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By G. A. Hellstrand

IN 1915, H. A. Guess, Vice President of American Smelting & Refining Co., in charge of its Mining Department, learned that the Anglo-New-foundland Development Co., Ltd., a pulpwood and paper-mill enterprise, had found upon its large concession in Newfoundland, and had opened up by shaft to the third level and some drifting, a lenticular orebody indicat-ing about 100,000 tons, as an extremely fine-grained sulfide ore, averaging about 0.05 oz. Au, 4 oz. Ag, 1.5 per cent Cu, 10 per cent Pb, 18 per cent Zn; and that having sent parcels of this ore to Minerals Separation, Ltd., and various other metallurgical testing concerns without obtaining any success in commercial separations thereon, had discontinued work thereon and let the workings fill. Mr. Guess wrote to the general manager of that company and obtained a few hundred pounds of the typical ore, which he sent to his company's metallurgical testing laboratory at Flat River, Mo., outlining various flotation tests desired thereon, in an endeavor to obtain separation into a commercial lead concentrate and a zinc concentrate. But the art of flotation had not then progressed far enough to treat such ore, the galena and zinc blende being so fine grained that grinding to about 300 mesh was required to release the mineral particles in their gangue. Mr. Guess had flotation and other tests continued upon this ore from time to time with whatever new reagents and flotation devices were evolved as time went on, and finally, in 1925, he succeeded in effecting in his company's testing plant, then at Wallace, Idaho, separations into lead concentrates and zinc concentrates of satisfactory commercial grade. Mr. Guess then proceeded to unwater, examine and sample the property and made with the owners a partnership operating agreement upon the mine itself and a considerable area surrounding it, and in the early summer of 1926 began to prospect for additional orebodies, utilizing for such prospecting geophysical methods, under the direction of Hans Lundberg, methods which up to that time had been little used in mining in the western hemisphere.. This geophysical work found two large flat-lying orebodies of a type precisely similar to the smaller body of the original discovery. The larger orebody, some 3500 ft. west of the original

Jan 1, 1934

By Augustus J. Bowie

THE discovery of the auriferous cement gravel deposits in and near Deadwood Gulch, Lawrence County, Dakota Territory, in 1876, created a mining excitement, and rush to the Black Hills. Numerous ten and twenty-stamp mills were built on Deadwood Gulch ; Central City and the town of Deadwood sprang into existence, and became the centres of the mining industry of the Hills. Gold quartz deposits were subsequently discovered and located on a so-called mineral belt, extending from Whitewood Creek on the south, to Deadwood Gulch on the north. A northerly group of these quartz locations was purchased in December, 1877, by parties in San Francisco,, who formed a company, incorporated under the name of the Father de Smet Consolidated Gold Mining Company. This company immediately commenced the work of exploration. The deposits were proved to be extensive, and easily mined, but it was found that the ore, on an average, would not. yield more than $10.00 per ton* of 2000 pounds. At this time the cost of supplies and materials in the Hills was high. Miners' wages were $3.50 per diem, and custom mills charged $6:00. per ton. The successful working of mines on "the belt" necessitated cheap milling. The ores being of so low grade,† this could be accomplished only with large and economically running mills. To insure the greatest possible economy, the Father,& Smet mill * Up to December 31st, 1879; the de Smet mine had produced bullion of the value of $718,211.68 from 76,155 tons of ore, being an average value of $9.41 per ton. During the year ending December 31st, 1879, the mine produced 46,344 tons, which yielded $425,360.42, or $9.18 per ton. The total gross cost of working for the corresponding period, including deadwork, exchange, legal expenses, fete., wits $219,914.82. The yield of the mine for the year 1880 (Engineering and Mining Journal, February 5th, 1881), was $600,011, with total expenses of mining and milling, of $313,108. † The first 4083 tons extracted from the de Smet mine, were selected, yielding $62,783.97. The next 25,728 tons produced $230,067.24. The total 29,811 tons were weighed, and worked at custom mills. The yield of the first 409 tons from tine Golden Terra Mine was $11.44 per-ton.

Jan 1, 1882

By Edgar Schweitzer

The original Dorrance breaker of the Lehigh Valley Coal Co. was erected in 1883. The coal beds were clean and dry, consequently a dry preparation system was used, consisting of revolving cylindrical screens for sizing and hand-picking, to remove the few impurities from the run of mine coal. The picking or cleaning room contained long parallel rows of chutes with seats mounted on them, for the use of the breaker boy, who bent over the chute and picked out the refuse material from the coal as it gravitated down the chute. The introduction of dry mechanical pickers, of, the sliding frictional type, in the early nineties lessened the number of boys, but hand-cleaning on the coal and refuse discharge ends of the mechanical picker was necessary. The Pardee spiral pickers, which were brought out about 1900, were better than the gravity pickers and gradually replaced them. In 1912 the breaker was entirely remodeled, although the original frame was retained. The revolving screens were replaced by shaking screens, and Pardee spirals were installed on all sizes of coal from egg to pea coal, inclusive. Hand-picking still was necessary on the coal and refuse ends of the spirals, although the changes did result in a reduction of the former breaker force. As mining advanced, and the thick clean bed became exhausted, it was necessary to mine veins containing a high percentage of impurities, which complicated the preparation problem. The most serious difficulty was the increase in the quantity of damp or wet run of mine, which could not be fully cleaned on the spirals. When this quantity exceeded approximately 5 per cent. of the feed, it was necessary to send the excess of the wet coal to the company's Prospect colliery for wet washing. This plan worked well for a time, but as the amount approached 15 per cent., with the prospect of a further increase, the company considered the building of a wet-washing plant. The Dorrance breaker was the only dry-cleaning plant operated by the company. At the seventeen other collieries, wet washing was employed, and jigs, both plunger and pan, were used. All the practical methods used in the anthracite fields were investigated, and it was finally decided to adopt the Rheolaveur system. The decision was due largely to the experience gained from the the operation of a Rheo-

Jan 1, 1931

By E. T. Knight, John D. Gill

Much has been written and said concerning the alleged wasteful and uneconomic use of natural gas and petroleum. Espccially condemned has been the use of natural gas for the production of carbon black and the use of heavy fuel oil under steam boilers.' The critics of these usages of gas and oil have sought to make effective their verbal attacks on the industry by the repetitive expression of the words "inferior" and "superior" uses2 of petroleum. Thus, to employ natural gas for residential heating was to use it in a superior way; to use it for the production of carbon black was to use it in a wasteful and uneconomic way. To use petroleum for the production of automotive fuel was to use it in a superior way; to employ it as a residential fuel and as the prime source of power in an industrial plant was to use it in an inferior and uneconomic way. No doubt the objections to such employment of gaseous and liquid natural hydrocarbons originated in the belief that natural gas and petroleum are limited, nonregenerative mineral resources, and that the functions they perform can be just as well performed by other natural resources like coal13 of which practically unlimited reserves are known. The generations that have dominated each of the last four decades have counted reserves4 of petroleum in terms of a few years supply. Meanwhile, domestic demand for motor fuel rose spectacularly from a few million barrels in 1900 to more than 500,000,000 bbl. last year.5 The more imaginative and vocal critics drew startling word pictures of the catastrophe of 25,000,000 motor vehicles made useless and of the great automotive manufacturing and allied industries brought to an untimely end, and millions of workers left hopelessly unemployed by what they called the deplorably rapid depletion of the petroleum reserve. Many of the critics have been sincere advocates of the conservation of natural resources; many others, and in recent years probably the majority, have espoused the doctrine of conservation to promote their own self-interest rather than that of the public. The latest advocate of severe restriction in the use of petroleum for the alleged purpose of conserving the petroleum resource proposes to achieve that end by a bill,6 now before

Jan 1, 1938

By J. R. Long, T. R. Graham, C. W. Matthews, R. S. Dean

IN a previous paper§ the authors reported on the mechanical properties of a 65 per cent copper, 10 per cent manganese, 25 per cent zinc alloy as compared with similarly processed cartridge brass. Additional investigations by these laboratories, on higher copper alloys, have demonstrated that at lower zinc concentrations even larger amounts of pure manganese may be added to copper-zinc alloys without exceeding the single-phase solid solution limits, and that similar increases in tensile strength, yield strength, and hardness may be obtained without excessive decreases in ductility. Several compositions in this range showed also a decided color change with increasing manganese. The normal "brassy" color was considerably lightened and reduced to a faint yellow cast at 15 per cent manganese. With higher manganese contents the alloys were essentially white and similar in appearance to the nickel-silver alloys. From this work it appeared that it would be desirable to determine more completely the properties of the wrought and annealed white alloys. Accordingly, a more detailed study was planned of an alloy having the composition 70 per cent copper, 20 per cent manganese, and 10 per cent zinc. This alloy remained single-phase throughout the working and annealing cycles of the preliminary tests and appeared to be about the strongest of the white single-phase alloys. The project included also an investigation of additional alloys, deviating from this composition by 5 per cent of each of the three components to evaluate the effects of variation in composition; also a study of the properties of the central alloy made with silicothermic manganese. MATERIAL PREPARATION Electrolytic manganese, wirebar copper, and electrolytic zinc were used for the preparation of the alloys. Representative analysis of the electrolytic manganese seldom exceeds 0.01 per cent iron, 0.02 per cent sulphur and 0.02 per cent lead, with no silicon or aluminum. A typical sample of the silicothermic manganese metal contained 2 per cent iron, 0.81 per cent silicon, 0.i6 per cent carbon, and 0.36 per cent aluminum. Melting and alloying were performed in a high-frequency furnace with magnesia crucibles. Melts were deoxidized with small aluminum additions and cast into 25-lb. slab ingots. Care was exercised in deoxidation to avoid excessive amounts of residual aluminum, which has been found to have significant effects on alloys in this system. All ingots were hot-rolled at 1200° to 1300°F. and then cold-rolled with intermediate anneal-

Jan 1, 1945

By Michael Shaughnessy, O&apos

The outstanding features of the Coloinbian situation for the year 1929 were legal and political. The passage of Law 84 and the promulgation of the Regulatory Decree 150 were recounted in the review for 1928, as was also the Presidential proclamation suspending this law and its accompanying decree until decision could be reached in the suits filed against them before the Supreme Court and the Council of State. Early this year the Minister of Industries, Jose Antonio Montalvo, announced the appointment of a commission of foreign experts to aid in drafting a new petroleum law. He requested all of the foreign experts employed not to consult with the oil company representatives in Bogota, and these experts were therefore shut off from receiving any suggestions from those who had actually operated in the country and knew the conditions under which operations would take place. It was to be expected that the provisions of a law suggested under such circumstances would not meet operating conditions satisfactorily. The specific objections are stated in O'Shaughnessy's South American Oil Reports (April, 1929). An especially qualified commentator observes that one of the curious provisions of the proposed law was the high royalty on gas—5c. per 1000 cu. ft. of gas produced. There was also a provision requiring 20 per cent. of the stock of the company operating in Colombia to be offered for sale to Colombians. The bill failed to pass Congress in the closing hours of the session. The Supreme Court, in the meantime, handed down its decision on Law 84 of the previous year and Regulation 150 covering the enforcement of that law. Contrary to expectation, the majority opinion of the Court practically affirmed the constitutionality of both the law and the regulatory decree, with the exception of Article 20 and parts of Article 21 of the decree which referred specifically to the registration of private properties. At the time the suit was filed against Law 84 and Decree 150 the operation of these measures was suspended by the Executive. Law 84 and its Regulatory Decree 150 still remain suspended as the Council of State has not yet brought in a decision upon the questions raised in the suits instituted by the various companies against the law and decree, and at the moment of this writing it appears unlikely that such a decision will be reached by that body.

Jan 1, 1930

By T. B. Massalski, Horace Pops

The occurrence and the temperature dependence of the athermal martensitic transformation in bcc Cu-Zn ß-phase alloys have been studied by cold-state microscopy, differential thermal analysis, and electrical -resistivity measurements. CinenzatograpJzic studies have shown that in the majority of alloys the transformation occurs in two stages. A thermoelastic phase, having a 'needlelike" uppearance, forms initially at the MS temperature and grows relatively slowly, chiefly in the edge (lengthwise) direction. With further cooling, an additional martensitic phase forms in rapid bursts at a lower temperature, MB, Both martensitic phases appear to have the same cry stallographic habit hut their modes of formation and growth are different. For the composition range studied, between 38.55 and 41.49 wt pct Zn, the habit planes determined are close to the (2.17 ,12) plane of the matrix, in general agreement with the prediction of the phenomenological theory of martensite formation. Thermal cycling through the MB temperature produces permanent plastic deformation in the 0 matrix and gradutally eliminates the typical burst phenomena. Thermal cycling only through the MS temperature produces no noticeable deformation effects. THE bcc Cu-Zn ß-phase alloys tend to become unstable at low temperatures and undergo a martensitic transformation,'-3 but the details of the transformation have not been completely determined. Following earlier metal log raphic and X-ray work1 Tichener and ever' determined by means of electrical-resistivity measurements the temperature range of the martensite transformation during continuous cooling. The transformation temperature was found to decrease with increasing zinc content, becoming about -130°C for an alloy containing 40.04 wt pct Zn. Hull and Garwood3 made a metallo-graphic study of Cu-Zn 0 brasses at temperatures down to -160°C, and determined the habit plane of the transformation product for an alloy containing 38.88 wt pct Zn. No metallographic studies below liquid-nitrogen temperatures have been reported. The martensitic transformation in ß-brass alloys can also be induced by deformation.1,4 The MD temperature corresponding to the appearance of the strain-induced martensite is some 300°C higher than that observed without strain, and hence the transformation can be strain-induced in alloys containing a higher percentage of zinc. Massalski and Barrett4 found that alloys containing as much as 51.89 wt pct Zn could be transformed into a faulted hcp structure by cold working at liquid-helium temperature. Because the details of the MS temperature and morphology reported in the literature are somewhat incomplete, a further study has been made of some of the above features. A design of a cryogenic stage for optical metallography5 has permitted the examination of specimens at temperatures down to 4.2oK, and the use of a cinecamera has permitted a study of the morphology on cooling and heating. The particular aim of the present work was to examine the transformation temperatures, the habit planes, and the growth morphology over a wide composition range in the ß-phase field. The effect of thermal cycling upon the subsequent transformation was also examined.

Jan 1, 1964

By Albert J. McIntosh

With petroleum consumption declining temporarily after V-J day, the oil industry is urged to use this period as a kind of stopgap to rebuild its war-depleted inventories and help cushion the effect of this decline on producers and refiners. Higher inventories should be reestablished, since recent experiences have indicated that, by and large, the present inventories of crude oil are too low even with the tremendous current production available. The following analysis indicates that inventory levels could be built up to about 490,000,000 bbl. by the end of 1947, an increase of about 40,000,000 bbl. over the reported stock estimated for the war's end. If at the end of the war the military have some 20,000,000 bbl. on hand, this inventory will either be resold to the industry or certain demands that have been assumed to be met by industry will be supplied out of these military stocks, which would leave about 20,000,000 bbl. (net) to be built up from current production. For stock rebuilding the industry could use 10,000,000 bbl. of crude plus 10,00,000 bbl. of products, totaling 20,000,000 bbl. If this were spread over a year, this would mean 55,000 bbl. a day. By analyzing the average inventories held in a year with the total quantity of goods handled during the year, the following study and tables indicate how far the inventories should increase in the immediate postwar period. Introduction For the period immediately following V-J day, most of the petroleum economists have forecast a considerable decline in the total consumption of petroleum and its products in the United States. This will be caused by the elimination of most of the military demands and the inability of civilians to immediately replace automobiles, burners, etc., and thus increase their requirements to make up for the military decline. When the automobile industry has been back on full production for two or three years, civilians will be able to consume much larger quantities of gasoline. Delay in the manufacture of new oil burners and the time it takes to construct new homes, adds up to the same story for distillate fuels. In reviewing this outlook, the question has arisen whether the petroleum industry should not use this period of lower consumption as a kind of stopgap to rebuild its war-depleted inveritories and help cushion the effect on producers and refiners of this sudden drop in requirements. Some persons have indicated that hundreds of thousands of barrels a day could be used for this purpose extending over a year or more. Refineries will be in existence, which could run over 5,000,000 bbl. of crude oil a day and crude-oil production might be running 600,000 to 700,000 bbl. a day above the demands now forecast for the period after V-J day. Reasons for. Making Inventories In order to plan intelligently for this period, the petroleum industry should determine the needs for the establishment of higher inventories for crude and petroleum products than have been carried during the war. The reasons for trying to make such a determination are as follows:

Jan 1, 1945

By J. F. Gallie

From the standpoint of exploration and new discoveries, South Arkansas had a discouraging year in 1944. In January there were 73 untested drilling blocks, and 60 additions were made during the year. Of the total, 65 were condemned by dry holes on or adjacent to them, while 5 proved productive. The latter resulted in the discovery of the Salem Church, Calhoun Wilks, and Strong fields, and the extension of the Village field to the southeast. The year ended with 63 untested blocks, 41 of which were scheduled for tests to the Smackover lime, the state's deepest oil-producing formation. Geophysical activity in 1944 totaled 164 crew weeks, of which 110 were seismic, 43 gravity, and 11 radioactive (Fig. I), in contrast with 674 crew weeks reported for 1943, of, which 563 were seismic and in gravity, Five seismograph and two gravity crews were engaged in exploration in South Arkansas during January 1944. but only two seismograph crews were working there at the end of the year. In addition, exploratory core drills were used for a total of 38 weeks during the year. The year's few discoveries, none of which is considered as having added appreciably to state reserves, were the meager results obtained in the drilling of 62 wildcat wells 2000 ft. or deeper. Of this total (a detail of which appears in Table 2), 42 were drilled to the Smack-over lime or below, The average depth of the 62 wells was 5384 ft., as compared with 4992 ft. in the preceding year, while the average depth of the 42 wildcats in the lime was 5913 ft. in 1944. Fig. 2 has been prepared to show all , wells penetrating to the Reynolds oölitic lime. The 1944 dry holes are circled lightly, while discoveries are heavily circled and shown as producers. Smackover lime fields, producing from the Reynolds oolitic lime member, are indicated in black, and the locations of dry wildcat wells drilled prior to 1944 are also shown. Table 3 provides a listing of all Smackover lime wells drilled through the end of 1944. Production for the year was slightly more than in 1943, totaling 29,282,747 bbl., as compared with 27,521,943 bbl. for the preceding year. The increase was 1,760,804 bbl., or 6.4 per cent, bringing production to a peak exceeded only in the 1923 to 1928 period of flush production from the older shallow fields, principally Smackover. The increase was largely attributable to additional development in the Dorcheat-Macedonia, Atlanta, Fouke, Stephens-Smart, Haynesville, and Village fields, little production deriving from 1944 discoveries. These six fields accounted for loo of the 122 field wells drilled during the year. Annual and cumulative production for the producing life of the state are presented graphically in Fig. 3. Fig. 6 has been prepared by the author to show the producing ages and present known productive limits of all fields in South Arkansas. Production data, as usual, are assembled in Table 2, and provide a further breakdown of producing formations in the individual fields.

Jan 1, 1945

By A. Andreas

New Mexico established an annual record by producing 38,897,741 bbl. of oil during 1940. This was approximately 6 per cent greater than the 1939 production of 36,746,840 bbl. The daily average produc-tion was 106,569 bbl. New Mexico retained its position as the seventh oil-producing state. The recommendations of the United States Bureau of Mines were followed by the Oil Conservation Commission in setting the monthly state allowable. At the beginning of the year the average top allowable for each qc-acre unit was 40 bbl. and at the close of the year it was 36 bbl. Remedial work by the operators has been extremely beneficial and satisfactory in reducing the gas-oil ratios in various fields. Gas formerly blown into the air is now being processed by numerous casinghead plants. The Oil Conservation Commission, with the full cooperation of the Proration Office and operators, has taken bottom-hole pressure surveys and has done considerable remedial work in various fields. Two new oil fields and one gas field were discovered in New Mexico during 1940. Numerous extensions to the existing fields were made. Some of these were definitely wildcats in the same townships designated as fields and some, although called extensions, were more than 3 miles from production. Lea County continued to be the largest oil-producing county in the state, with a production of 33,976,394 bbl. It had the largest number of completions during 1940, with 303 oil wells, 9 gas wells and 13 dry holes—a total of 325 wells. Eddy County was the next most active county, with 239 completions, of which 163 were oil wells, 8 gas wells and 68 dry holes. It produced 4,405,158 bbl. of oil during the year. The increased activity in Eddy County and the completion of a large number of producing oil wells have created a transportation problem that can be solved only by additional pipe-line facilities. During the year Eddy County was unable to produce 1,500,000 bbl. of its allowable oil, because there was no pipe-line outlet. There were 601 wells completed in New Mexico in 1940, of which 478 were oil wells, 22 gas wells and IOI dry holes. This was a decline of approximately 9.5 per cent in the number of completions compared with 1939, when 659 wells were drilled. Southeastern New Mexico Lea County.—The largest producing field in Lea County was the Monument field, with 6,894,475 bbl.; followed by Eunice with 6,559,348 bbl. and Vacuum with 4,743,065 bbl. The Hobbs pool, which for years was the largest producing field in the state of New Mexico, was fourth with 3,790,477 bbl. The Vacuum pool was the most active area, having 68 completions, of which 67 were oil wells and one was a dry hole. Only one new field was discovered in Lea County during 1940; the discovery well was in the Caprock area, the Livermore State No. I, in the SE. 1/4 SE. 1/4 sec. 30, T. 12 S, R. 32 E. This well was drilled to a

Jan 1, 1941

By A. Andreas

New Mexico established an annual record by producing 38,897,741 bbl. of oil during 1940. This was approximately 6 per cent greater than the 1939 production of 36,746,840 bbl. The daily average produc-tion was 106,569 bbl. New Mexico retained its position as the seventh oil-producing state. The recommendations of the United States Bureau of Mines were followed by the Oil Conservation Commission in setting the monthly state allowable. At the beginning of the year the average top allowable for each qc-acre unit was 40 bbl. and at the close of the year it was 36 bbl. Remedial work by the operators has been extremely beneficial and satisfactory in reducing the gas-oil ratios in various fields. Gas formerly blown into the air is now being processed by numerous casinghead plants. The Oil Conservation Commission, with the full cooperation of the Proration Office and operators, has taken bottom-hole pressure surveys and has done considerable remedial work in various fields. Two new oil fields and one gas field were discovered in New Mexico during 1940. Numerous extensions to the existing fields were made. Some of these were definitely wildcats in the same townships designated as fields and some, although called extensions, were more than 3 miles from production. Lea County continued to be the largest oil-producing county in the state, with a production of 33,976,394 bbl. It had the largest number of completions during 1940, with 303 oil wells, 9 gas wells and 13 dry holes—a total of 325 wells. Eddy County was the next most active county, with 239 completions, of which 163 were oil wells, 8 gas wells and 68 dry holes. It produced 4,405,158 bbl. of oil during the year. The increased activity in Eddy County and the completion of a large number of producing oil wells have created a transportation problem that can be solved only by additional pipe-line facilities. During the year Eddy County was unable to produce 1,500,000 bbl. of its allowable oil, because there was no pipe-line outlet. There were 601 wells completed in New Mexico in 1940, of which 478 were oil wells, 22 gas wells and IOI dry holes. This was a decline of approximately 9.5 per cent in the number of completions compared with 1939, when 659 wells were drilled. Southeastern New Mexico Lea County.—The largest producing field in Lea County was the Monument field, with 6,894,475 bbl.; followed by Eunice with 6,559,348 bbl. and Vacuum with 4,743,065 bbl. The Hobbs pool, which for years was the largest producing field in the state of New Mexico, was fourth with 3,790,477 bbl. The Vacuum pool was the most active area, having 68 completions, of which 67 were oil wells and one was a dry hole. Only one new field was discovered in Lea County during 1940; the discovery well was in the Caprock area, the Livermore State No. I, in the SE. 1/4 SE. 1/4 sec. 30, T. 12 S, R. 32 E. This well was drilled to a

Jan 1, 1941

By J. E. Hilliard

Isobaric sections of the eutectoid region of the iron-carbon phase diagram have been exgerimentally determined at 35, 50, and 65 kb. The phase boundaries were located by metallographic analysis of specimens quenched after equilibriatwn at known temperatures and pressures. With increasing pres -sure a pronounced decrease in the solubility of FesC in austenite was observed together with a depression of the eutectoid temperature. These two effects resulted in a shift of the eutectoid composition toward a lower carbon content; at 65 kb the eutectoid was at less than 0.2 wt pct C. These results are in qualitative agreement with thermodynamic calculations. It has also been shown by calculations that Fe3C in contact with saturated austenite will be stable with respect to both graphite and diamond formation at all pressures above -3.5 kb. 1 HE investigation described in this article was part of a more general study of the effect of high pressure on transformations in Fe-C alloys. Thermodynamic calculations and exploratory runs made in 1959 at the start of the program indicated an appreciable change with pressure in the phase equilibria of Fe-C alloys. However, the calculations were not considered reliable enought to provide the quantitative information required for the interpretation of the effect of pressure on the kinetics of transformations. An experimental investigation was therefore made to determine a series of isobaric sections of the eutectoid region of the phase diagram at pressures up to 65 kb. EXPERIMENTAL PROCEDURE Materials. Seven alloys with analyzed carbon contents of 0.10, 0.20, 0.38, 0.60, 0.77, 0.93, and 1.20 wt pct C were prepared from Ferrovac" iron and high-purity graphite induction melted in magnesia crucibles under argon. The ingots were hot worked and swaged down to 0.19-in.-diam rod which was then centerless ground to a final diameter of 0.125 in. Samples for chemical and spectrographic analyses were taken from each end of the rods. The prin- cipal impurities were found to be Ni, Al, Co, and Si which were present in amounts up to 0.03, 0.02, 0.01, and 0.01 wt pct, respectively. Specimens were prepared by slicing the ground rods into pills 0.06-in. thick which were silver plated to reduce decarburization during the equilibration. Silver was chosen for this purpose because of its very low solubility for carbon and its mutual immisicibility with iron. High-Pressure Apparatus. The high-pressure runs were carried out in the "Belt" apparatus.' As shown in Fig. 1, this consisted of a cylindrical cell compressed between two Carboloy punches loaded by a uniaxle press. Radial support to the cell was given by the "belt" which was a Carboloy die heavily prestressed by a series of steel binding rings. Laminated gaskets of lava and metal separated the punches from the inner surface of the "belt". A cross-section of the high-pressure cell is shown in Fig. 2. Two specimen pills were located inside a resistance heater of 0.20-in.-diam Nichrome tubing. The ends of the tube were sealed with alumina and lava pills tamped in place after the

Jan 1, 1963

By F. C. Miller

The metallurgical fuel of Colorado, Utah, and New Mexico has been a Veiny tardy member in the caravan of western industrial progress. The history of western coke has naturally been closely related to the development of the metallurgy of iron and steel and the precious metals, in the State of Colorado. It was at Leadville, with a population of 300 in 1877, that the Sentinel was published by Richard S. Allen. The Sentinel gave very full accounts of the various mineral discoveries at the new town of Leadville, which found their way to the more widely circulated journals of the East, and attracted the attention of many people. At the close of 1878, a census slowed a total of 5040 persons. The first smelter was established in 1877, at Malta, two miles from Leadville, by A. R. Meyer, but was not successful. It was succeeded by the Harrison Reduction Works, in 1878. The La Plata began with one furnace in June, 1878, and in 1879 had four furnaces in active operation. These furnaces used charcoal for fuel, and, because of hot tops, suffered a tremendous loss in lead and silver. This difficulty was overcome by the erection of 50 single-bank 10-ft. beehive ovens at Crested Butte, Colo., in 1880. The slack coal sent to these ovens was very pure, and yielded a coke carrying as little as 4.5 per cent. ash. Among the pioneers in the Leadville district were Grant, Eddy, James, Billings, Eiler, and Dickson. To these men the West owes the present expansion of its mining industry, and the erection of metallurgical processes for the treatment of precious metals. On Mar. 1, 1876, Pueblo was connected to the Atchison, Topeka & Sank Fe by the Pueblo & Arkansas Valley branch. The first smelter was erected in Pueblo by Mather and Geist. This modest plant grew into the immense Pueblo Smelting and Refining Co., now a part of the American Smelting and Refining Co. Coke for these small furnaces was made from unwashed Engleville coal, in 186 single-bank 12-ft. ovens at El Moro, in the Trinidad district, and it was not uncommon for the percentage of ash to exceed the percentage of fixed carbon in the coke. On Jan. 23, 1880, the Colorado Improvement Co. consolidated

Jan 1, 1920

By J. R. Long, T. R. Graham, C. W. Matthews, R. S. Dean

In a previous paper! the authors reported on the mechanical properties of a 65 per cent copper, 10 per cent manganese, 25 per cent zinc alloy as compared with, similarly processed cartridge brass. Additional investigations by these laboratories, on higher copper alloys, have demonstrated that at lower zinc concentrations even larger amounts of pure manganese may be added to copper-zinc alloys without exceeding the single-phase solid solution limits, and that similar increases in tensile strength, yield strength, and hardness may be obtained without excessive decreases in ductility. Several compositions in this range showed also a decided color change with increasing manganese. The normal "brassy" color was considerably lightcncd and reduced to a faint yellow cast at 15 per cent manganese. With higher manganese contents the alloys were essentially white and similar in appearance to the nickel-silver alloys. From this work it appeared that it would be desirable to determine more completely the properties of the wrought and annealed white alloys. Accordingly, a more detailed study was planned of an alloy having the composition 70 per cent copper, 20 per cent manganese, and 10 per cent zinc. This alloy remained single-phase throughout the working and annealing cycles of the preliminary tests and appeared to be' about the strongest of the white single-phase alloys. The project included also an investigation of additional alloys, deviating from this composition by 5 per cent of each of the three components to evaluate the effects of variation in composition and a study of the propertics of the central alloy made with silicothermic manganese. Material Preparation Electrolytic manganese, wirebar copper, and electrolytic zinc were used for the preparation of the alloys. Representative analysis of the electrolytic manganese seldom exceeds 0.01 per cent iron, 0.02 per cent sulphur and 0.02 per cent lead, with no silicon or aluminum. A typical sample of the silicothermic manganese metal contained 2 per cent iron, 0.81 per cent silicon, 0.16 per cent carbon, and 0.36 per cent aluminum. Melting and alloying were performed in a high-frequency furnace with magnesia crucibles. Melts were deoxidized with small aluminum additions and cast into 25-lb. slab ingots. Care was exercised in deoxidation to avoid excessive amounts of residual aluminum, which has been found to have significant effects on alloys in this system. All ingots were hot-rolled at 1200' to I300°F. and then cold-rolled with intermediate anneal-

Jan 1, 1945

By D. E. Furman

The thermal coefficients of linear expansion for several stainless steels have been determined over the temperature range from —300° to 1000°F. The steels studied include types 301, 304, 316, 347, 310 and 330. This wide selection of compositions allows an insight into the effects of austenite stability and alloy content on the expansion characteristics. THE recent increased use of materials in low temperature applications has created a field for which the properties of austenitic iron, chromium, nickel alloys are particularly suited. Tensile and impact values of stainless steels at subzero temperatures have been made available in the technical literature but, as yet, little information has been published with respect to expansion characteristics. In order to supply this need, a study was made of several of the more common compositions. Those selected were types 301, 304, 316, 347, 310 and 330 stainless steel. Both the mean and instantaneous coefficients of linear expansion were determined over the temperature range from —300°F to 1000°F. Procedure The materials used were commercial grades with the exception of type 301 which was made in a 10# high frequency furnace. The compositions are listed in table I. All steels were given an anneal at 1950°F for 30 min and water quenched prior to machining the expansion specimens. Expansion readings were taken on specimens 0.250 in. in diam by 4.000 in. long with a fused quartz tube expansion apparatus similar to that described by Hidnert and Souder.1 Temperature measurements were made with a chromel-alurnel thermocouple calibrated for use at subzero temperatures. A bath of propane was used for temperatures from —300° to —100°F and one of alcohol from —100°F to room temperature. These baths were contained in large mouthed Dewar flasks and cooled to the desired temperature levels by passing liquid nitrogen through glass cooling coils placed in the flasks. The baths were stirred constantly for temperature equalization and were heated by immersing metal rods which were replaced frequently enough to give a heating rate of approximately 150°F per hr. A resistance wound furnace was used for heating from room temperature to 1000°F and throughout this range rates of about 450°F per hr were maintained. The furnace was designed so that the temperature gradient over the specimen was within 5°F. In most instances, the expansion readings were taken during heating from —300° to +300°F at

Jan 1, 1951

By Frederick F. Frick

SPONGE iron as produced at Anaconda is a fine, -35 mesh, impure product, about 50 pct metallic iron, obtained from the reduction of iron calcine at a temperature of 1850°F by use of coke resulting from slack coal. The metallic iron particles are bulky and spongey and precipitate copper readily and rapidly from a copper sulphate solution. Investigation of the treatment of Greater Butte Project, Kelley, ore at Anaconda early showed the desirability of using sponge iron as a precipitant for the copper in solution resulting from desliming of the ore in a dilute sulphuric acid solution. Anaconda had done considerable work on the production of sponge iron in 1914 for use as a precipitant of copper from leach solutions. Some success and considerable experilence were attained at the time. indicating that, sponge iron might be successfully made by a modification of the process used in 1914, a batch process in which an iron calcine was reduced by means of soft coke, resulting from noncoking coal, in a Bruckner-type revolving horizontal cylindrical furnace widely used 50 years ago. The coke and calcide formed the bed in the Bruckner furnace, which was rotated at about 1 rpm. The bed was brought to a temperature of about 1800°F by means of an oil flame over the surface. Although results were reasonably satisfactory, they did not warrant full development of the process at that time. A good deal of work has been done in the last 50 years on the production of sponge iron. The objective in some cases has been the production of a precipitant for copper from solution, but the bulk of the work has been done for the production of open-hearth steel furnace stock. The production of an open-hearth stock presents two problems rather than one: first, producticon of the sponge iron, and second, what is perhaps of equal difficulty and importance, conversion of the sponge iron into a form suitable for use in the open-hearth furnace. So far as is known to the writer, none of the sponge iron processes tried in the past have proved to be economically feasible. However, Anaconda had a combination of conditions appearing to justify an attempt to produce sponge iron which would serve for the leach-precipitation-float process. It was thought that the process used in 1914, if changed to a continuous one, might work out satisfactorily. The following favorable conditions at Anaconda justified the investigation: 1—A sufficient tonnage of good grade iron calcine resulting from the roasting of a pyrite concentrate in one of the acid plants, at substantially no cost. 2—Reasonably cheap natural gas. 3-—The fact that there was no need for production of a high grade product. 4— The fact that there was no need for obtaining a consistently high reduction of' the iron in calcine. A small revolving Bruckner-type furnace about 2 ft ID by 4 ft long was set up for early pilot work at the research building. This pilot furnace showed that a satisfactory product could be obtained at reasonable cost. It also indicated a marked advantage in preceding the reduction furnace with a furnace of similar size and capacity for preheating and roasting out any residual sulphur from the feed. The small furnace was operated for several months, various details of the process were worked out. and sponge iron was produced to supply a pilot LPF plant which treated 300 lb of Kelley ore pel- hr. Later a second pilot furnace 5 ft in diam and 12 ft long inside was set up at our reverberatory furnace building. This furnace confirmed the data of the small furnace and gave a basis for design of the final plant. At Anaconda a pyrite concentrate, running about 48 pct S, is recovered from copper concentrator tailings by flotation. This concentrate is roasted to sulphur of 3 pct or less at the Chamber acid plant. The iron calcine contains about 57 pct Fe and 18 pct insoluble. The iron calcine feed, as mentioned before, is re-roasted and preheated in a reroast furnace preceding the reduction furnace. Both are of the Bruckner type. The reroasted calcine is fed into the reduction furnace at 800" to 1000°F along with 30 pct slack coal. In the feed end of the furnace the volatile is burned from the slack, giving a soft coke which readily serves for reduction of the iron. Hard metallurgical coke will not serve the purpose. since it does not reduce CO readily at a temperature of 1850°F. All indications are that the actual reduction of the iron is accomplished by carbon monoxide below the surface of the bed, which is 30 in. deep at its center. Apparently there is a constant interchange: Fe²O³ + 3CO = 2Fe - 3CO², CO² + C = 2CO Actually iron oxide is reduced by CO at somewhat lower temperature than the 1850 °F used in the process. but this temperature is necessary to obtain a satisfactory rate of furnace production. The furnace atmosphere is generally reducing, and typical blue carbon monoxide flames satisfactorily cover the bed. Gas flames from four 3-in. Denver Fire Clay Inspirator burners are played directly on the bed, which is slowly cascaded by the 1 rpm of the furnace. An excess of coke is necessary to assure maintenance of good reducing conditions in the furnace bed. Part of this coke is recovered for re-use.

Jan 1, 1954

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By J. M. Tobin, L. H. Cadoff, L. M. Adelsberg

The reaction between liquid zirconium and graphite at temperatures above 2000 °C has been investigated. The reaction products were found to be carbon-saturated zirconium metal and ZrC which formed between the graphite and the metal. Parabolic growth behavior was observed for the ZrC Phase at all temperatures of this investigation. The parabolic growth constant at temperatures between 2000° and 2860°C was measured to be 1.83 exp 84,300/RT) sq cm per sec. The reaclion mechanism was proposed to be the rapid carbon saturation of the liquid metal and the formation of ZrC at the metal-carbide interface with diffusion of carbon through the ZrC, the "rate - determining step" of the reaction. The concentration-independent diffusion coefficient of carbon in ZrC, (DZrC), was expressed as 0.95 exp? 78,700/RT) sq cm per sec. This value mas calculated using the temperature-invariant ZrC phase fields proposed in the literature. The [ZrQiq)] — [ZYQiq) + ZrC] phase boundary over the temperature range 2000° to 2800°C was determined and the ZrC + C eutectic temperature was found to be 2890° ± 50°C. ThE Group IV and VB transition-metal refractory carbides are of interest because of their high melting points, high temperature strength properties, and relative inertness in certain corrosive environments. The present-day understanding of these materials, however, is limited by the general unavailability of accurate and reliable physical and chemical property data. This is due primarily to the difficulties associated with the preparation of suitable, high-density, high-purity carbide samples, and the achievement and control of uniform high-temperature environments. Accurate measurement of temperature is also an important factor limiting the reliability of reported data. The Zr-C reaction was selected for investigation because of the high melting point (>34000C) and favorable nuclear properties of the reaction product, ZrC. The direct reaction method afforded an opportunity to obtain kinetic data on the fully dense carbide. In this paper, layer-growth techniques were used to estimate the diffusivity of carbon in ZrC and to investigate the phase equilibria in the Zr-C system at temperatures above 2000°C. EXPERIMENTAL PROCEDURES AND DATA Crystal bar zirconium (99.9 pct Zr), purchased from the Nuclear Materials and Engineering Corp., and ZTA graphite (99.9+ pct) were used in this study. The analyses of the materials are listed in Table I. A schematic of the high-temperature carburization apparatus is shown in Fig. 1. The sample was a zirconium metal charge in a 1/2 -in.-ID graphite crucible which was capped with a tightly fitting graphite stern. The crucible and stem were designed to closely approximate black-body conditions. The graphite crucible was packed in lampblack (outgassed 1 hr at 2100°C) which provided insulation and thermal stability to the system. The inert atmosphere was maintained by a constant flow of high-purity argon or helium gas. The nozzle-diffuser section on the top flange was sufficient to prevent back-diffusion of air into the system. Chemical analysis of the carburized samples revealed oxygen and nitrogen concentrations of less than 44 and 20 ppm, respectively. The sample was heated by induction with a Westing-house 5 kw-450 kc power source. Temperature was measured with a Milletron two-color pyrometer which was sighted into the crucible by reflection from an overhead front surface mirror. Optical losses due to glass absorption and light reflection at air-glass interfaces were minimized by the employment of the dynamic-gas seal. It was found that no correction was required for the front surface reflector. The pyrometer was calibrated periodically against a U.S. Bureau of Standards tungsten ribbon secondary standard. Temperatures inside the crucible were also calibrated against the Zr-ZrC eutectic (1850°C)1 and the Nb-Nb2C eutectic (2335°C)2,3 temperatures and agreed to within ±10°C of these values. The temperature was controlled by manually adjusting the power input; variations of

Jan 1, 1967

By K. I. Savage, S. C. Sun

This paper describes a process developed to recover coal, clays and pyrite from coal wastes. The process consists of fine grinding followed by coal and pyrite flotation which leaves the clays in the flotation pulp. A bituminous coal refuse containing 10% sulfur and 30% carbonaceous material was treated by this method to yield a coal product containing 4% sulfur, 10% ash; a pyrite product containing 45% sulfur (84% FeS2), 1% carbonaceous material; and a clay product containing 2% sulfur (3.5% FeS2). The coal yield was about 89%. The pyrite yield was about 77%. The process steps may be entirely flotation, or gravity separation (hydrocycloning) may be used to increase the pyrite : coal ratio in the flotation feed. Cost estimates for the process show a profit of $2.28 per ton of low pyrite grade refuse, but these do not include labor, maintenance, overhead and plant depreciation. The development of this process consisted of three parts: (1) exploratory tests, (2) op-timazation tests and (3) confirmatory tests. The objectionable qualities that sulfur imparts to coal have been commented upon from early times, and they have become more objectionable as the uses of coal have grown. In whatever form coal takes — raw, carbonized or gasified —the sulfur content remains objectionable, and therefore its compounds are removed as completely as possible. It has long been known that sulfur occurs in coal in different forms. In 1861, sulfur was said to exist in the state of sulfuric acid in combination with a base; in combination with iron as iron pyrites; as bisulfides of iron; and in combination with the organic elements of coal.' Pyritic sulfur is a term loosely used to cover the sulfur associated with iron in its various forms. The mineralogically recognized forms are pyrite (FeS2), pyrrhotite (Fe 1-x S) and marcasite (FeS2). The particle sizes of pyrites vary widely. Isolated grains of marcasite smaller than 15 microns have been found disseminated through coal.2 Hair-like "veins" of pyrite filling cracks in vitrain have been found. At the other extreme, lumps or nodules of pyrites large enough for removal by hand picking have been encountered. Organic sulfur, unlike pyritic sulfur, does not exist as discrete particles, but is instead intimately associated with the coal structure and thus it is impossible to remove it or reduce its concentration by physical or mechanical means.2 In the preparation of coal for its various markets, the pyrite minerals (pyrites) are separated from the raw coal feed. This separation process concentrates the pyrites in the tailings or other waste products. It would be desirable to recover these pyrites for three reasons: (1) Pyrites are potential sources of sulfur and iron. In 1967, for the fifth consecutive year, Free World consumption of sulfur exceeded production.3 Propelled by the shortage, the domestic price of sulfur has risen from $24 to $38 per long ton (bright). (2) The refuse, when placed in piles, becomes ignited. The pyrites (FeS2) bum, giving off SO,. Thus, the pyrites are a cause of air pollution. (3) Also, the pyrites undergo chemical reaction when exposed to air. The refuse is leached by waters which result in stream pollution due to the water-soluble iron and acidic reaction products. Coal refuse also contains coal minerals and clay minerals. Therefore, any process for recovering the pyrites must successfully separate them from the coal and clay minerals. In the study discussed here, ten different bituminous coal refuse samples were successfully upgraded in pyrite content. These samples represented a wide variety of coal waste materials from Pennsylvania and other states. The variabilities of the sulfur and coal contents are shown in Table I. The extremes are Sample J, a high sulfur-low coal, and Sample B, a low sulfur-high coal. Definitions of some of the symbols or terms used in this report are given below: Mesh size—Tyler standard mesh screen sieves with an opening based on the square root of two. Fe —Indicates iron, as determined by a stannous reduction-dichromatic oxidation method. S—Indicates sulfur, as determined by the ASTM "Eschka" method for sulfur in coal.

Jan 1, 1969

By S. R. Balajee, I. Iwasaki

The adsorption mechanism of corn starch and its derivatives at mineral-solution interfaces was investigated by the adsorption of cationic starch, unmodified corn starch, British Gum 9084, and anionic starch on quartz and hematite. The adsorption of these starches, which decreases in the order mentioned, is dependent on the balance between the magnitude of the electrostatic interaction and the magnitude of the hydrogen bonding. There exists a critical starch concentration for both optimum flotation and flocculation conditions of iron ores, which corresponds to a point where the starch adsorption reaches a saturation coverage. Flocculation occurs due to the adsorption of starch via electrostatic and hydrogen-bonding forces and by interparticle bridging as a result of the conformation of starch molecules at the interface. The depressant property of starches and starch derivatives in flotation' and their flocculation char: acteristics in clarification and filtration2.3 have long been recognized on a wide variety of ores. The effectiveness of a starch as a depressant for iron minerals has been the subject of much investigation in recent years both in the amine flotation of siliceous gangue and in the anionic flotation of activated silica from iron ores. It has been reported that the depressant activity of starches and dextrins in the cationic flotation of quartz from hematite increases with molecular weight, branching, and number of hydroxyl groups, 1 and that the selectivity is affected by changing the configuration of starch molecules and the composition of its polar groups.4 ,5 The manner in which starches are solubilized was shown to exert a significant influence as a depressant in the anionic silica flotation, and a series of articles covering the practical aspects of flotation and flocculation have already been reported.618 Chemical modification of the starch structure, the pulp pH, the calcium ion, and the residual starch concentration were identified as some of the more important variables affecting the flotation behavior. In the flocculation of iron ores, it was noted that most starches flocculated suspensions of hematite in water but did not flocculate similar suspensions of quartz,9 and that an excessive use of starch restabilized the suspensions due presumably to protective action. 6 An admirable application of such an observation to practice may be cited in the selective flocculation and desliming in the anionic silica flotation of iron ores, which resulted in superior metallurgy and lower reagent cost. 10 From detailed adsorption measurements, Schulz'and Cooke4 established that the adsorption of starches and their derivatives depended on the types of minerals and of starches, pH, and electrolytes present. Their adsorption data and the foregoing flotation and flocculation observations suggested that an electrical interaction between starches and charged mineral surfaces might be playing a role in their adsorption process. Adsorption of organic polymers, particularly of synthetic origin, at solid-liquid interfaces has been extensively studied in recent years,' and it is realized that their adsorption mechanism is considerably more complex than that of simple ions or molecules. A polymer molecule possesses a number of functional groups, and the adsorption at a point may restrict the adsorbability of adjacent groups. The mechanism may be further complicated by the conformation of the polymer molecules which may exist as coiled spheres, helices, or extended chains as a result of intramolecular interactions among functional groups as well as intermolecular interactions with solvent molecules. The object of the present investigation was to examine the effect of the chemical modification on the adsorption characteristics of starches and starch products on quartz and hematite at several pH values, so that by correlating this information with flocculation and flotation results, adsorption mechanism of starches on mineral-solution interface may be elucidated. EXPERIMENTAL MATERIALS Quartz: St. Peter sand was screened at 35 mesh and the undersize was scrubbed and deslimed at a Fagergren cell. The deslimed sand was cleaned with 0.1 N hot hydrochloric acid and washed repeatedly with distilled water, For anuscript, measurementsl the -200-mesh fraction of the sand was ground dry in a porcelain mill for 3 hr. The specific surface of the finely ground quartz was

Jan 1, 1970