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By R. F. Krueger

Results are presented from tests of dynamic fluid-loss rates to cores from clay-gel water-base drilling fluids containing different commercial fluid-loss control agents (CMC, polyacrylate or smt,ch), organic viscosity reducers (quebracho and complex metal lignosulfonate) and oil at several different levels of concentration. In the dynamic system the most effective individual additives to the clay-gel drilling fluid, based on cost-equalized concentrutiom, were found to be starch and the viscosity reducers. These results do not conform with the rankings determined by API fluid-loss rests, which indicate CMC, polyacrylate and starch to be the most effective and comparable. Generally, minimum dynamic fluid-losr rates were attained at cost-equalized concentrations of additive (including thinner) of about $1.00/ bbl, or less. For chernically treated clay-gel drilling fluids, both the standard and the high-pressure API filter-loss tests were found to he inaccurate indicators of trends in dynamic fluid-loss rates under the test conditions used, particulurly for drilling muds containing viscosity reducers. From a practical field viewpoint, restrictions on the applicability of the API fluid-loss test are such that it is open to question whether or not results of this test can be used routinely with confidence as an indicator of control of down-hole fluid loss under field treating conditions. INTRODUCTION The petroleum industry spends large sums of money during drilling operations to control the fluid-loss properties of drilling fluids based on the standard API filter-loss test,' which is a static filtration system. Laboratory studies' ' of dynamic filtration have shown that in a given time period filtrate loss from a circulating mud stream is greater than from a static system and that it is a function of linear mud velocity, pressure and the properties of the drilling fluid. Ferguson and Klotz' and Horner, et al," observed that (I) the dynamic fluid-loss rates for the drilling fluids used were not related to the extrapolated API filter loss and (2) the drilling fluids with the lowest API filter losses did not have the lowest dynamic fluid-loss rates. However, there has been no published information on the relative effects on dynamic fluid-loss rate as a given drilling fluid is treated with increasing amounts of chemical additive to reduce the API filter loss. Such information is economically important because drilling-fluid costs rise rapidly as chemical requirements increase. This paper presents the results of a study of dynamic filtratioi rates to cores from a clay-gel water-base drilling fluid treated with various commercial viscosity reducers and chemical fluid-loss control agents. The dynamic fluid-. loss rates to cores are compared with the standard API filter-loss values at several different levels of additive concentration. Dynamic filtration rates were obtained in each experiment under two different simulated wellbore conditions: (1) filtration just above the bit through a new mud cake laid down dynamically on a freshly drilled formation and (2) filtration up-hole through a mud cake formed by deposition of a static filter cake on top of the initial dynamically formed cake. The latter case corresponds to the bottom-hole conditions existing above the bit when mud circulation is restarted after a stand of pipe has been added or a round trip has been made to change the bit. Except for the short-duration, high-rate filtration beneath the bit where no mud cake can form, these two conditions probably represent the two extremes of dynamic filtration. Because thickness of a dynamic mud cake formed on freshly exposed formation is limited by the shearing action of the mud stream, the filtration rate for this condition is high. On the other hand, once circulation is stopped and a static mud cake forms on top of the dynamic cake, re-starting circulation has only a small effect on the cake properties and filtration rate is much lower thereafter. A discussion of the mechanics of mud-cake deposition and dynamic filtration is outside the scope of this paper but may be found in more detail in publications by prior investigators. APPARATUS AND EXPERIMENTAL CONDITIONS The test equipment used to simulate the dynamic flow conditions existing during drilling was a modification of that described previously by Krueger and Vogel: A schematic flow diagram is shown in Fig. 1. In general, a power-driven, high-pressure mud pump capable of delivering up to 60 gallmin was used to circulate drilling fluid parallel to the faces of 1-in. diameter sandstone cores mounted in a 2 3/4-in. ID high-pressure test cell. Pump rates were controlled by means of a magnetic clutch to maintain an average axial fluid velocity of 110 ft/min in the annular space between the cell wall and a 1 1/2-in. rod positioned on the center line of the cell. The core specimens were Berea sandstone plugs sealed with plastic inside 1 1/8-in. OD tubes and were fluid-saturated prior to use. Burettes were used to accumulate fluid discharged from the cores. The mud sump shown was used for treatment and storage of the drilling-fluid samples during a particular test. The valve arrangement permitted either (1) circulating drilling fluid through the by-pass line while treating with

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

By C. C. Martin, M. C. Fuerstenau, R. B. Bhappu

Experiments revealed that quartz could not be floated in conductivity water at any pH with a long-chained sulfonate as collector. Various cations, Fe+++, Al+++, Pb++, Mn++, Mg++, Ca++, are shown to function as activators when the pH is such that the cation hydrolyzes. As the solubility product of the various cation-sulfonates was exceeded at the concentrations involved, precipitated cation-hydroxy-sulfonates, e.g. Fe (RSO3)2OH must be functioning as the collector in these systems. A number of interesting and important phenomena were revealed during a study of the response of beryl to sulfonate flotation.' Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH 3.0, about three ppm Fe+++ increased recovery of leached beryl from about 60 pct to 100 pct, whereas about four ppm Ca+ + reduced the recovery from 60 pct to 2 pct. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper Sulfonate Flotation of Beryl,' even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation-sulfonates are precipitated immediately in solution. That is, blueish-white clouds were noted to form after given additions of salts to known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe(RCO3)2OH and that bonding to the surface occurs through the hydrogen of the hy-droxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems in the presence of various cations at various values of pH. EXPERIMENTAL MATERIALS AND METHOD Sodium alkyl aryl sulfonate was chosen as the collector for the experimental work. The reagent, sup plied as a courtesy sample by the Shell Chemical Co., has the following physical properties: Physical form Solid — Finely ground Sulfonate content, pct wt 95 to 97 Molecular Weight 450 to 470 Number of carbon atoms in hydrocarbon chain 25 to 30 Melting Point, OF 250 to 260 Solubility Soluble in water with gel formation at concentrations higher than 25 pct by weight sulfonate This particular reagent was chosen because of its high active sulfonate content, long-chain length, and solid form. With the exception of the frother and sulfonate, all other chemicals were of reagent grade quality. Conductivity water was used in the experimental work. This water, made by passing distilled water through an ion exchange column, had an average measured conductivity of one micromho. Experiments were conducted at room temperature in a small glass flotation cell with the following procedure: 1) A redetermined amount of water and salt solution (e.g. CaC12 . 2H2O) were combined and the pH adjusted to a given value. 2) A given amount of sulfonate was added so that final solution volume was 130 cc. 3) One drop of Dow 250 frother was added. 4) Five g of quartz were added and the system conditioned for five minutes. 5) The pH of the system was measured (termed flotation pH).

Jan 1, 1963

By R. A. Grange, H. M. Stewart

Man.; steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering" and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully understood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually all marten . site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered martensite and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTENSITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1947

By H. M. Stewart, R. A. Grange

Man.; steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering" and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully understood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually all marten . site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered martensite and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTENSITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1947

By W. R. Crane

Mining of the red iron ores of the Birmingham district has been carried on energetically during the past 60 years, and their development has created a large iron and steel manufacturing center, the only important one in the South. The district produces approximately 10 per cent. of all the iron ore of the United States (80 per cent. of the Alabama ore mined is red ore); also, 40 of the 400 blast furnaces of the country are in the district tributary to Birmingham. The rapid growth of the district has been made possible through investigations that resulted in radical changes in furnace practice, and a still greater impetus will come from the study of the low-grade, high-silica ores, as a result on which they will be made amenable to treatment by concentration. Mining practice in this district has been comparatively simple because of the occurrence of the ore; but with the rapid extension of the workings and the disturbed condition of the ore bed at some distance from the outcrop, more difficult conditions are encountered and the tendency is toward worse rather than better conditions. Should the high-silica ores of the lower bench of the Big Seam become available through beneficiation, mining practice will have to be modified to meet the new conditions, which will be rendered more difficult by the increased weight of cover that will exist at considerable distances from the outcrop. Support of workings will require greater attention and the efficient and economical operation of the mines will depend largely on the successful solution of the problems of working and handling the ore. History and EaRly Development The first explorers of the coal and mineral lands of Alabama were blacksmiths and mechanics mustered out of the army after the war of 1812. These men recognized the red rock of the Birmingham district as iron ore, and utilized it in making cooking utensils and farm implements. The first blast furnace was built and operated at Russellville in 1818, where also was a foundry and rolling mill. Soft ore was used at that time, but, in 1864, the first red hematite ore of Red Mountain was smelted, near Irondale. Birmingham was founded in 1871, and the successful use of coke in making pig iron in 1876 was the beginning of

Jan 1, 1925

By L. W. McKeehan, W. C. Elmore

THE magnetic powder method, long used for roughly mapping magnetic fields, has recently been refined 1,2 for investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter' first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators3 have used Bitter's original technique, with slight modifications, to study the variation of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement in the powder technique which led us to the discovery of a new effect throwing considerable light on the magnetic secondary structure of alpha iron4 and of nickel' single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure. SPECIMENS The following list describes the specimens used in the present investigation. DESIGNATION DESCRIPTION A1 Silicon ferrite furnished to us by Dr. W. E. Ruder, of the General Electric Co., for which he gave the following typical analysis: C, 0.05; P, 0.038; 5, 0.026; Mn, 0.15; Si, 3.24. Disk, 0.60 cm. diameter, about 0.05 cm. thick.

Jan 1, 1935

By Arthur Taggart

THIS paper describes the result of a series of experiments run in the laboratory of the School of Mines, Columbia University, during the winter of 1927-28. It shows that the several operating adjustments of a pneumatic table produce effects in the action of a, given coal that may be grouped into two classes, viz.: stroke length, speed and rocker-arm angle, which affect longitudinal travel; air supply and table slope (transverse and longitudinal), which determine transverse travel. The magnitude of the effect of the different adjustments varies. Some of the adjustments affect stratification of the bed, both as respects size and specific gravity of the bed components, as well as direction of travel. Operation of a pneumatic table is fundamentally different from that of a wet table in that the former exerts, through the air supplied, a force on the particles upward away from the deck which is lacking on the wet table while, on the other hand, it lacks the positive control over cross travel that is supplied by the wash and feed water.

Jan 1, 1929

By L. T. Sicka, H. N. Thomson

The Tooele plant of the Internationa1 Smelting & Refining Co. is situated at the mouth of Pine canyon, Tooele county, Utah. It is connected with the main line of the San Pedro, Los Angeles & Salt Lake railroad by the Tooele Valley railway, and is about 7 miles from Tooele Junction. Fig. 1 is a general view of the plant. The copper plant has been in operation since July, 1910, arid the first blast furnace at the lead plant was blown in on Feb. 29, 1912. The location of the plant was selected on sloping ground with the idea of using gravity to the fullest extent and thus keeping labor at a minimum. Practically the entire plant is constructed of steel, reinforced concrete, and brick. Bingham ores, both lead and copper, are received over the Utah Consolidated Aerial Tramway. The tram buckets, each containing

Jan 1, 1914

By Leonard C. Grimshaw

The idea of bonding two dissimilar ferrous metals, and making use of both, is an old one. Tips have been brazed onto tool shanks for many years. The bonding of larger pieces to form whole bars and sheets has also been accomplished, but has received little attention in the technical literature, although a number of patents have been issued covering various methods for its accomplishment. There are three main motives behind the manufacture of composite steels. One is that the physical properties of one steel may supplement those of another; a useful, but at the same time, hard, brittle steel may be backed by a soft ductile one, or a stainless steel may be backed by a steel possessing greater strength. Another motive is direct lowering of cost; an expensive steel may be backed by a less expensive one, bringing down the cost of the piece as a whole. The third motive is an indirect lowering of cost, as when a useful steel is backed by a steel that is easier to machine, so that machining cost on a finished product is lowered considerably. Often more than one of these motives lead to a decision to use a composite steel. Previous Methods There are two methods in use that result in tolerably good bonds between ferrous metals: (1) the casting method, and (2) what we shall call the "heat-pressure" method. This "heat-pressure" method covers processes in which the bond is made between two prepared surfaces by heating them and then applying pressure. Usually sufficient pressure must be used to produce appreciable spread and elongation, or else we arc merely brazing and not truly welding. Casting methods for welding together ferrous metals have been used more than 74 years, and are described in the technical literature as applied

Jan 1, 1936

By Leonard C. Grimshaw

The idea of bonding two dissimilar ferrous metals, and making use of both, is an old one. Tips have been brazed onto tool shanks for many years. The bonding of larger pieces to form whole bars and sheets has also been accomplished, but has received little attention in the technical literature, although a number of patents have been issued covering various methods for its accomplishment. There are three main motives behind the manufacture of composite steels. One is that the physical properties of one steel may supplement those of another; a useful, but at the same time, hard, brittle steel may be backed by a soft ductile one, or a stainless steel may be backed by a steel possessing greater strength. Another motive is direct lowering of cost; an expensive steel may be backed by a less expensive one, bringing down the cost of the piece as a whole. The third motive is an indirect lowering of cost, as when a useful steel is backed by a steel that is easier to machine, so that machining cost on a finished product is lowered considerably. Often more than one of these motives lead to a decision to use a composite steel. Previous Methods There are two methods in use that result in tolerably good bonds between ferrous metals: (1) the casting method, and (2) what we shall call the "heat-pressure" method. This "heat-pressure" method covers processes in which the bond is made between two prepared surfaces by heating them and then applying pressure. Usually sufficient pressure must be used to produce appreciable spread and elongation, or else we arc merely brazing and not truly welding. Casting methods for welding together ferrous metals have been used more than 74 years, and are described in the technical literature as applied

Jan 1, 1936

By Valentin R. Garfias

The production of petroleum in the Mexican fields during 1931 followed the downward trend of the past nine years, with a decline of close to 6,600,000 bbl., or about 17 per cent from the 1930 total. The output was close to 32,964,000 bbl., the Tampico-Tuxpam fields showing the largest actual and proportional decline, while the production of the fields in the Isthmus of Tehuantepec remained practically unchanged. Wildcatting along the international border was carried on more actively than in previous years, the only successful completion being the Alberca No. 1 well located about eight miles from the international boundary, across from Roma, Tex. This well, completed at a depth of 2015 ft. and plugged back to 1550, is rated at about 6,000,000 cu. ft. of gas per day from a horizon between 1330 to 1540 ft., and is now connected to the gas line from the Jennings gas field, Texas, supplying the city of Monterrey. Favorable oil indications have been encountered in other exploratory wells along the border and drilling will probably continue as these lands are largely held under government concessions which require continuous development work in order to retain title. Development in the Isthmus of Tehuantepec has progressed in a systematic manner, the number of successful completions during the year being considerably larger than in the South or Northern fields. The oil pipe line from the south fields to Mexico City has been completed and its operation and that of the Azcapotzalco refinery is expected to begin early in 1932. The construction of this line will Tevolutionize the transportation of petroleum and its products from the fields to the high plateau and seriously affect the revenues of the government-owned railroads. General conditions in the oil industry were reflected in Mexican operations. Low prices and the imminent threat of an American oil tariff discouraged development work necessary to maintain or increase production, and the curtailment of activities resulted in considerable reductions in personnel by all companies. Early in 1932 the Mexican Government announced its intention to create a surface tax or yearly rental on oil lands equivalent to about 31/4 U. S. cents per acre. Such additional burden on this already harassed industry will not only create little or no

Jan 1, 1932

By R. B. Full

DURING the summer of 1949, the United Nations Scientific Conference on the Conservation and Utilization of Resources met at Lake Success. As summed up by one writer, the purpose was: "That everyone will try to learn how to feed more people from an acre of land." That objective is a stimulus to the phosphate rock industry as well as other industries. Phosphate rock was mined first in the Canadian province of Quebec where it was found as an apatite in pockets. In 1863, mining began near the Rideau Canal, first in open trenches and quarries until shafts were sunk. These operations were difficult since hard rock had to be drilled and blasted. Steam was the source of power. The phosphate rock was hand-selected and recovery ranged from 6 to 10 pct, averaging 70 pct to 85 pct bpl (bone phosphate of lime). Costs, f.O.b. Montreal, were $14 a ton, and selling prices averaged $17 a ton. In 1885, about 29,-000 tons were sold on this basis, but by 1892 the output fell to 8000 tons at an average price of $15 a ton at Montreal. South Carolina Deposits Phosphate rock was first discovered in South Carolina in 1837, but a mining company was not formed until 1867. It was immediately successful, and the industry continued to develop and ship an increased tonnage of land and river rock, shipments increasing from approximately 20,000 tons in 1868 to 537,000 tons in 1890, when the shipments began to decrease. In 1892 only 350,000 tons were shipped. In this field there were two types of deposits: land rock and river rock. More land rock tonnage was mined until about 1887 when river rock production began to equal it. The land rock was mined adjacent to and in the river marshes by pick, shovel, and wheelbarrow. Each worker dug daily a space 6 ft wide, 15 ft long and 6 ft deep, which was overburden, and then loaded about 3 cu yd of phosphate rock into wheelbarrows. His helper would wheel the barrows to small steam railroads up to 250 ft distant. Water was kept from the pits by steam pumps connected to railway cars. The phosphate rock was loaded into railroad cars, hauled and dumped into a log washer to which water was added, and run over trommel screens to eliminate the clay and loose sand. Steam shovels for loading were introduced about 1891. River rock was mined by floating dipper dredges and at low tide was loaded into barges by laborers using oyster tongs, the large lumps being hand-loaded. Barges and bateaus were unloaded by wheelbarrows which were wheeled to the same type of land rock washers. The washer product was piled with stacked pine cordwood in alternate layers and fired for drying. Usually this was done under sheds along the river bank. The dried rock then was transferred to ships, usually three or four-masted schooners. Cost of production of both land and river rock, including $1 a ton royalty paid to the state for state-owned property, was approximately $4.25 a ton averaging 60 pct bpl. The selling price was approximately $7 a ton f.O.b. In 1886 the courts handed down a decision permitting anyone to mine, and many additional companies were organized immediately. As a result, the selling price was lowered to a profit margin of 50Ø or less per ton. The South Carolina mines were eventually shut down when a more profitable source of phosphate rock was discovered in Florida. Florida Deposits Phosphate rock was discovered in Florida in 1882, and in 1883 a small quarry was opened near Hawthorne. In 1886 phosphate rock of good grade was discovered on Peace River, and the Arcadia Phosphate Co. was formed. In 1888 the company began shipments amounting to 3000 tons that year. During the latter part of 1888, hard-rock phosphate was discovered near Dunnellon. Exploration extended rapidly, and deposits of hard-rock phosphate were mined over a wide area so that shortly after 1900

Jan 1, 1952

By G. W. Binkley, R. E. Collins, G. K. Dumbauld

A mathematical analysis has shown that the primary factors affecting the deposition of cement in unfractured perforations during squeeze-cementing operations are: the properties of the cement slurry, the geometry of the perforations, and the filtration time. The validity of the analysis has been substantiated by laboratory investigations. The information presented in this paper makes possible the prediction of the rate of deposition of cement in and about unfractured perforations under given squeeze-cementing conditions, the proper filtration time to control the amount of deposition to any desired value, and the deposition properties needed in cement slurries to restrict to any desired degree the formation of nodes of cement .Solids inside the casing. INTRODUCTION The deposition of solids against a permeable medium by the process of filtration is an important property of a cement slurry. General recognition of the role of filtration in the use of cement in wells is evident in view of the fact that several patents on low-water-loss cements have been issued during the past few years. In the conventional, high-pressure squeeze-cementing technique, a large volume of cement slurry is usually displaced into the area surrounding the perforated interval after the formation has been fractured hydraulically.&apos; Near the end of the job, the pumping rate is slowed or stopped intermittently in an effort to obtain a high pressure in the wellbore. The way in which a high pressure is obtained is not understood thoroughly. but it is be- lieved to be caused by the deposition of a rigid mass of compacted cement particles either in the fractures of the formations or inside the casing opposite the perforated interval. In a method of squeeze-cementing introduced several years ago, a small amount of cement slurry is squeezed into the perforations at a low pressure to avoid fracturing the formation. The filling of the unfractured perforations with cement particles by the process of filtration is important to the success of this technique. Early in the development of this low-pressure squeeze-cementing technique, laboratory and field-size experiments showed that conventional, neat cement slurries were unsatisfactory if the tubing was extended into or through the perforated section of the casing. The extremely high filtration rate of neat cement slurries caused the deposition of a compacted mass of cement inside the casing and made it impossible to remove excess cement by reverse circulation and difficult to withdraw the tubing. Because the need for cements with a reduced filtration rate was obvioils and urgent, modified cements containing 12 per cent bentonite were used until research was completed on modified cements containing 25 per cent bentonite.< These modified cements were useful in the solution of the immediate problem, but the following questions remained unanswered: (I) what is the optimum filtration rate of cement slurries for this application, (2) how long should the squeeze pressure be applied. and (3) how great are the effects of squeeze pressure and well temperature on the rate of deposition? Furthermore, the relationship of the filtration properties of cement slurries to the dimensions of the perforations and the wellbore was unknown. In order to obtain information relative to these basic considerations, a systematic evaluation of all the factors involved in the deposition of Cement during low-pressure squeeze-cementing operations was initiated. Although the work was directed toward an evaluation of the factors influencing the deposition of Cement in the low-pressure squeeze-

By Franklin Moeller

CONSIDERING the really short time that has elapsed since hydro-metallurgical processes of extracting copper from ores have been extensively developed, and the large scale on which this method is practised at Ajo, the successful operation of the plant must excite the admiration of every visitor. The application of the mechanical unloader to the purpose for which it is employed at Ajo is but an extension of the use for which it was originally designed, some 20 years ago, for unloading iron-ore vessels at the lower lake ports. At a time when the maximum output of a single machine, with men shoveling the ore into buckets, did not exceed 40 tons per hour, G. H. Hulett invented and constructed a mechanical unloader with a bucket of 10-ton capacity. This machine was of the steam hydraulic type, and it is still in operation after nearly 20 years of service. Several more machines of the same type were built, but the difficulties of power transmission, and the rapid development of electrical machinery, soon led to the adoption of electrically operated machines, and practically all of the later installations have been thus equipped. This electrically operated unloader has proved so well fitted for the work that the design of the lake boats has been practically revolutionized, with special view to the ease and rapidity of unloading. It is now possible to unload a 12,000-ton vessel with four machines in a little over 2 hr. This has necessitated an increase in the capacity of the machine, and the largest yet built handles an average load of 17 tons, with a possible maximum of 20 to 21 tons.

Jan 8, 1918

By C. A. Hansen

Page Introduction............................206 Power Characteristics in Zinc Sulfate Electrolysis........... 207 Current Efficiency......................... 207 Corrosion Rates..........................216 Voltage Required by the Zinc Cell..................219 Power Requirements of the Zinc Cell ................221 Impurities in Zinc Electrolyte.....................222 Non-cumulative Impurities.....................223 Cumulative Impurities ....................226 Impurities in General........................228 Temperature and the Stability of the Zinc Cell..............229 Practical Expedients for Control of the Zinc Cell...........234 Acknowledgments...........................234 Appendix................................235 Discussion...................:.......... - 236 Introduction It has been the experience of the writer, during some five years&apos; work with electrolytic zinc, that the zinc cell is perhaps more sensitive to impurities in the electrolyte than the analytical methods as yet developed for the chemical identification and determination of these impurities; but that, when proper purification methods have been applied to a given solution, the behavior of the cell is quite independent of the original sources from which the zinc sulfate has been derived. It has also appeared that the behavior of the zinc cell is the best and surest check on the correctness and thoroughness of the purification methods used, because it indicates the presence of both current impurities and cumulative impurities derived from the leaching of the ore; it also indicates whether these impurities are current or cumulative, at least in so far as they are of serious importance commercially.

Jan 1, 1919

By David J. Mack, Dennis R. O’Boyle

The mechanical properties of three polycrystalline intermediale Phases that have the y bvass structure were measured in compression between 400° and 900°K. At the lower testing temperatures— termed Region I— no plaslic deformalion occurred prior to brittle fracture. A1 higher temperatuves— lermed Region III—the three phases deformted plaslically for all strain rules from 1.5 to 36.0 x 10-4 sec-1. The homologous temperature for the inilialion of plaslic flow increased in the same order as tile atomic size difference between atoms in each plmse (0.50Tmp for y AgZn, 0.62Tmp for y CuZn, and 0.76 Tmp for y CuCd). The increased flow resistance oj. y CuCd above 0.50Tmp is explaitzed in terms of the more random arrangement of copper and cadmiwn atoms on the laltice sites of&apos; the y bvass slrilctlire. Plaslic deformation of the three intevmiediate phases in the smooth plaslic flow region appears to be controlled by oacancy-induced dislocation climb. RESULTS are reported in this paper on the mechanical properties of three binary intermediate phases having the complex cubic y brass structure (D82, 143m) containing fifty-two atoms in the unit cell. The structure of the prototype y brass phase, y CuZn, was first analyzed by Bradley and Thewlis&apos; based on the X-ray work of Westgren and Phragmen.2 The y brass structure can be visualized as an arrangement of twenty-seven body centered cubes (3 by 3 by 3) into a unit cell containing fifty-four atoms. From this cell the center atom and the four corner atoms are removed and the remaining fifty-two atoms are slightly displaced, resulting in the y brass structure. Approximately thirty-five binary intermediate phases that have an electron to atom ratio of 21:13 have been reported to form the y brass structure. The three y brass intermediate phases selected for this study are formed from elements in groups IB and IIB of the first and second long period. Each compound exists over a composition range that includes the stoi-chiometric composition A5BB (Cu5Zn8, Ag5Zn8, Cu5Cd8). y CuZn (a0 = 9.944A) has solubility limits extending from 57 to 67 at. pct Zn at 500°C apd melts peritecti-cally at 834°C; y AgZn (a0 = 9.326A) has a solubility range from 58 to 63 at. pct Za and melts peritectically at 661°C. y CuCd (a, = 9.596A) melts congruently at 563°C and has a maximum range of solubility extending from 58 to 64 at. pct Cd. In order to minimize coring and microporosity during solidification, the composi- tion of the compounds that form peritectically (y CuZn and y AgZn) was chosen so that the temperature difference between the liquidus and the solidus is only a few degrees centigrade. In selecting y brass compounds for this study, phases were avoided that contained a transition element or that had an electron to atom ratio greater than 1.70. Hume-Rothery et a1.3 has observed that, when the electron to atom ratio of y brass intermediate phases exceeds 1.70, atoms begin to drop out of the unit cell to maintain a constant electron to unit cell ratio. EXPERIMENTAL PROCEDURE Each of the three intermediate phases was prepared from elements having a purity >99.999 pct. Only trace quantities of impurities (<0.0001 pct) were detected by spectrographic analysis of the four elements. A master alloy of each compound weighing approximately 130 g was prepared by melting the elements in evacuated sealed quartz tubes heated in an electric furnace. Specimens having the desired diameter for the mechanical property measurements were obtained by remelting the master alloy in a Vycor tube under argon and drawing specimens from the melt into 4-mm-diam quartz tubes. To obtain a smooth surface on specimens drawn from the melt, the inside of the quartz tube was coated with a thin layer of graphite formed by thermally decompositing acetone. All specimens were imbedded in sealing wax and cut to the proper length with a diamond-impregnated cut-off wheel. The individual specimens (4 mm diam by 8 mm long) were then sealed in evacuated Pyrex tubes and homogenized at 500°C for 72 hr. Chemical composition, variations over the length of the rod (10 cm long) were generally less than 0.2 pct and the analyzed composition differed from the desired composition by less than 0.5 pct.4 Metallographic evaluation of the specimens after homogenization showed no evidence of a second phase in any of the compounds. The average grain size of the specimens after homogenization was 1 to 2 mm. All mechanical property measurements were carried out in an argon atmosphere using a compression apparatus described previously.5 Prior to applying the load to the specimen, the test apparatus was evacuated, back-filled with argon, and heated to the test temperature for 20 min to establish thermal equilibrium. EXPERIMENTAL RESULTS Mechanical properties measured as a function of temperature and strain rate for each of the three y brass phases were similar. From room temperature to the ductile-to-brittle transition temperature, only elastic deformation was observed prior to fracture.

Jan 1, 1968

By F. P. Nichols, F. A. Renninger

At one time, mineral aggregates were considered physically and chemically inert substances whose junction was that of an inex-pensive, easily obtainable source of bulk. This philosophy applied regardless of the use to which the aggregate was put. Research approaches dealing only with such gross physical properties as hardness, toughness, impact resistance, etc., dominated the early growth years of the industry and influenced specifications to a large extent. The accelerated pace of highway construction, which began toward the end of the depression years, focused attention on the need for extensive aggregate research. The realization in the early 1940&apos;s that aggregates interacted chemically as well as physically with their environment provided the stimulus necessary to translate the drab, systematic aggregate technology of the early 20th century into the changing, dynamic, challenging field it is today. Current research problems are discussed in detail. These efforts being pursued by contract research organizations, universities, governmental agencies, and industry transcend many fields. The mineral aggregate industry is the world&apos;s largest mining and processing endeavor, yet it is graced with little of the romance or public awareness that accompanies mention of gold, silver, iron, copper, uranium, or aluminum mining efforts. Much of this reaction is undoubtedly due to the fact that the uses to which crushed stone and sand and gravel are normally put are not fully recognized or appreciated by the general public. Almost 2 billion tons of mineral aggregates are quarried or mined, processed, and sold yearly in the United States alone.= The largest uses to which this vast tonnage is subjected are as ingredients of portland-cement concrete, bituminous concrete, and dense-graded aggregate-base course mixtures in the highway and building construction fields, two industries closely related to the expenditure of public funds. It is for these uses, partially in justification for the expenditures of vast sums of public funds, that mineral aggregate research truly finds its emphasis. The research efforts expended relative to the highway and building construction uses to which mineral aggregates are subjected are those of primary concern to the industry. These efforts, while of direct consequence to the industry due to the volume market represented, are of interest as well to public agencies, universities, and contract research firms. All actively conduct research, exchange information, and make contributions to the overall knowledge relative to aggregate usage and limitations. The research efforts of the mineral aggregate industry is the subject to be discussed throughout this paper. It covers all aspects of highway and building design, construction, and technology. The effects of research pertaining to quarrying and mining methods, blasting and processing techniques, storage and handling facilities, and equipment employment and development have left their mark on the crushed stone and sand and gravel industries. Such specialized efforts have resulted in dramatically increased production rates which in turn have served to keep costs, and hence prices, down. Despite the many inflationary pressures over the years, the cost of a ton of aggregate today is little more than it was 25 or 30 years ago. Mention is made of these efforts simply to emphasize the diversity of research in the mineral aggregate field. The remainder of this paper focuses on the complexity of what might be termed "product knowledge" research.

Jan 1, 1971

By J. W. Spretnak, G. W. Cunningham

A study has been made of the growth and disappearance of voids in the interface of pressure bonded copper. The formation of visible voids is primarily due to spheroidization and coalesence of microvoids produced during the application of pressure. The microvoids could be prevented from forming by the application of high pressures or by increasing the ductility of the copper. Migrating grain boundaries were found to be more effective in void removal, than stationary grain boundaries. DURING the course of an investigation on the mechanism of pressure bonding, it was found that voids formed in the bonding interface which inhibited migration of the interfacial boundary and grain boundaries in the bond region. Therefore, an effort was made to determine the nature of the voids and how they form, grow, and disappear. This paper reports the results of such an investigation. The existence of interfacial voids is not solely a characteristic of massive components of metal which have been bonded by the application of heat and pressure, but is a phenomenon which has been observed in sintering as well. Simonsen attempted to study the sintering process by hot-stage microscopy and thereupon observed the formation of interparticle porosity as sintering proceeded. It was assumed that the porosity was due to grooves created at the location where grain boundaries joined the surface of the particle. Pranatis, Castelman, and seigle2 have also observed voids along the areas of contact in wound-wire specimens used for sintering studies. They did not discuss the point in detail since this behavior was not general, but they did suggest that the voids might develop as a result of stresses along the interparticle contact area. In previous investigations on pressure bonding, workers3 have suggested that voids may exist in the region where mating surfaces are placed in intimate contact, but the existence of the voids was not verified and no attempt was made to study the growth and disappearance of these voids. Durst noted the existence of pores in roll-clad structures prepared by cold reducing two sheets to force them in contact and then annealing to improve the bond. Since his unbonded regions contained a gas which he assumed to be insoluble, he proposed a mechanism which consisted of spheroidization of the unbonded regions and a growth of the contact area, but no speculations were made regarding disappearance of the gas filled pores. One interesting comment made by Durst was the suggestion that flattened voids with sharp corners which are produced during roll bonding will have a greater driving force for spheroidization than the more rounded pores created by pressing metal powders and thus spheroidization and neck growth will occur at lower temperatures. In this study it was necessary to demonstrate conclusively that voids can actually exist in the interfacial bond area. Experimental work was then directed toward a study of the mechanism whereby the voids grow and subsequently disappear.

Jan 1, 1963

TWO recent developments in open hearth steelmaking have had a substantial impact on metallurgical practices and operating procedures. These are: (1) the use of oxygen roof lances for accelerating the refining reactions, and (2) the use of a spring-arch, basic roof for prolonging the life of the furnace. Although these practices can be used separately, they are generally used to complement each other in an effort to obtain minimum heat time consistent with an acceptable rate of wear of the refractory roof, walls and port ends. DECARBONIZATION BY OXYGEN INJECTION The use of oxygen to speed carbon elimination was perceived by Sir Henry Bessmer but its practical use in steelmaking could not be realized until processes were developed for the manufacture of low cost, tonnage oxygen. However, as early as 1922 Bigge1 obtained a patent covering the use of gaseous oxygen to speed decarbonization of a molten steel bath. At that time, oxygen was available only in bottles and at a cost of $240 per net ton. At the end of World War II the price of oxygen had dropped to $80 per net ton, and as a result, metallurgical oxygen (99.5 per cent began to come into widespread experimental use for decarbonization in open hearth and electric furnace shops.2-8 Even this price prevented oxygen&apos;s routine use for other than decarbonizing the bath in shops producing substantial quantities of steels containing less than 0.40 per cent carbon. Today, tonnage metallurgical oxygen can be manufactured for less than $15 per net ton, and commercial purity oxygen (95 per cent is reported to cost less than $5 per ton. Thus, it is not at all surprising to find many open hearth shops effectively using large quantities of oxygen to accelerate decarbonization. Equipment for Oxygen Injection. The oxygen may be injected by a lance pipe inserted through the wicket hole and pushed several inches into the steel bath, or by a water-cooled jet inserted through the back- wall, endwall, or roof, and immersed in the slag or set just a few inches above the slag. Oxygen at approximately 100 psi is piped directly to control stations adjacent to each furnace. The installations should include adequate safety devices such as fire checks and emergency valves,

Jan 1, 1964