unless these variables be eliminated. As a basis of comparison between coals, ash- and moisture-free coal is much to be preferred to " dry coal," and still more is it to be preferred to moist coal," as ordinarily reported in analyses. There are, however, two constituents other than ash

Jan 1, 1908

By Cloyd M. Smith

B. F. TiLLson*— The manifold difficulties of accurate anemometry in irregular sections of mine passageways, the irregular distributions of velocities in cross sections of the same, and the disturbing influence of the observer upon the air flow, all indicate an undesirable inaccuracy of results obtainable by any standardized method of traversing the section by an anemometer. It seems obvious that another, and simpler, method should be used to determine the volume of air flow in mine passages, namely: 1. At appropriate locations cement or calked framework rings should be installed permanently to equalize the irregularities of sectional contour and provide a place and means of attachment for a temporary cloth brattice which bears a rigid orifice. 2. The measurement of the velocity of air flow through the orifice may then be by anemometer or, preferably, by Pitot tube measurements of the differential pressures on both sides of the orifice in accordance with the standard practices available in engineering 1iterature. † The constants may be determined for various measuring positions in relation to the resulting "vena contracta." 3. The position of the person who makes the measurements is behind the brattice out of the air stream. The Pitot tube does not offer as disturbing an obstruction as the anemometer. A recording gauge may be employed to integrate fluctuations in air flow through that portion of the mine. No traverses are required because the reading may be at a single central point. An anemometer can be used with an orifice flow. The orifice will increase the air velocity at the measuring point, with correspondingly more accurate measurements where the normal air velocity through the passageway is low. Portable brattices might be devised with the cushioning rims which would seal against irregular rock surfaces where permanent rings were not available or feasible. The development by the Ventilation Committee of standard procedures and devices for the orifice measurement of the flow of mine ventilating air might be a desirable project for this coming year. C. M. Smith (author's reply)—Thank you for your discussion of my paper on underground anemometry. Your suggested method of measuring underground air flow is a novel one which might be applicable in some situations. It should be tested along with other suggested methods in any investigation of this subject. G. E. McElroy*—In spite of the adverse publicity that vane-anemometer methods of air measurement have had in the past and that contributed by the present paper, I endorse Mr. Erickovic's statement that anemometer traversing "has proved to be widely applicable, expeditious and simple" and add that available methods are accurate enough for the purposes for which they may be used. The fact that the great majority of minor mine officials assess relative changes in rates of air flow by comparison of crude vane-anemometer measurements, known to average 20 to 30 pct high, has no important bearing on this subject, because state inspection standards were based originally on such methods of air measurement. Federal inspection standards are based on actual rates of flow as determined by traversing, and interest in traversing methods is rapidly increasing. In considering traversing methods, three aspects are of major importance: (1) the absolute accuracy of calibrations; (2) the degree of interference with normal flow conditions introduced by traversing methods designed for accurate measurement by shaft-mounted instruments; and (3) the proper "method" factor to use for approximate measurements by hand-held instruments. With respect to absolute accuracy of calibrations, we have always placed reliance on calibrations made by the National Bureau of Standards, with which manufacturers' calibrations have usually agreed very closely. It is therefore particularly disturbing to find7 that calibrations made previous to June 1947 are presumably about 5 pct in error because of excessive registry caused by the thin flat plates on which anemometers were mounted for calibration. Velocities corrected for calibration have therefore averaged about 5 pct low in all probability. In this connection, it is interesting to note that an anemometer calibrated against Pitot-tube measurement by a single-point method in the Bureau of Mines experimental coal nine in 1923 indicated this same difference of about 5 pct and that the same instrument calibrated by a traversing method in a metal mine some months later indicated a difference in the same direction of about 4 pct. These results are reported by the Bureau of Mines.8 Regarding the degree of interference, or changes in velocity distribution, caused by the position of the observer's body in traversing operations, misconceptions seem to be especially prevalent, resulting in increasing advocacy of methods, such as the "clear section" method outlined in this paper, that cause just the type of interferences that they are designed to avoid. The degree of interference for any method may be gauged easily by a few experiments with a velocity-pressure gauge connected to a Pitot tube or with an indicating velocity meter such as the Velometer. In an experiment cited by McElroy and Richardson,# a decrease of 5 pct was noted at ten widths upstream from a 6-in. plank, whereas an observer's body at about the maximum practical distance of 6 ft downstream from the instrument is only about four widths away. In the Bureau of Standards paper previously mentioned, it is recommended that supports used in calibrations be at least 16 widths downstream. In practice, therefore, a downstream position of the observer is ruled out as far as accurate measurement is concerned. Operation of the anemometer by rigid shaft support from a point outside the section is seldom practicable; however, accurate results can be obtained, with the anemometer rigidly attached to a short shaft and held at arm's length, by an observer advancing across the traversed section while he faces the opposite wall and stands sideways to the current, provided that he keeps the instrument at least 3 ft away from his body at all times and traverses the entire section with it. If the traverse can be started with the observer in a side recess, the entire section can be covered in one operation. Normally, it would be covered in two half-sections. The presence of the observer's body does not, as is commonly supposed, increase the average velocity throughout the remaining part of the section. Rather, the velocities 1 to 2 ft on either side of his body are increased, but the distribution of velocities throughout the rest of the cross section remains normal, and a traverse made as stated gives a true average velocity for normal-flow conditions. Regarding the proper "method" factor for accounting for interference in the approximate methods of traversing with hand-held instruments, here again confusion prevails, for which the writer must assume some of the blame. Comparison of consecutive traverses made by shaft-held and hand-held 4-in. anemometers in field work after the tests reported by McElroy and Richardson' gave method factors

Jan 1, 1950

By T. C. Desollar

THE group of iron-ore mines known as the Red Ore Mines, owned and operated by the Woodward Iron Co., is on Red Mountain approximately ten miles southwest of Birmingham, Ala. At the, present time No. 1 and No. 3 mines are active, No. 2 mines having been abandoned in 1928. Ore from this group of mines was first mined in 1882, and originally came from open cuts along the outcrop, but, when the "soft ore" (weathered hematite) was mined out and the harder ore was encountered, it became necessary to develop the orebody by means of slopes driven in the ore formation. The three mines to date have produced more than 22,000,000 tons, and the two operating mines now have a capacity of over 1,000,000 tons per year.

Jan 1, 1933

By Edward L. Fidler, Thomas E. Finch

Thin seam coal mining in the western US nominally equates to recovery of stray seams associated with thicker, major seams. The thin or stray seams encountered are generally recovered, but not in all cases. The alternative to extraction is, of course, spoiling. The majority of thin seams are encountered somewhere in the overburden above the major seam or in the parting between thick seams. Although some are true strays and appear anywhere in the geologic sequence, others might be classified as thin "rider" seams immediately above or below a thick seam and separated by some equally thin parting. For the purpose of this discussion, stray or thin seams are defined as those which are less than 1.2 m thick or represent less than 10% of the expected extractable coal. [Figure 1] is a graphic representation of typical thin, stray, or rider seams which actually appear in a western operation. Operationally, stray seams create irritating scheduling problems and require special handling techniques which do not always lead to efficient equipment utilization. Additionally, coal recovery from a thin seam is considerably less than the 95% usually recovered from thick seams. Higher recovery in thin seams leads to dilution problems, which depreciates Btu quality, and most western coals are not in a position to lose heating value. Thin western seams also undulate and pinch or swell more than thick seams, and this leads to more difficult recovery. Often they are associated with equally dark carbonaceous shales and visual selectivity is difficult at best during daylight hours. Resource Recovery Regulations Thin seam recovery in western mines is encouraged by both federal and state regulations and by the mining industry's concern for total resource recovery. [Table 1] lists the western coal states and their recovery regulations. The federal regulations are found in the Surface Mining Control and Reclamation Act of 1977. They state, "General performance standards shall . . . require the operation as a minimum to … conduct the surface coal mining operations so as to maximize the utilization and conservation of the solid fuel resource being recovered." Economic stimulation for thin seam recovery appears to be marginal or at the least controversial. Scheduling and operational problems often outweigh the nebulous profits created by engineering analysis. The only alternative to extracting thin seams occurring above major production seams is to strip directly through them and lose the resource to the spoil pile. Although this is not palatable to environmental emotions or resource promoters, it is the most simple expedient to operations people.

Jan 1, 1981

By William B. Phillips

The concentration of natural magnetites has been carried on in this country for several years, and more or less information has been collected on the subject. Various inventors, availing themselves of the magnetism which is inherent in such ores, have devised machines for separating the impurities from the ore by means of the electric current; and a greater or less degree of success has rewarded their painstaking and persevering efforts. We are now fairly in position to judge of the value of the process as applied to such material. It is not my purpose to speak of this matter further than may be required by the emergencies of the case. I shall assume that most engineers and metallurgical chemists are already acquainted with what has been done at the Chateaugay mines, at Mineville, at the Benson mines, at the Weldon and Ogdensburgh mines, and at Cranberry; although, at this latter place, there has not been so much done as we could wish. I shall not now speak of the various types of separators. From the time of William Fullarton, to whom was granted an English patent, in 1792, for separating iron-ore by the application of magnetic attraction, down to the present time, a great. many devices have been suggested, and a great many patents taken out for this purpose; but it is not necessary now to enter upon a discussion of their merits. Perhaps, at some future meeting of the Institute, after we shall have experimented further with some of the machines on the market, there may be an opportunity to contribute something to the current knowledge of the efficiency and economy of separating-machines. In this paper I propose to give, as briefly as possible, the results already reached in converting a non-magnetic ore into magnetic ore, and then concentrating it over a magnetic separator of the alternate-polarity type. I am aware of the work

Jan 1, 1896