Search Documents

By A. E. Dwight, P. A. Beck

A search was made for ordered phases of AB3 composition in various combinations of Ti- and V-group elements with CO-and Ni-group elements. Three new TiNi3-type phases ZrPd3, HfPd3, and HfPt3 were found. In addition, twelve new Cu3Au-type phases TiRh3, Tilr3, ZrRh3, Zrlr3, HfRh3, Hflr3, VRh3, VIr3, CbRh3, Cblr3, TaRh3, and TaIr3 were also found. The lattice contraction for all three structures considered increases with increasing relative size of the A atom, suggesting that it is mostly the A atom that cont~acts. It was noted that, for the same radius ratio the lattice contraction is larger when the A atom is Ti than if it is Cb OY Ta. It is well known that elements or disordered solid solutions, which have structures with spherical close-packing, may be described in terms of various stacking schemes of close-packed layers. Stacking of the type abab corresponds to the hexagonal close-packed structure, and stacking of the type abcabc corresponds to the face-centered-cubic structure. In binary alloys of the first, second, and third long period transition elements various AB3 phases occur with close-packed ordered structures. It was observed that these ordered structures also may be described by suitable stacking of close-packed ordered layers, Fig. 1, as first shown by Laves and Wallbaum for TiNi3.' It is clear that the units of translation in such a close-packed layer consist of four atoms, one of which (black circle) is atom A and the three others (empty circles) are atoms B. Because of the alternation of A and B atoms in every second row of each layer, the unit-cell dimension in the layer is equal to the sum of the diameters of atoms A and B: a0 = 2(rA + rB). Stacking of such layers in the sequence abab results in a hexagonal close-packed structure of the MgCd, type. The unit-cell dimension in the basal plane is approximately double of that for the disordered hexagonal close-packed structure, but in the direction of the hexagonal axis it is about the same, so that 2co/uo = 1.63 in case of spherical close-packing. Ordered hexagonal close-packed structures of this type were found to occur in MoCo3,2 WCo3,, and UPt, .4 When the ordered layers shown in Fig. 1 are stacked according to the scheme abcabc, the resulting ordered structure is of the AuCu, type (cubic). Structures of this type were found to occur in TiPt3,5 CrPt,,' CrIr,,' and URu, .4 Finally, the stacking scheme abacabac of the same ordered layers results in a hexagonal close-packed structure of the TiNi3 type.' In this case, the unit-cell dimension is doubled not only in the basal plane, but also in the direction of the hexagonal axis, so that co/ao = 1.63. Structures of this type were found to occur also in TiPd3,5 ZrPt,," and UPd,.4

Jan 1, 1960

By H. Foster Bain

FROM time to time geologists and mining engineers, impressed by the heavy demands made on our mineral reserves' by modern industry, and particularly by the steadily mounting rate of production necessary to meet that demand, have issued warnings as to the danger of exhaustion. There can be no dispute as to the fact that mineral deposits are exhaustible. New mineral, is not created to replace that taken from the earth and when a crop of mineral is once harvested another cannot be grown in the same area. The evidence of exhaustion 'of particular oreshoots, deposits, or even of whole districts is familiar to all who have mined. If one were to judge solely from the abandoned mills and prospect holes he would rightly conclude that mining is but a short-lived industry. If one were, furthermore, to assemble the data as to known reserves of almost any of the commonly used minerals, and divide them by the annual tonnage mined, he would come to the same conclusion. If, again, one were to consider the most carefully made estimates of competent men seeking to measure the earth's reserves of minerals and plot against them a projection of the curve of past consumption, he would be justified in viewing the situation with alarm.

Jan 1, 1930

The following discussion was held on August 2.2, 1927, during the meeting of the Institute at Salt Lake City. It. IIIatch, Garfield, Utah.—The object of the meeting, I belicve, is to determine the proper chemical composition to insure long wear of a ball in a mill. This might also apply to rods. I feel that there is only one way of determining accurately the wearing qualitites of balls in mills, and that is by actually wearing out 400 or 500 tolls of different kinds of balls. Two things add to the wearing qualities of a ball: (1) the tenacity, with which the particular particles of iron or steel are cemented together; (2) the individual hardness of each partiele. My cxperience is that a ball that has a Brincll of 550 to 650 will give comparatively long life. There is considerable difference of opinion as to the best steel and iron alloys neressary to produce a satisfactory grinding ball. Some favor chrome, somr manganese and some nickel. Personally, I believe cast iron alloyed with chrome makes the best ball for small sizes; for large sizes (31/2 in. arid up) steel alloyed with mangancse is best. L. O. Howard, Pullman, Wash.—How would this method apply to hning? A. Kissock, New York, N. Y.—I do not subcrribe to that exactly. As I am connected with the Climax Molybdenum Co. you would hardly expeet me to. We have been much interested in trying to work out this grinding-ball problem and have spent a, great deal of thought and effort on it. As we are associated with the American Metal Co. and have a number of Proprrties of our own, we are in poaition to try our ideas on ourselves first. We have tried different compositions, but, have not done anything very remarkable with them yet,, except that we have been able to say that the combination of chrome and molybdenum has given the best, wearing ball. Mr. Hatch feels that iron is the best. medium for grinding, hut since toughtiess as well as hardness is a factor in wearability we feel that a well made steel is better for this purpose. Another difficulty with cast, or chilled, iron is lack of uniformity front day to day or from heat to heat, and the impossibility of protlucing balls free from blow or shrinkage holes which matcrially affect their life. If cast iron is made hard it becomes brittle and lacks strctc11 or toughness. This prevents its use in the larger sizes, aS break:lgc, is a sorious hantlic:~p to efficiency. We have trirtl hard and brittle balls and softer but very tough balls and have proved that maximum hardness, with sufficient toughuess to prevent hrcakagv, is the most important factor. in resistarnce of a steel to abrasion. It is well known that. chromium is one of the best hardening agencies for cither iron or. steel; and molybdenum is recognized as an clerment capable of introducing tonghness. In other words, the proper combination of chromium and molybdenum permits unusual hadness with still sufficient touglmess to stand up under severest impact. It is yet too early to give any actual mill results of this new Combination and though we are proving our ideas at our own properties we have to depend on others to help us make the data more general and more worth while and would like to get some testa 206

Jan 1, 1928

By L. O. Howard

R. HATCH, Garfield, Utah.-The object of the meeting, I believe, is to determine the proper chemical composition to insure long wear of a ball in a mill, This might also apply to rods. I feel that there is only one way of determining accurately the wearing qualities of balls in mills, and that is by actually wearing out 400 or 500 tons of different kinds of balls. Two things add to the wearing qualities of a ball: (1) the tenacity, with which the particular particles of iron or steel are cemented together; (2) the individual hardness of each particle. My experience is that a ball that has a Brinell of 550 to 650 will give comparatively long life. There is considerable difference of opinion as to the best steel and iron alloys necessary to produce a satisfactory grinding ball. Some favor chrome, some manganese and some nickel. Personally, I believe cast iron alloyed with chrome makes the best ball for small sizes; for large sizes (3 1/2 in. and up) steel alloyed with manganese is best. L. 0. HOWARD, Pullman, Wash.-How would this method apply to lining? A. KissocK, New York, N. Y.-I do not subscribe to that exactly. As I am connected with the Climax Molybdenum Co. you would hardly expect me to. We have been much interested in trying to work out this grinding-ball problem and have spent a great deal of thought and effort on it. As we are associated with the American Metal Co. and have a number of properties of our own, we are in position to try our ideas on ourselves first. We have tried different compositions, but have not done anything very remarkable with them yet, except that we have been able to say that the combination of chrome and molybdenum has given the best wearing ball. Mr. Hatch feels that iron is the best medium for grinding, but since toughness as well as hardness is a factor in wearability we feel that a well made steel is better for this purpose. Another difficulty with cast, or chilled, iron is lack of uniformity from day to day or from heat to heat and the impossibility of producing balls free from blow or shrinkage holes which materially affect their life. If cast iron is made hard it becomes brittle and lacks stretch or toughness. This prevents its use in the larger sizes, as breakage is a serious handicap to efficiency. We have tried hard and brittle balls and softer but very tough balls and have proved that maximum hardness, with sufficient toughness to prevent breakage, is the most important factor in resistance of a steel to abrasion. It is well known that chromium is one of the best hardening agencies for either iron or steel, and molybdenum is recognized as an element capable of introducing toughness. In other words, the proper combination of chromium and molybdenum permits unusual hardness with still sufficient toughness to stand up under severest impact. It is yet too early to give any actual mill results of this new combination and though we are proving our ideas at our own properties we have to depend on others to help us make the data more general and more worth while and would like to get some tests

Jan 1, 1928

By Etienne A. Ritter

INTRODUCTION. THE Evergreen mine, located at Apex, in the northern part of Gilpin county, Colorado, has opened a very peculiar and interesting copper-deposit, in which both bornite and chalcopyrite occur as rock-minerals. The country-rocks are crystalline schists cut by dikes of granulite and of pegmatite. At the Evergreen property they have been cut by a dike of a new kind of eruptive rock, to which I have given the name " Evergreenite" The rock is composed of quartz, alkali feldspars, orthoclase and albite (often interlocked as microperthite), with augite of the aegirine variety and long needles of enstatite and diallage. For reasons stated below, I believe the dike to be of Tertiary age. It is- easily traced on the surface of the ground, from a point in the bottom of Pine creek, about a mile below Apex,. to the top of Nevada hill, 1,500 ft. beyond and 600 ft. above it. (See Fig. 1.) It varies from 3 to 12 ft in width, and is bounded on both sides by contact-zones about 60 ft. wide, in which the crystalline schists have been changed into pseudo-quartzites or pseudo-gneisses, according to the injection of an excess of quartz or of feldspars through the special layer of the schists.. The most interesting feature is the presence of the pyroxenes, which are always found, though in very variable proportions from place to place, in the layers of these' metamorphosed crystalline schists. The dike has torn from its walls a large number of fragments of the wall-rock. It must have been in a viscous state when that happened, because these fragments of the wall-rock do not show any sign of resorption or of assimilation by the magma. In places they are so distinct and so numerous that the rock looks to the naked eye like a pseudo-breccia, of which, never-

Jan 1, 1908

By William L. Langdon

PRELIMINARY COMMENTS Recent years have been difficult for the mining industry, as reported in the most recently published Minerals Yearbook (Volume III), the estimated value of world crude mineral production has been generally declining since an historical peak in 1979 (16).* The costs of mineral extraction have, however, been rising rapidly. Individual project costs are, in general, exceeding the growth rate of mining companies, while operating and technical risks continue to increase (16). Risks resulting from currency flotation and political actions in the host country are also on the increase. Labor difficulties (such as those experienced by Phelps Dodge) and the Reagan Administration's recent rejection of a proposal by the International Trade Commission for higher tariffs and/or quotas on copper imports have also contributed to the mining industry's difficulties. The net result of these factors has been financial difficulties for mining companies with respect to paying for their current financial obligations as well as trouble finding new financing. It may be that one of the main factors in determining the future of the mining industry will be centered upon capital structure, i.e. how its assets are financed. Historical Perspective on Capital Structure In The Mining Industry As discussed by Isreal Borenstein in (4) and Thomas Navin in (7), mining firms typically have used a financial model based upon high financial leverage, i.e. large amounts of debt relative to equity. This has been especially true for American firms developing orebodies discovered overseas. Problems sometimes occurred for those who were forced to commit themselves to completion guarantees in order to obtain bank loans. Mines under these circumstances must be brought into operation regardless of market conditions. Politicians in overseas countries also may use the high profits required by these high risk ventures to argue for nationalization of mines. Coupled with the frequent use of high leverage, mining companies traditionally have paid out a higher percentage of earnings in the form of dividends than manufacturing firms. This is significant, in that such funds paid out in dividends are not available for other uses. Hence, a greater reliance upon debt and/or additional stock issues than would ordinarily be the case for manufacturing firms. Thomas Navin has stated in (7), that the theory behind the high dividend payout was that, "most mining investors thought of themselves as investing in a wasting asset, one that would gradually deplete over time until it ultimately became valueless." Investors, therefore, required a receipt, in the form of dividends, of a percentage of current earnings and a return on original capital. This view of reality, apparently, has not changed in some quarters, even though modern mine management ordinarily replaces depleted mines with new ones. It may be that this practice of high dividend payout coupled with relatively high financial leverage should be reexamined. Current capital structure theory could prove interesting and useful for those concerned with current conditions. Capital structure patterns and related practices in this industry are not, in many cases, congruent with those thought by some to be theoretically optimal. Prelude to Capital Structure Discussion With a few notable exceptions (such as the Guggenheims and Anaconda's chief operating,. officer in 1971) mining companies' chief executives and boards of directors have not been persons with financial backgrounds. This, one could conjecture, might have accounted for the relatively nonsophisticated nature of capital structures of mining companies. In order to appreciate the possibilities with respect to alternative influence on a firm's performance, one must be acquainted with the basics of financial theory. This paper is an attempt to familiarize the reader with (1) capital structure in general, (2) the usual components of this structure, (3) the general theory behind the use of financial leverage, and

Jan 1, 1985

William P. Blake, TUCSON, Ariz. (communication to the Secretary): As one who in youth, now nearly half a century ago, had the privilege of participating in the initial explorations which have alreacly resulted, within a single lifetime, in the establishment and Development of a vast continental empire, so well described by Dr. Douglas, I may be permitted to supplement with some additional details the comprehensive sketch given in his paper. Before the War Department, in 1853, sent out the Pacific railroad exploring parties, Fremont had already made his memorable expeditions, exploring the Great Basin and the passes into California; Sitgreaves had traversed, from east to west, the Zuni and Moqui country; and, still later, Emory had examined the region along the boundary-line between the United States and Mexico. The services of these pioneers deserve to be mentioned in even an outline of the history of continental development. Concerning the five practicable railroad-routes, suggested in the Reports of Explorations aid Surveys," etc., as published

Jan 1, 1900

By Frank C. Greene

The wildcatting in northern and northwestern Missouri, which started in 1939, was continued in 1940. Two new gas fields were found and one discovered in 1939 was further extended. The total number of completions was 94, of which 5 were oil wells with about 48 bbl. initial production, 30 were gas wells with an initial open-flow capacity of 37,655,000 cu. ft., and 59 were dry holes. The outstanding discovery was the Polo gas field, T. 55 N., R. 28 and 29 W., in Caldwell County. A sand now believed to be a lens in the Bandera shale at a depth of 400 ft. yielded flows of more than 12,000,-000 cu. ft. In all, I0 wells with 31,490,000 cu. ft. of gas, were drilled. The rock pres-sure is 80 lb. At present no arrangements for an outlet have been made. In Platte County, the Prairie Point gas pool in sec. 7, T. 51 N., R. 33 W., and sec. 12, T. 51 N., R. 34 W., and the Lake-side pool in sees. 5 and 6, T. 50 N., R. 33 W., were further developed, and in the latter both oil and gas have been found, but data are not available for publication at this time. Drilling for gas continued in proven areas in Clay County, and for both oil and gas in proven areas in Jackson and Cass Counties. Table 1 summarizes the results of drilling in Missouri in 1940.

Jan 1, 1941

By Frank C. Greene

The wildcatting in northern and northwestern Missouri, which started in 1939, was continued in 1940. Two new gas fields were found and one discovered in 1939 was further extended. The total number of completions was 94, of which 5 were oil wells with about 48 bbl. initial production, 30 were gas wells with an initial open-flow capacity of 37,655,000 cu. ft., and 59 were dry holes. The outstanding discovery was the Polo gas field, T. 55 N., R. 28 and 29 W., in Caldwell County. A sand now believed to be a lens in the Bandera shale at a depth of 400 ft. yielded flows of more than 12,000,-000 cu. ft. In all, I0 wells with 31,490,000 cu. ft. of gas, were drilled. The rock pres-sure is 80 lb. At present no arrangements for an outlet have been made. In Platte County, the Prairie Point gas pool in sec. 7, T. 51 N., R. 33 W., and sec. 12, T. 51 N., R. 34 W., and the Lake-side pool in sees. 5 and 6, T. 50 N., R. 33 W., were further developed, and in the latter both oil and gas have been found, but data are not available for publication at this time. Drilling for gas continued in proven areas in Clay County, and for both oil and gas in proven areas in Jackson and Cass Counties. Table 1 summarizes the results of drilling in Missouri in 1940.

Jan 1, 1941

AT THE dinner at the Cosmos Club in Washington, tendered to Herbert Hoover on Jan. 5, on the occasion of his retirement from the presidency of the Federated American Engineering Societies, he made an informal speech in which he pointed out not only the unique position which the engineer now occu-pies by virtue of the new Federated Societies but also the opportunity that is thus presented for national service. In this connection and in pointing out some of the reasons for the present economic maladjust-ment, Mr. Hoover said in part: This body has entered upon a path of public serv-ice that is unique in the whole United States. The engineer has devoted himself all these years to the upbuilding of the material values of the United States. He has done that effectively more effectively than-has been accomplished in any other of the great countries of the world. The birth of this society marks the evolution of the engineer into an interest in public affairs. With his intelligence, his experience and training and the unique knowledge that he possesses not only of the material but the intangible values among our people, he is now organized so that his united voice may become heard outside of his profession. We have probably 175,000 engineers in our country, representing an intellectual possibility for service possessed by no other group. It is therefore an augury of real social development when the engineers of the United States join together for purposes of public service.

Jan 3, 1922

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-'has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.' to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By Leo Horvitz

Microanalysis of near-surface soils for hydrocarbons is the basis of a method for locating gas and oil deposits. To substantiate this technique, evidence of vertical migration of hydrocarbons from petroleum accumulations is presented. Tabulated data relevant to hydrocarbon surveys conducted in several petroleum provinces are included. PEROLEUM and natural gas are composed principally of the saturated hydrocarbons ranging from methane, the lightest, to nonvolatile liquids and solids containing approximately thirty-five carbon atoms. A technique for locating buried accumulations of these hydrocarbons before drilling obviously requires that some of the hydrocarbons leave the deposit and migrate toward the surface of the earth where they may be detected in their original form. Earliest attempts to link near surface hydrocarbons to petroleum at depth were apparently made by Laubmeyer' in Germany and by Sokolov in Russia. These investigators collected samples of soil air from boreholes one to two meters deep and analyzed them for traces of hydrocarbons. They found that soil air over producing areas is richer in these constituents than is soil air over barren areas. Since 1936 work on petroleum exploration techniques of this type has been going on in this country. However, instead of determining hydrocarbon content of soil air collected in the field, investigators analyze samples of the soil itself for adsorbed and occluded hydrocarbons, which are released by suitable treatment and found in larger amounts than are the quantities reported for soil air. Difficulties often encountered in collecting gas samples in the field, moreover, are eliminated when soil is used as the sampling medium. Field Procedure: Sample locations are first surveyed over the area to be investigated. Care is taken to locate the stations at considerable distances from roads, pipelines, drilling wells, and other sources of contamination. The borehole pay be dug with a bucket-type hand auger or with mechanical drilling equipment. Lubricants are avoided in either case. When the desired depth is reached, a sample is brought to the surface, placed in a pint glass jar or can, and securely sealed. Sample containers are carefully labeled and delivered to the analytical laboratory. Generally a satisfactory sampling depth range is 8 to 12 ft. In some regions, however, satisfactory data are obtained from samples collected at much shallower depths. Such is the case, for example, in areas of west Texas where the limestone and caliche near the surface occlude hydrocarbons and prevent their rapid escape to the atmosphere. In carrying out broad reconnaissance surveys in search of large features, considerable time is saved by first taking samples one-fourth to one-half mile apart along profiles about one mile apart. If the analytical data indicate a hydrocarbon anomaly of interest, additional samples are taken to produce a more dense and uniform sampling pattern within the interesting area. This sampling program is particularly adaptable to areas that are sectionized. In areas covered with a network of roads, sampling along these roads facilitates the reconnaissance survey. Actual sampling density used depends upon areal extent of features expected. When flanks of piercement-type domes where accumulations may be only several hundred feet wide are sampled, stations are often no more than 200 ft apart. Analytical Technique: Of the hydrocarbons composing petroleum, only the more volatile would be expected to reach the surface of the earth. The analytical technique, therefore, was developed to determine only those constituents that exert a vapor pressure at room temperature. Actually, in near-surface soils, only a very small part of the hydrocarbons are heavier than pentane. Details of the analytical technique have previously been reported. Only a brief description of the methods will be presented here. A weighed portion of the sample, about 100 g, is first treated with an aqueous solution of copper sulphate and then with phosphoric acid in a partial vacuum. The copper sulphate prevents the reaction of the acid with carbides that may be present because the sample has been contaminated by auger particles. Such a reaction may produce spurious methane. The role of the acid is to decompose any carbonates present, thereby helping to release the hydrocarbons. The carbon dioxide is removed with potassium hydroxide and the flask containing the

Jan 1, 1955

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 P. G. Winchell, A. J. Heckler

An experimentally simple method for determining the effect of alloying elements on the activity of carbon is validated in Fe-Ni-C austenite. The technique consists of the equilibration of carbon between specimens of different nickel contents within a sealed silica capsule. The attainment of carbon equilibrium within each capsule is evidenced by: 1) in each capsule specimens of the same nickel content attained the same final carbon content regardless of their initial carbon contents, 2) in every capsule the final carbon content was reached for most nickel contents by carburizing and by decarburizing. The activity of carbon attained within each capsule was calculated from the carbon content of a binary Fe-C alloy placed within the capsule, and from the activity coefficient of carbon in the Fe-C system as found by Smith for CO/CO2/C equilibrium. The activity of carbon in Fe-Ni-C austenite determined by this method at 1000°C agrees with prior work by Smith, who used mother method. The measurements are extended to 800°and 1200°C. The activity coefficient of carbon 7c, in Fe-Ni-C austenite is given by: where xC is the ratio of carbon to metal atoms and XNi is the ratio of nickel to metal atoms and where the standard state is chosen such that yC = 1 as xc approaches zero in Fe-C alloys. This equation appears to be valid for xni < 0.3, and 1073° < T<1473°K. ThE activity of carbon in Fe-C austenite has been measured by smithL at 800°, 1000°, and 1200°C. Smith has also studied the effect of nickel on the activity A. J, HECKLER and P. G. WINCHELL are Graduate Student and Associate Professor of Metallurgical Engineering, respectively, School of Metallurgical Engineering, Purdue University, Lafayette, Ind. This paper is based on a thesis submitted ty,to Purdue University, in partial fulfillment of the requirements for the degree of M.S. in Metallurgical Engineering which A. J. HECKLER received from Purdue in January 1962. Manuscript submitted August 13, 1962. IMD of carbon in austenite at 1000°C. In both these studies the activity of carbon was fixed by a flowing CO-C02* *Gas mixtures of hydrogen and methane were also used in Ref. 1 but these results are not incorporated in Ref. 2 or in the present study. gas mixture. In the present work, Smith&apos;s results for Fe-Ni-C austenite are confirmed and extended to 800" and 1200°C by a different experimental technique. EXPERIMENTAL PROCEDURE In essence the experimental technique consisted of enclosing specimens of various nickel contents in an initially evacuated silica capsule and annealing the capsule until carbon equilibrium was attained among the enclosed specimens. The carbon activity obtained within the capsule was determined from the final carbon content of the binary Fe-C alloy included in each capsule and the results of smith.&apos; In order to evaluate this method the absence of nickel transfer between specimens must be established and the attainment of carbon equilibrium between samples must be assured. The absence of nickel transfer was demonstrated in the case of an originally pure iron sample which was annealed at 1200°C in a capsule with a 27.3 at. pct Ni alloy. The final nickel content of the iron specimen was less than 0.1 at. pct, a change which has a negligible effect on carbon activity. The attainment of carbon equilibrium was demonstrated within every capsule and in over half the results by achieving the same final carbon content in a sample which carburized during equilibration and in a sample of the same nickel content which decarburized during equilibration. The base Fe-Ni alloys were vacuum melted from Ferrovac E or electrolytic iron and Mond or electrolytic nickel. The samples were rolled and/or swaged and their carbon content adjusted to the desired pre-equilibration level either by methane-hydrogen carburization or by direct carbon transfer from a graphite source in a sealed silica capsule. As mentioned previously, high-carbon and low-carbon samples were prepared for most nickel levels in each capsule. The specimens were cleaned and

Jan 1, 1963

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation&apos; dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,&apos; and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.&apos; A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By Elizabeth L. Robinson

INTRODUCTION The financial structure of the mining industry has changed strikingly over the last thirty years. The changes that have taken place in the last ten years include both the acceleration of adverse trends in familiar balance sheet numbers and ratios, and the subtle but extensive increase in the complexity and diversity of funding sources, both on and off the balance sheet. The objectives of this paper are: 1. to briefly trace the evolution of trends in the mining industry&apos;s financial structure; 2. to focus in more detail on changes in the last decade; and 3. to analyze those trends both within the framework of capital structure theory, and in the context of changes in business and economic conditions. This survey focuses primarily on the mining companies listed on the major U.S. stock exchanges, since financial data for these firms are readily available. The producers of minerals are a diverse lot, however, and the quantitative data on "the mineral industry" as characterized in this survey fails to encompass the financial arrangements for the bulk of production worldwide, whether owned by governments or private-sector enterprises. Even large portions of the U.S. minerals industry - subsidiaries of still larger firms, medium-sized privately-held companies, and the small miners - were not included in the quantitative part of the analysis. THE EVOLUTION OF THE INDUSTRY&apos;S FINANCIAL STRUCTURE In the aftermath of the business failures of the Great Depression, most borrowers and lenders considered minimal debt on the balance sheet the soundest policy. By the 1950&apos;s, however, a body of literature was developing which demonstrated that the use of leverage could improve the value of the firm, given a corporate tax structure which allows interest, but not dividends, to be deducted from income. Optimal Capital Structure The objective of undertaking a new project is to improve the wealth of the current owners of the firm. If internally-generated funds are insufficient to allow growth at the desired rate, the company can raise funds either by issuing new equity, or by incurring debt. The most attractive source is the one which will provide the funds for the lowest cost. Both stockholders and lenders expect to receive compensation for use of their funds at a rate which reflects two things: (1) the return they could earn in alternative investments, and (2) the riskiness of the projected return. Factors which increase business risk include the variability of demand, sales prices and input prices, and "operating leverage", or the proportion of fixed to variable costs. In addition, from the investors&apos; point of view, the use of financial leverage concentrates risk onto the shareholders, because lenders enjoy a prior claim in the event of bankruptcy. So although financial leverage can increase a project&apos;s expected rate of return, and therefore, presumably, earnings per share, too much debt will be perceived as uncomfortably risky by equity investors, and have a negative effect on stock prices. In theory, then, there should be an optimal level of debt which the firm&apos;s managers should seek to obtain in its financial structure. The desirable proportion of debt should in general be lower for a firm with a higher inherent business risk. In addition to their own judgement, financial managers are sensitive to the attitudes of lenders, rating agencies, and investment bankers in setting financial targets (Scott and Johnson). In practice, financial structure will also depend upon the company&apos;s growth rate and level of profitability, and conditions in the capital markets at a given time.

Jan 1, 1985

By P. E. Rider, K. A. Gschneidner, O. D. McMasters

The solid solubilities for thirteen rare-earth metals in gold were determined by using the X-ray parametric method. Solubilities ranged from 0.1 at. pct for lanthanum in gold up to 8.8 at. pct for scandium in gold. The solubilities from lanthanum to gadolinium were very small and essentially constant, but a sharp increase occurred from gadolinium to scandium. The large solubilities for the heavy rare-earth metals were not expected because of the large size and electrochemical differences between rare-earth atoms and the gold atom. Contributions from first- and second-order elasticity theory plus an electronic contribution were found to reasonably account for a more favorable size factor. Electron transfer from the rare-earth metal to the gold Is thought to occur such that the resultant rare-earth and gold electronegativities are favorable for solid-solution formation. It was also found that this mutual adjustment of size and electronegutivity does not occur if the pure-metal size factors are greater than a critical value of 25 pet. The eutectic temperatures for ten systems were determined and these remained fairly constant at approximately 809 "C for the lighter lanthanide metal-gold systems until the Er-Au system was reached, at which Point the eutectic temperature successively increased reaching a maximum of 1040°C in the Sc-Au system. This rise was correlated to the size factor becoming more favorable for solid-solution formation at erbium. The valence state of ytterbium was found to change from two in the pure metal to three when ytterbium is dissolved in the gold matrix. RECENT results1 reported concerning the solubility of holmium in copper, silver, and gold, showed that the solubility of holmium in gold was quite large, 4.0 at. pct, compared with 1.6 in silver and 0.02 in copper. The small solubilities of holmium in silver and copper are quite reasonable in view of the large size difference (22.2 and 38.2 pct, respectively), large electronegativity difference (0.59 for both systems), and possible unfavorable valency factor (assuming one for silver and copper and three for holmium). The large solubility in gold, however, is unexpected because these same factors are also unfavorable for holmium and gold (22.5 pct size difference and 0.69 electronegativity difference), and because the light rare-earth metals, lanthanum, cerium, and praseodymium, have negligible solid solubilities in gold.2 In view of this unexpected behavior, it was felt that a study of the solid solubilities of most of the rare-earth metals in gold would be desirable to better understand the factors involved in the formation of solid solutions. Of the rare-earth metals added to gold in this study, only ytterbium is divalent in the pure metallic state (the other rare-earth metals are all trivalent) and many of its physical properties (such as the metallic radius, electronegativity, and so forth) are much different from those of the normal trivalent rare-earth metals.&apos; The properties of ytterbium are such that one would expect solid-solution formation to be less favorable for ytterbium in gold than for any of the normal trivalent rare-earth metals. But chemically ytterbium is known to possess a stable trivalent state, and it is quite possible that ytterbium may alloy as a trivalent metal under certain conditions rather than as a divalent metal. Because of the dual valency nature and because so little is known about the alloying behavior of ytterbium, the gold-rich ytterbium-gold alloys are of special interest. EXPERIMENTAL PROCEDURE Materials. The gold used in this investigation had a purity of 99.99 pct with respect to nongaseous impurities. In general the rare-earth metals were prepared by reduction of the corresponding fluoride by calcium metal.3 The impurity contents of the metals used in this study are given in Table I. Preparation of Alloys. Two- or 3-g alloy samples were prepared by arc melting. The samples, with the exception of some of the Er-Au alloys, had weight losses of 0.5 pct or less. All alloy concentrations noted in this paper are nominal compositions. After arc melting, the alloys were wrapped in tantalum foil, sealed off in quartz tubing under a partial atmosphere of argon, homogenized for approximately 200 hr at 780°C, and then quenched in cold water. X-Ray Methods. The X-ray parametric method was used in determining the solubility of the rare-earth metals in gold. filings were sealed in small tantalum tubes by welding under a helium atmosphere. The tantalum tubes were then sealed in quartz tubing under a partial argon atmosphere, and annealed for times ranging from 1/2 to 3 hr (the length of time was inversely proportional to the an-

Jan 1, 1965

By C. T. Malcomson

An elaborate series of experiments has been conducted during the past three years at Irvington, N. J., which has resulted in the perfection of a process for the manufacture of smokeless fuel from high-volatile coals, and for the recovery and refinement of the coal-tar products derived therefrom. These experiments have been financed by Messrs. Blair & Co., of New York, and were conducted under the direction of Charles H. Smith, a member of this Institute, and the inventor of the process. The low-temperature distillation of coal has interested investigators for many years. Sporadic attempts have been made to solve the mechanical problems, but until the Smith process was developed, they were not carried to conclusions of economic value. The present coal shortage and the increasing demand for smokeless fuels make this subject one of timely interest. DescRiption of Plant The following equipment was installed and operated during the experimental period: Four horizontal and two vertical units of commercial size for the low-temperature distillation of the coal; two vertical, two horizontal, and two inclined benches for distillation of the briquets at medium and higher temperatures; presses and auxiliary equipment necessary for making briquets; and a complete byproduct recovery and tar-refining plant. This commercial equipment is provided with gas and electric meters, pyrometers and other apparatus for recording accurately the results of all experiments. There is, in addition to the commercial equipment, a complete chemical laboratory with distillation and recovery apparatus, including facilities far refining and cracking the tar and measuring the yields and calorific value of the gas. This apparatus makes possible a study on a small scale, of the various problems involved in the process. Description of Process Mr. Smith&apos;s experiments have resulted in the production on a commercial scale of: 1. A fuel, called Carbocoal, which, for convenience in handling, is prepared in briquet form.

Jan 1, 1920

By R. E. Goodman, M. A. Mahtab

The, state of stress around a vertical wellbore in rock following nonlinear stress-strain laws is examined by means of finite element analysis. The wellbore, is considered an axisymmetrier body with axisymmetric loading. The initial vertcal and borizontal stresses are "locked" in the rock elements around the wellbore and a new state of stress is generated by the displacements which occur around the borehole. A point-uise variation of the elastic moduli is made on the basis of the new stress state and the triaxial data. The initial stresses tire now reintroduced along with tile changed moduli and original boundary constraints. This procedure is repeatrd until convergent stresses are reached. The effect of nonlinearity on streases is examined for a 6,000-ft wellbore in a scbistose gnezss and Berea sandstone using results of laborratory triaxial compression tests. The results sbou that the effect is restrited to one well radius from the bottom periphery of the bole. Beyond a distance of one-quarter radius, the elfect of nonlinearity on stresscs IS almost always less than percent for the cases conszdered, The consideration of a static pressure inside the well does not magnify the effect of monlinearity on borehole stresscs. INTRODUCTION The terms " wellbore" and "borehole" here designate cylindrical openings in the ground with vertical axis and a circular cross-section. A knowledge of the stress redistribution that occurs on excavating a wellbore is important in understanding (1) the behavior of the lined or unlined hole, (2) hydraulic fracture response, and (3) the effect of stress redistribution on drillability; also it is important in predicting initial stresses in the virgin ground, and in analyzing the response of measuring instruments placed in the borehole. Our knowledge of the state of stress around a wellbore has been restricted to homogeneous, isotropic, elastic material and derives chiefly from the analysis by Miles and Toppingl and the photoelastic work of Galle and Wilhoit2 and Word and Wilhoit.3 In this investigation the state of stress is examined for a nonlinear elastic material by means of finite element analysis. Many rocks possess stress-strain curves that depart notably from straight lines in their initial or final portions. While the literature contains abundant stress-strain data from triaxial tests (axisymmetric loading) on cylindrical rock specimens, there is little information on rock deformability under nonaxisymmetric loading conditions such as occur at each point around the bottom of a wellbore. Although there is some knowledge of the effect of intermediate principal stress on rock strength, there is virtually nothing known about its effect on rock deformability; therefore, we have assumed here that the effect of intermediate principal stress can be ignored. A schistose gneiss4 and Berea sandstone5 were selected as representative rocks for this analysis. The traditional graphs of deviator stress (ol -o3) vs axial strain were reworked to give the tangent modulus as a function of the deviator stress for varying values of the minor principal stress. The result is a nesting family of skewed, bell-shaped curves for tile gneiss (Fig. 1A) and the sandstone (Fig. 2A). A similar replotting of the lateral strain data defines the variation of Poisson&apos;s ratio (v) with the deviator stress and confining pressure. These curves, shown in Fig. 1B for the gneiss and in Fig. 2B for the sandstone, are not so well ordered as the tangent modulus curves. However, all of these display an increase of v with deviator stress application, but the rate of increase diminishes with confinement. The ET and v curves for the two rock types are tabulated in Tables 1A and 1A for use in a digital computer so that material properties corresponding to a given state of stress can be assigned by interpolation. STATEMENT OF THE PROBLEM Given a state of stress in the ground prior to drilling a hole (initial stresses), we assume that

Jan 1, 1969