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By K. E. Manchester, A. H. Clark

Hall measurements have been made on three groups of silicon samples, which were implanted with boron, aluininunz, and phosphorus ions. Boron and phosphorus implants show essentially bulk properties when annealed under previously determined conditions, i.e., 15 min at 80O°C for boron and 10 mirz at 600°C for phosphorus. Bulk properties were also observed in alu?rrilzum-implanted samples when ion concentrations were below 1015 cm-'; however, strange low- terrzperalure behavior and a falloff in cavrier concenlralion was observed for sarnples with ion concenlration abozle loL5 ern-'. This can be attributed to solid-solubility effects since the average bulk concentration f0.r the sample exhibiting bulk properties was below the reported solubility limit for aluminum, while the other samples were above the limit. A detailed study of the annealirzg process indicates that mobilities reach bulk c~alues in phosphorus implants at 250DC, in alutninurn ivnplanls a1 500°C, and in boron implants at 700°C. A simple rnodel has been proposed to fit the annealing data. THE technique of semiconductor doping by direct injection of energetic ions is being actively investigated at this Center. Previously published results from this laboratory have been concerned with the investigation of implanted profiles in silicon and the electrical properties of the resultant p-n structures.1'2 Diode properties have been reported for junctions produced by implantation of boron ions and aluminum ions in n-type silicon and phosphorus ions in p-type silicon. Reverse current characteristics, as well as electron diffraction data, have indicated that the damage to the structure produced by the energetic ions during the stopping process can be minimized by a gentle anneal. The time-temperature conditions for this process have been determined by sheet resistivity studies.3 Electrical profiles of implanted phosphorus ions which have been determined by a differential sheet conductivity technique are based on the assumption that the carrier mobilities and activation energies for ionization are the same as in bulk silicon. These assumptions have been substantiated experimentally by measurement of Hall constants and resistivities of these implanted structures and the results are presented herein. After establishing the bulk property equivalence of the annealed layers, a more detailed examination of the annealing process was undertaken. The sheet resistivity technique initially used to determine anneal conditions has been broadened to include Hall constants and mobility behavior with anneal conditions. PROCEDURE The three groups of samples prepared for Hall measurements were implanted with mass-separated beams of boron, aluminum, and phosphorus ions. Ion concentrations are equivalent surface concentration and they have been determined from beam current measurements during implantation. Implant conditions for the samples are shown in Table I. In all cases, the samples had previously been angle-lapped on one edge and the junction delineated with an HF-copper sulfate solution. The surfaces of the implanted regions of the samples were exposed to the delineating solution and in the case of the "n"-type phosphorus-implanted areas it was later discovered that a finite amount of surface could be etched by this solution. This is discussed in the section on results. The implanted samples were ultrasonically cut into the conventional six-probe configuration shown in Fig. l.* In the annealing studies, for which the meas- urements were taken at room temperature, the sample holder was a Bakelite jig incorporating tungsten mechanical probes. The other measurements were taken using a conventional liquid-nitrogen cryostat, in which the temperature could be varied from 77" to about 400°K. For these measurements, 10-mil aluminum dots were evaporated onto the samples and alloyed with the silicon at 530°C for 15 min. The samples were then mounted in flat-packs, and gold wires were bonded to the aluminum dots. The electrical measurements were made with either a Leeds & Northrup K-5 Potentiometer, a Keithley 147 Nanovolt Null Detector, or a Keithley 601 Electrometer. No external bias was applied to the substrate. There is an inherent self-biasing arrangement at one or the other of the current contacts (depending upon the polarity), and this suffices to limit the current flow to the implanted layer. The magnetic field was generated by an A. D. Little electromagnet. Except for occasional checks of linearity of the Hall voltage with

Jan 1, 1969

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By A. Lubinski, W. D. Greenfield

Bumper subs are currently used in offshore operations to permit a constant weight to be carried on the bit while drilling, regardless of the vertical motion imparted to the drill pipe by drilling vessel heave. As shown in this paper. the vertical motion of the lower end of the drill pipe (the bumper sub end) may be appreciably greater than the vessel heave. Therefore, the necessary stroke of bumper .rubs for successful operation is greater than thought in fie past. Also, there is an appreciable tendency of the drill pipe to buckle above the unbalanced type of bumper sub. Thus, more drill collars than previously used should be carried above unbalanced bumper subs to keep drill pipe straight. INTRODUCTION Drilling bumper subs are placed in the drilling string for various reasons. This paper is concerned with their use only as an expansion and contraction joint while drilling from a floating rig. In this application the bumper subs are normally located just above the drill collars and their function is to allow the driller to maintain accurate weight control on the bit regardless of up-and-down movement of the drilling vessel. This paper analyzes the effects of bumper subs on the drilling string and presents recommendations for their future use. When subjected to vertical oscillations, the drilling string behaves like a long, distributed system of mass and spring. The magnitude of vertical motion at the bumper sub is always greater than the heave of the drilling vessel due to the dynamic reponse of the drilling string. The ratio of these motions increases with the length of the drilling string, and may reach values of 1.5 or even 2 with strings 16,000 ft long. Thus, the total travel required in bumper subs can be considerably more than the motion of the drilling vessel. Lack of knowledge of this fact could have contributed to problems previously experienced with bumper subs. This fact can also lead to fatigue problems in the drilling string for very deep wells. Satisfactory operation should be obtainable whether hy-draulically balanced or unbalanced bumper subs are used in the drilling string. Theoretically, the balanced sub is preferable since its use does not require placing drill collars above the bumper sub to prevent drill-pipe buckling, an inherent characteristic of the unbalanced bumper sub. The current method of calculating weight of drill collars required to prevent helical buckling of drill pipe above unbalanced bumper subs is erroneous. Placing drill collars above the sub to prevent drill-pipe buckling has the same effect on dynamic response as increasing the length of the drilling string by an equal weight of drill pipe. Thus, total travel required in the subs is increased. Means for calculating the correct weight, which is much greater than previously thought, are given in this paper. BALANCED VS UNBALANCED BUMPER SUBS A drilling bumper sub is essentially a telescopic joint capable of transmitting torque at every position of its stroke. Thus, it allows the operator to isolate the weight of the drilling string from the weight of the drill collars above the bit. This permits the driller on a floating rig to maintain accurate control over the weight on bit — a control that is unaffected by vertical motion, due to wave and tide action of the drilling vessel. UNBALANCED BUMPER SUBS The unbalanced bumper sub is simply a splined tele~copic joint (Fig. I). Ordinarily, this arrangement will operate satisfactorily, but the presence of drilling fluid under pressure results in a pressure force that acts downward on the drill collars and bit, tending to open or extend the bumper sub. This downward force is equal to the pressure drop across the bit times the area indicated by diameter d2 in Fig. 1. Denoting this force by Fd, and the pressure drop across the bit by ?p yields Fb = (p/4)d22(?P) .........(1) There is also an upward-directed force given by Fu = (p/4) d22-d21)(?p) .......(2) which puts the drill pipe immediately above the bumper sub in compression, resulting in helical buckling. However, buckling is actually more severe than expected in that buckling occurs as if the compression were equal to Fd, rather than to Fu. This surprising phenomenon is well known as far as tubing is concerned;1-3 but, in contrast with the case of tubing, this force may shorten drill pipe only a few inches. Thus, this cannot explain the operating difficulties that sometimes have been encountered. However, having the drill pipe in compression and helically buckled is contrary to current practice; therefore, drill collars whose weight in mud is equal to the force Fd should be added above the bumper sub. Since the value of Fd depends on the pressure drop across the bit, the

By T. A. O’Hara

SINCE May 1948, when tungsten carbide bits were introduced at the Flin Flon mine, they have been popular with the miners because of their fast drilling speed and low gage loss. The high cost of commercial carbide bits and tipped drill steel, however, prevented their use except for the hardest rock. In an effort to extend the use of tungsten carbide on a basis economically competitive with detachable steel bits, experimental work was begun in 1950 to test the feasibility of making tungsten carbide tipped drill steel in the mine drill steel shop. This work showed that tipped drill steel could be made locally at less than half the cost of the commercial product. The performance of the local tipped drill steel was comparable to that obtained with commercial carbide bits and tipped drill steel and the cost per foot drilled was much lower. Local tipped drill steel was adopted for all mine drilling in November 1951. Since then drilling costs per foot have been sharply reduced and footage drilled per manshift has increased markedly. Experience at Flin Flon has shown that production of satisfactory carbide tipped drill steel is not difficult and that highly skilled labor and costly equipment are not required. As long as wise selection of brazing materials is made and certain simple precautions are rigidly maintained, there is no reason why small mines with relatively unskilled labor cannot produce a satisfactory product. The following description outlines the technique used at Flin Flon for making carbide tipped drill steel and discusses characteristics of the brazing process that make special precautions necessary. Drill steel is forged to four-wing shape in a conventional steel sharpening forge. Standard steel dies are modified to minimize forging cracks around the central waterhole and to forge a blunt bithead on the steel. The steel is preheated to 1500°F and held at this temperature for at least 2 min. When the temperature has equalized throughout the steel section, the drill steel is transferred to the forging furnace and heated rapidly with a reducing flame up to 2000°F. This two-stage method of heating minimizes the grain growth and decarburization of the steel while ensuring that the steel temperature does not vary greatly throughout the forging zone. After forging the steel is allowed to cool in air to about 1600°F before being annealed in a bath of vermiculite. Despite the high hardenability of the 3 pct Ni-Cr-Mo drill steel used, this simple treatment anneals the drill steel sufficiently for milling. The forged and annealed drill steel is slotted on a plain horizontal milling machine that is equipped with a quick opening chuck and a slot depth stop. The full depth of the slot is milled in a single pass of the 3-in. milling cutter which is fed at 33/4 in. per min across the crown of each bit wing. The slots are cut to a width of 0.342 to 0.344 in. Maintenance of this slot width is necessary to ensure that the optimum brazing clearance of 0.002 in. will result after assembling of shims and carbide in the slot. Prior to March 1953, when the milling machine was installed, drill steel was slotted on a small manually fed ¾ hp milling attachment mounted on the bed of a lathe. Over 16,000 drill steels were slotted on this unit, and in view of its small size and low cost it gave excellent service. Brazing of Tipped Steel Drill steel that has been milled and cleaned in carbon tetrachloride is mounted in a rotating cradle holding six drill steels, the length of which may be from 2 to 12 ft. The slots in the drill steel, the shims, and the tungsten carbide inserts are thoroughly fluxed with a fluoride flux and assembled as shown in Fig. 1. Fig. 2 shows the brazing equipment in use. As the ring burner is lowered over the bithead a spring valve opens the gas lines, and the gas mixture, preset to give a slightly reducing flame, is fed to the ring burner where it is lit from a pilot flame. The ring burner heats the drill steel over a zone about 1 to 2 in. below the bithead, which becomes heated by conduction through the steel. By this means the bithead is heated rapidly and evenly, and contamination of the brazing joint with soot from the flame is avoided. The bithead is heated to the melting temperature of the brazing alloy within 1 min. This rapid heating minimizes the disadvantage of a non-eutectic brazing alloy. The brazing alloy, a nickel-bearing quaternary alloy, is placed at the bottom of the slot below the carbide insert, as shown in Fig. 1. As the brazing alloy melts it is drawn by displacement by the carbide and by capillary action into all parts of the joint to displace liquid flux from metal surfaces. As soon as the brazing alloy melts, each insert in turn is wiped by being moved back and forth along the slot. This action assists wetting of the carbide by the brazing alloy and assists in displacing molten flux from the joint. After continuous heating for about 75 sec, when the bithead has reached a temperature of about 1500°F, the ring burner is raised and the gas supply is shut off automatically by the spring valve. As soon as heating is stopped a hand press is placed on the bithead and the inserts are squeezed down firmly. This action minimizes the clearance between the bottom of the insert and the slot. Correctly brazed steel should maintain a clearance at the bottom of the slot of 0.001 to 0.002 in. After six steels have been brazed they are removed from the cradle and allowed to cool in air. As soon as each drill steel is cool it is dressed on a grinding wheel to remove excess flux and braze and is ground to the gage appropriate to the length of the drill steel.

Jan 1, 1955

William B. Phillips, Birmingham, Ala.: The analysis of Pratt coal made by myself, and given by Mr. Ormsbee in his paper (p. 113), is likely to mislead the reader as to the real nature of this coal. It represents the very purest coal that I have been able to get, and does not represent the average composition of the lump-coal as prepared for market. I wish it were true that the coal had no more than 2.50 ash and 0.83 sulphur. The analysis of McCalley is nearer the real figures than any of the others. There is no use in giving an

Jan 1, 1896

T. M. Drown, South Bethlehem, Pa.: Mr. Thackray's paper shows in a striking way the high degree of rapidity and ac curacy exhibited by the chemists of our steel-works in ordinary everyday practice. That determinations made in an hour should present only slight differences in the third place of deci male is certainly matter for surprise and congratulation. This remarkable result has been due, perhaps, in part, to a remark able cause. The managers of works, ignorant of all the diffi culties of the laboratory, have demanded "the impossible " of their chemists—and the chemists have done it! Andrew A. Blair, Philadelphia, Pa.: Mr. Thackray's paper is extremely interesting, especially in its bearing on the question of a standard method for the rapid determination of phosphorus in the laboratories of steel-works. Before discussing the re sults in general, I desire to explain the results obtained by me under method A'. This is the method which I have used in the work of the sub-committee on Methods of the Interna tional Steel Standards Committee. It may be described briefly as follows: Solution in nitric acid; oxidation of carbonaceous matter by permanganate; precipitation of phosphoric acid by molybdate solution; reduction of molybdic acid in the reductor, and titra tion by permanganate. This method was used apparently by only three chemists, Dr. Dudley, Mr. Crowell, and myself. In determining phosphorus by this method, among the most essential points to be considered are the ratio of iron to molyb dic acid, or the reducing action of zinc on molybdic acid as compared to its reducing action on iron, and the ratio of molyb dic acid to phosphorus in the ammonium phospho-molybdate obtained by precipitation from the solution of the steel. In regard to the first point, the usually accepted ratio is 1 to 0.90756, or, as it is roughly stated, 0.9076, which is based on the assumed reduction of the molybdic acid to Mo12019,. This

Jan 1, 1896

By Charles Catlett

THE rapid development of the Portland-cement industry implies that the country is being very carefully searched for material suitable for its manufacture. Such material can be found at a great many places ; but deposits thoroughly satisfactory in chemical composition, and at the same time meeting all the other requirements connected with the economic production and profitable marketing of the product, are exceedingly few, if I may judge from the investigations which I have had to make in a number of States. The raw mixture which by its clinking and grinding forms Portland cement contains approximately 75 per cent. of carbonate of lime. This is found in nature as limestone or marl. The natural rock commonly carries either more than the required percentage of carbonate of lime (in which case it has to be reduced by suitable admixture of clayey ingredients) or less-in which case purer lime carbonate has to be added. The controlling ingredient, therefore, is carbonate of lime, or limestone of the right composition. Among the most serious difficulties is that of finding limestones low enough in magnesia to meet the exacting requirements of certain specifications. All engineers recognize that there is a limit beyond which it is not safe to let the magnesia go; but within that limit there is considerable difference of opinion. Until that difference is finally settled, no one would be willing to invest the large sum of money necessary for a Portland-cement plant, if it were not certain that the usual requirements in this particular could be satisfied. The usual limit in well-established specifications is 5 per cent. of magnesium oxide in the finished cement, but many specifications limit the amount to 3 per cent. These figures

Jan 9, 1907

By R. C. Weed

LEACHING in place at Cananea began in the 1920's on a limited scale. The first plants were small wooden boxes located underground in the Capote and Oversight mines, and output was low. Scrap iron was used as precipitant. Later several other small plants were started up. Leaching was limited entirely to underground areas, and production remained low. The Veta precipitating plant, the first on a larger scale, was put into operation in the late 1920's. After a period of intermittent service it was rebuilt in 1946 and has since been running continuously. In 1943 work on the Colorada open pit was started. This produced 40 million tons of waste, which averaged 0.20 pct capper. When these dumps had aged a few years it was decided to leach them on a large scale, and after considerable research and investigation a leaching system of pumps and pipelines was laid out and installed. At the same time the Ron-quillo precipitation plant was built to treat the copper solutions from the pit dumps. This plant started operation in March 1953. Leaching areas consist of the Colorada pit dumps and various mined out and caved underground stopes. The principal mineral, chalcocite, leaches readily in a weak sulfuric acid solution containing ferric iron. Enough pyrite is contained in the areas to produce an acid-ferric iron solution strong enough to dissolve the copper. Each area is studied to determine the best method of distributing the water over it and the best method of collecting the copper-bearing solutions after leaching has taken place. Water is generally distributed by means of ponds, ditches, and sprays. Spraying has proved the best method of spreading the water evenly; however, in a dry climate some water is lost through evaporation. After passing through the leachable material the solution is collected underground by dams and bulkheads and on surface by dams. An effort is made to give the maximum storage capacity practicable.

Jan 1, 1957

By D. M. McFarland

A FEW years ago a novel electric detonator known as the split-second or millisecond delay electric blasting cap was introduced for use in quarry blasting. Regular electric blasting caps fired in series may be depended upon to fire within a millisecond or so from the first to the last in a series. Regular delay electric blasting caps are provided that fire one period after the other period in intervals of 1/2 to possibly 1 1/2 sec. Most split-second or millisecond delays are designed to fire one period after the other period in possibly 25 to 50 millisecond intervals. The ear is not capable of detecting time intervals of this magnitude. The primary thought at the time millisecond de- lays were introduced was to investigate the results on rock breakage by firing a line of holes in a quarry face.so that charges in adjacent holes would not be detonated simultaneously. This could not be accomplished satisfactorily with regular delays. The time interval between successive periods of $5 to 1 sec was sufficient to permit considerable movement of the burden. If the burden of one hole was reduced to a great extent by the firing of an adjacent hole, the firing of the hole with the reduced burden would likely reveal this lack of confinement by a terrific report and wild throw of rock.

Jan 1, 1950

Jan 1, 1928

By T. S. Lovering

Jan 1, 1965

Jan 1, 1930

Jan 1, 1918

Jan 1, 1935

Jan 1, 1902

Jan 1, 1932

Jan 1, 1931

Jan 1, 1913

Jan 1, 1932