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The first phase of our work for PMSRC on this contract was devoted to a comprehensive and in-depth assessment of electromagnetic (EM) noise measurements and data taken by several contractors for use in the design of operational and emergency mine communications. Pertinent measurements and data of other selected investigators were also included in the evaluation. This assessment treated the measurements and instrumentation used, the data analysis and presentation methods, and the utility of the final results. This phase concluded with the identification of the most useful results and methods, the remaining data gaps, the contractor most qualified to fill these data gaps, and the definition (with PMSRC and this contractor - NBS, National Bureau of Standards) of a follow-on noise measurement program, instrumentation system, and data processing methods tailored to obtain the necessary but missing noise data. A partial bibliography of references related to electromagnetic and seismic noise and propagation in the frequency bands of interest was also compiled during this first phase. The body of this Part of the final report presents a summary of the findings of our EM noise assessment, together with detailed recommendations regarding the new noise measurements to be taken and the instrumentation and data processing methods to be used. This work was done during the latter part of 1971 and the early part of 1972. During subsequent phases of the contract ADL was asked to perform on-going evaluations of the continuing program of electromagnetic (EM) noise and propagation measurements made by Bureau contractors, and to utilize pertinent data from these measurements to make performance estimates for

Jan 1, 1974

This Volume documents the Phase 111 effort on the Seismic Detection and Location of Isolated Miners on Contract H0122026 undertaken during the fall of 1972 by a task team composed of ADL staff and several seismic consultants. The team was assembled specifically to work together on complementary tasks, at an accelerated level of effort for four months, to meet the Bureau of Mines' time schedule for obtaining independent, objective, technical judgments regarding seismic methods and systems for detecting and locating isolated miners. The impetus for this work resulted from a compilation and analysis, during the first half of 1972, of new experimental data obtained from a series of in-mine field tests conducted by Westinghouse Corp .+ using the CMRSS* interim seismic location system. The Bureau of Mines took advantage of the availability of these new data to reassess the potential and limitations of various seismic methods and systems, and to direct its seismic system improvement program accordingly. ADL assisted the Bureau in this reassessment by drawing on the skills of seismic consultants from industry, universities and government, to supplement the skills of the ADL project team. The consultants were principal resources of broadly-based and detailed technical expertise in the areas of seismic signal-source and signal-propagation characteristics, natural and cultural seismic noise, seismic sensors and field instrumentation, seismic signal and data processing for detection and location, and overall seismic system utilization in the field under operational emergency conditions. Specifically, the participating consultants were: F. Crowley, Air Force Cambridge Research Laboratories ; W. Dean, Teledyne Geotech, Alexandria Laboratories; R. Greenfield, Pennsylvania State University; J. Kuo, Columbia University; D. Peters and R. Crosson, University of Washington; and F. Pilotte, U.S. VELA Seismological Center. The principal ADL participants were J. Ginty, R. Lagace, M. Roetter, and R. Spencer.

Jan 1, 1974

This Part describes a mine pager phone to public telephone interconnect sys tem that permits mine paging telephones to be selectively interconnected with the public telephone system, as illustrated by Figure 1. This interconnect concept was first conceived and demonstrated in breadboard form by H. E. Parkinson of Industrial Hazards and Communications, PMSRC, as one means for providing improved emergency and off-hours communications. The third-generation prototype unit described in this Part was designed and fabricated by Arthur D. Little, Inc. This unit is a small desk-top or wall-mounted unit that connects directly to both the public telephone line and the mine pager phone line, and requires no modifications to either the public dial telephone or mine pager phones. As part of this task, ADL also built, under a very compressed time schedule, a second-generation prototype unit suitable for reliable demonstration of the interconnect concept during the Bureau's technology transfer seminar on mine communications in March 1973. * A major objective of the design of the third-generation unit described in this Part was that it be compatible with present mine pager phone systems utilizing DC voltage on the mine phone line to activate the phone loudspeakers. Therefore, this unit was designed to operate in a push- to-talk, push-to-listen mode that accommodates the inherent design differences and operation modes of the mine phones of different manufacturers. Though this push- to- talk, push- to-listen mode of operation may seem slightly unusual at first sight, we have found it is easily learned by new users. However, mine phone manufacturers wishing to expand their product lines with such an interconnect system will probably find it to their advantage to customize the design of this system to their particular mine phones, thereby utilizing the unique attributes offered by their individual product lines. This customization should not be difficult, and Section III below suggests some of the features that can be easily added to future designs. Detailed parts lists and circuit schematics for the present third-generation proto- type system can be obtained from the system manual submitted to PMSRC and placed on public file.

Jan 1, 1974

By John T. Kuo

The miner's seismic source strength can be approximately estimated on the basis of a single force acting in an infinite medium. Because of the uncertain- ty involved in estimating the amount of conversion from mechanical energy to seismic energy, the source strength thus estimated may be in error by as much as a half-order of magnitude. Calculations of wave transmission must take into account geometrical spreading, dissipation of energy by internal friction, and energy partition due to reflection and refraction of waves impinging on inter- faces in the layered earth. Theoretically derived peak-to-peak particle velocities in microinches per second (PIPS) are given for two models ; viz: (i) 50-feet thick and (ii) 100- feet thick 4000 ft/sec layers with Q = 20, overlying a half-space of 10,000 ft/sec material with Q = 5O;for the cases .of a hammer blow and a timber impact, at the frequencies of 50 Hz and 100 Hz. Comparison of the theoretically derived peak-to-peak particle velocity with experimental data taken at the Copper Queen Mine indicates that the theoretical particle velocity may be overestimated. A discussion of the distortion of seismic wavefronts by mine tunnels indicates that it is unfavorable to use a seismic source impact on the floor of the tunnel, since deceptive delays in arrival time are liable to occur at the surface. A program of parallel theoretical and experimental work is required to clarify uncertainties still associated with the nature and strength of the miner's seismic source signal which cannot be resolved within the approximations of this work. Its major components include theoretical investigations of the (1) Wave diffraction and scattering of an impact source on a face of a cylindrical cavity. (2) Impact of an elastic object on an elastic medium.

Jan 1, 1974

By Frank Pilotte

Proper design characteristics for a seismic system to locate miners during a mine disaster are considered in terms of a total system concept. Field hardware, processing equipment, operating personnel, deployment, training, and supportive R and D are necessary elements of the total system. Each of these elements is discussed and an indication given as to the requirements necessitated by each one. Hardware must be portable, rugged, and fieldworthy. Processing equipment must be simple to operate, expandable for future processing improvements, and ruggedized for field use. A small well-trained team must be available for quick response in times of emergency. Alternative deployment procedures are necessary to allow for a variety of situations including both ground and air delivery. Supportive R and D is used to support training and upgrading of the system.

Jan 1, 1974

This part of the final report treats some problems related to coal mine carrier frequency communication systems using the trolley wire/track transmission line. This work was undertaken for a brief period of time during the summer of 1972 to help understand, quantify, and improve some of the trolley wire carrier system behavior observed and/or predicted. Calculations and estimates of transmission line characteristic impedance, inductance and capacitance per unit length, mine motor loading effects, parallel line effects, and connection impedances are presented in Chapter I. Chapter II treats the design of r-f isolators for reducing the undesired and troublesome r-f loading that mine motors present to the trolley transmission line. Chapter III treats a diversity method for combatting standing wave nulls. I. CALCULATIONS RELATED TO TROLLEY WIRE COMMUNICATIONS A. ESTIMATION OF INDUCTANCE AND CAPACITANCE PER UNIT LENGTH OF TROLLEY LINES To estimate the L and C per unit length of trolley lines, we use the eccentric line model of Section G of this Chapter, "Characteristic Imped¬ance Estimates for Mine Trolley Lines." The capacitance per unit length for an eccentric line is given by (1)

Jan 1, 1974

By Roy Greenfield

During the detection phase, several procedures can be used to improve the signal-to-noise ratio (SIN) . • Subarrays of up to 10 seismometers should be used. The apparent failure to obtain improvement in SIN in the Westinghouse subarrav work is probably due to excessive noise in the electronics. The spacings needed for sensors in the subarray must still be established. • The sensors should be buried. Even burial to a few feet will probably give appreciable reduction of noise. A deeper burial will probably further reduce the noise; and, if the seismometers can be put below the weathered layer, the signal level will probably be increased. The reduction in noise by burial will be especially effective during high noise periods due to wind or rain. • Before attempting detection, the waveforms should be bandpass filtered. The bandpass should go from 25 Hz to an upper frequency of 100 to 200 Hz. Further measurements with a low noise system must be done before the signal-to-noise ratio can be determined for the 100 to 200 Hz range. Any narrow band noise should be removed by notch filters. • If noise levels differ among seismometers of a subarray, weights inversely proportional to the noise power should be applied to the seismometers. • Automatic methods of screening data for possible signal arrivals should be developed, but the final determination that the signal on a subarray output appears to be from a miner should be made by an analyst. Detection of "signal" on several subarrays should be required for positive identification. In the location phase, after detection: • If repeated signals are received, they should be coherently added (stacked) to give as good a SIN as possible for use in determining signal arrival times, to be used in location computations. The miner should, if possible, repeat the signal 25 to 50 times.

Jan 1, 1974

Coaxial cable structures form the subject of substantial theoretical and experimental investigations either directly related, or which can be extrapolated, to the communications needs and environments of U.S. coal mines. Communication systems based on "guided" waves, of which "leaky" coaxial cables are one implementation, are attractive candidates for providing a range of communication functions primarily along haulage ways, and possible also within sections up to the working face. (However, there are still strong reservations as to whether a practical coaxial cable sys tem could provide sufficient communications coverage within a section. ) In this Part, we present the results of some theoretical calculations of the performance of leaky coaxial cable communication systems. We also analyze the applicability of the theoretical and experimental results obtained by other researchers to the needs of U.S. coal mines. In particular, this investigation has been focused on the utility of relatively low cost, conventional, flexible, coaxial cable at frequencies covering the LF through HF bands and extending into the lower part of the VHF band, as opposed to relatively high cost, special semi-rigid, coaxial cable* at frequencies in the VHF and UHF bands. There are three major design alternatives for coaxial cable communication systems considered in this chapter: • Base station feeding a coaxial cable with high surface transfer impedance (holes in outer conductor, e.g., braid construction). • Base station feeding a coaxial cable with repeaters (U.K. experiments). • No base station, direct communication via a coaxial cable with periodic radiative structures.

Jan 1, 1974

By David C. Peters, Robert S. Crosson

A method of error analysis has been applied to the location technique of non-linear least squares iterative inversion in order to evaluate the resolving power of several seismic array configurations with various assumed earth models and errors and inaccuracies in arrival times. The results obtained demonstrate that lateral accuracies of location are improved significantly when the depth of the miner is known. Lateral location to within 100 feet appears achievable in many instances. If it is possible to refine earth models significantly beyond what has normally been assumed in this work by the use of on-site data, or if the mine is shallow (300 feet or less), accuracies of-about 30 feet or so may be attainable. Inaccuracies in earth models of about 5% are found to contribute much more heavily to these location inaccuracies than errors of a few milliseconds in picking arrival times; however, arrival time errors of 15-20 ms or above will dominate these model inaccuracies. The expected accuracy of location is found to fall off very rapidly as the miner moves outside the array. The strength of this effect depends markedly upon the geometry of the array configuration and can be reduced by careful design. Also, as the size of the array is increased, expected location errors within the array are not altered much, but continue to match the error associated with the smaller array over a larger area (assuming that all stations can still pick up the miner's signals). Better location accuracy, especially with respect to depth control is achievable in an earth where the velocity is depth-dependent (increasing with depth) than in one which is homogeneous. This is an advantage since the

Jan 1, 1974

In this Part, we have included copies of the flip charts and overhead projector viewgraphs used in the two briefings we conducted as part of this seismic detection and location task. The first one was an overview and problem definition briefing given to the seismic consultants on September 7, 1972. The second was a formal oral presentation of study results to technical staff members of the Pittsburgh Mining and Safety Research Center on November 21, 1972.

Jan 1, 1974

By Roy Greenfield

Estimates are given for the distance from a seismometer at which a miner can probably be detected. The procedure in making these estimates was to first establish the natural noise levels at the output of a surface seismometer for the 25 to 100 Hz frequency passband. The noise levels give the range of values which may be expected in areas with no man-made noise. For each noise level, we give the detection threshold which, when exceeded, indicates that a signal has been received. Based on the signals recorded by Westinghouse, curves are given which show the peak signal amplitude as a function of source- to-receiver distance (slant range). Curves are given for the Westinghouse seismic thumper, a 50-pound timber, and a sledge. For a given type of source, the receive signal strength depends more strongly on slant range than on any other factor. However, there is approximately a five-to-one scatter in the amplitudes. Thus, further study of factors affecting the signal amplitude might allow better estimates to be made for any particular geological setting. Combining the signal amplitude with the detection thresholds for the different noise conditions gives the distances at which a miner should be detected. These are given in Table l* below. [ ] The text also gives the increase in detection ranges which should occur if steps are taken to increase S/N by 10 dB. We feel that 10 dB is a conservative estimate of the improvement possible. During an actual rescue operation, the seismic crew and system should be capable of making on-site estimates of their detection capability, based on measurements of the site noise, and upon the best available estimates of the

Jan 1, 1974

By J. Gurland

The wmk is concerned with the estimate of the degee of continuity of a particulate phase dispersed in a matrix. The first section is a verieu: of the parameters nzeasurable by quantitative rnetallogvaphy, namely the contact area and, under certain conditions, the number of contacts between particles of one phase. In the second section, the frequency of particle contacts is related to the degee of continuity of a randomly embedded phase orz the basis of the lattice-percolation model of Hamrnersley and others. THE extent of continuity of the constituent phases may greatly influence the structure-sensitive properties of phase mixtures, particularly if the phase properties differ significantly. An example from the literature1 is shown in Fig. 1. The marked decrease of the electrical resistivity of sintered silver-alumina bodies near 25 pct by volume of silver presumably occurs because the more conductive phase changes from a discontinuous to a continuous structure. Other example of electrical- and thermal-conductivity transitions are cited by kingery In view of these observations, a knowledge and understanding of the connectivity of the microstructure may be of considerable practical importance. This study is concerned with one aspect of the genera1 problem, namely the estimate of the degree of continuity of a particulate phase dispersed in an opaque matrix. The first section reviews the parameters measurable on a polished cross section by auantitative metallography, such as the contact area and under certain conditions, the number of contacts between particles of one phase. In the second section, an attempt is made to relate the frequency of particle contacts to the degree of continuity of a randomly embedded phase. For the purpose of this discussion, the aggregate has two constituents: the particulate phase and the matrix. The latter is considered to be homogeneous. The term "particle" is used with the meaning of "grain", i.e., a minute unit of matter which is usually a single crystal of a readily distinguishable substance within the confines of a simply connected boundary. While many of the concepts which are used here to describe the structural variables characterizing the microstructure of phase mixtures are qualitative and ill-defined, they are presented with the intent of stimulating further work of a more general and rigorous nature. I) PARTICLE CONTACT, CONTIGUITY, AND MEAN FREE PATH 1) Measurement of Contiguity. The fraction of the total internal surface of a phase a shared with particles of that same phase in a two-phase mixture of and $ is indicated by the contiguity ratio:3 whereis the area of the interface between o particles, and Sap is the area of the interface between a particles and matrix P, per unit volume of mixture. The contiguity ratio ranges from 0 to 1 as the distribution of the a phase changes from a completely dispersed to a completely agglomerated structure. The interfacial areas may be obtained from simple intercept measurements on a random plane, after Smith and Guttman where and N are the numbers of intercepts between a random line of unit length on a plane of polish and the interparticle and interphase interfaces, respectively. The equations are valid for any distribution of particle sizes and shapes.

Jan 1, 1967

By R. B. Gordon, D. A. Koss

Ultrasonic-atlenuation changes due to the formation of free dislocations have been observed during tensile tests of magnesium and LiF single crystals and samples of polycrystalline Results on the LiF and samples are similar: A preyield attenzration increase is observed which, however, be-corlzes smaller as the magnitude of the drop in load al yielding increases. This indicates that the yield point observed in these materials is due to dislovation rather than dislocation unpinning and that the initial density ' free dislocations must be low if the yield point is to be sharp,. Tests on the magnesium ere conducted at both 27" and 200C. Magnesium has the unusual property that the yield drop is larger at the higher test temperature and is accomplished by a decrease in attenuation. The latter is due principally to the temprovary pinning of detained dislocations by highly solute atoms. After strain aging., a stress as low as 0.3 bur suffices to unpin dislocations; microstrain measuements of sufficient sensitivity should. reveal plastic flow at stress levels this low IN another paper,' we describe the technique of simultaneously observing ultrasonic-attenuation changes and plastic microstrain during deformation of spher-oidized carbon steels. Changes of ultrasonic attenuation indicate damping effects caused by the oscillation of long, freely moving dislocation segments. Simultaneous microstrain measurements are used to indicate total dislocation motion. The dislocation-damping observations are most useful in the study of the early stages of deformation where the dislocation density is low and the plastic strain is small and relatively difficult to measure. Particularly interesting results are found in materials which display sharp yield points. Observations of these phenomena are reported here for three materials: single-crystal LiF and magnesium, and poly crystalline molybdenum. EXPERIMENTS Dislocation-damping effects were observed by measuring changes in acoustic attenuation with the ultrasonic-pulse method. The end faces of each of the specimens were ground flat and parallel and a quartz 10 Mc per sec, x-cut transducer was attached to one face. The bonding agents used were: a) "Nonaq" stopcock grease with magnesium, b) beeswax with LiF, and c) salol with molybdenum. With the LiF, the best acoustic signals were obtained at 45 and 50 Mc per sec; all other measurements reported are at 10 MC per sec. The Sperry Ultrasonic Attenuation Comparator2 was used to measure attenuation changes. In the

Jan 1, 1967

By C. C. Koch, M. L. Picklesimer

PHYSICAL metallurgists interested in the alloying behavior and phase transformations in rare-earth metals and alloys require a strain-free polished and etched surface for both metallographic and X-ray examination. However, the rare earths have presented a problem in this respect since they are difficult to polish free from strain and are very reactive to the atmosphere. Their tendency to oxidize readily even at room temperature necessitates careful preparation and rather elaborate protection if their surface is to be examined for any length of time. The "light" lan-thanides (i .e., atomic numbers less than 63), especially lanthanum and cerium, are particularly bad in this regard; they oxidize very rapidly at room temperature. To eliminate the problem of plastic deformation remaining on the surface after mechanical polishing, electropolishingl and chemical polishing techniques2 have been developed. The electropolishing technique requires the specimen to be immersed in an electrolyte at -77°C and thus obviates a metallographic study of, for example, the fcc —double-hexagonal close-packed (dhcp) transformation in cerium which begins at -10°C. The chemical polishing solution has been used only on several of the "heavy" rare-earth metals. However, a convenient method for protecting the polished and etched surfaces from atmospheric corrosion has not been available. Our interest in the superconducting properties of lanthanum, and in the phase transformations in lanthanum and cerium, has led us to develop a technique for the metallographic preparation of lanthanum and cerium which clearly reveals the microstructure and preserves the etched surface for days. The specimens are chemically polished and anodized. The chemical polishing is performed at room temperature, the anodic oxide film provides the required protection from the atmosphere, and colors produced in the film provide a simple positive technique for phase identification. Lanthanum and cerium metal ingots obtained from Johnson Matthey and Co., Ltd., were remelted to suitable shapes and heat-treated to produce various microstructures. The samples were placed in epoxy mounts and, after a small hole was drilled in the back of the mount for electrical contact, were ground on silicon carbide

Jan 1, 1968

By R. G. Fenish

THE B-Ni system was chosen for this study because of the great interest being shown in boron-fiber-strengthened composite materials. Boron fibers were obtained from Texaco Experiment, Inc. They average 4.2 mils in diam with a 0.5-mil tungsten wire in the center. In order to make the diffusion couple, the fibers were included in the nickel matrix by electroforming. The samples were placed in a preheated furnace for the desired temperature and length of time. Sectioning and polishing the samples revealed concentric rings as shown in Fig. 1. The average penetration distance, X, was calculated by measuring the radius of the second phase (the white shell in Fig. 1) and subtracting the original radius. The second phase was identified as NiB by X-ray diffraction. This allows the kinetics of the formation of the phase NiB to be calculated by Eq. [I], which is taken from Hoffman:"

Jan 1, 1967

By R. N. Orava

TO the author's knowledge, only one satisfactory high-resolution technique for etch-pitting dislocations in Cu-Zn alloys has been published.' In that account, pits in 70/30 brass single crystals were produced by etching electrolytic ally in a 30 pct orthophosphoric acid bath. Thereafter, observations were made from surface replicas by electron microscopy. The method of pitting and observation permitted the high resolution necessary for the distinction of individual dislocations in arrays of pile-ups. However, no comment was offered concerning the possibility of obtaining pits which are amenable to optical resolution. Moreover, for adequate results, the electrolytic pitting process is invariably preceded by a polishing stage which could obscure the surface features of interest. Consequently, it would be desirable to be able to delineate, by solely chemical means, dislocations which could be detected by both optical and electron metallo-graphic techniques. This was achieved by the simple expedient of modifying two etchants reported by young2 to reveal dislocations on the (100) planes of pure copper. Single crystals of 70/30 a brass, described previously,3 were sectioned to provide a surface parallel to a set of {100) planes, mechanically polished, and subsequently electropolished at 2.4 v in a solution comprised of 2 parts H3PO4, 4 parts ethanol, and 3 parts water. The inclusion of ethanol tended to inhibit nonuniform surface attack. Etch-pitting was effected by a 2 to 3 sec immersion in a 70 pct aqueous solution of HNO3. The samples were then washed in a fast-flowing stream of water, and rinsed further in distilled water, and ethanol, before drying. It is important to note that this reagent should be either used immediately after mixing, or, if allowed to cool, reheated to about 35°C prior to use. No pitting was obtained at room temperature. Typical results are shown in Fig. 1 where (a) is an optical view of the pitted surface and (b) is an electron micrograph of a silicon monoxide replica shadowed with tungsten oxide. The former is characteristic of a somewhat longer etching time (-6 to 8 sec) which varied with bath temperature. Similar pits accrued from a 1/10 aqueous dilution of another of Young's solutions2—2 M FeC1,6H20 and 7.8 M HBr.

Jan 1, 1968

By J. Stringer, I. W. Edington, C. R. Rarey

THE geometrical interpretation of transmission electron micrographs of hcp metals is more complicated than the equivalent interpretation of cubic metal for two reasons: firstly, prominent zone axes are not in general normal to prominent planes, so that a simple diffraction pattern often corresponds to a nonra-tional foil plane; and secondly, the Miller-Bravais sys-tem of indexing directions is not easy to visualize. In this, the indexing is referred to the Bravais four-axis system, and the direction is labeled [hkil], chosen so that and I are shown in Fig. 1. Some geometrical relationships useful for the interpretation of transmission micrographs have been calculated and are tabulated below: 6) Direction of the intersection of two planes; this is easily calculated by applying Condition 4 to both planes: a direction that lies in both planes is clearly their direction of intersection. Some of the above expressions have also recently been given by Otte and Crocker;' Expression 5 is of course in most standard crystallographic texts. It is generally considered easier and quicker to use graphical methods for the interpretation of electron micrographs than analytical methods. For this purpose, it is most convenient to use a "double stereo-gram" in which both the poles alzd the rational directions are plotted. It is, of course, necessary to orient

Jan 1, 1967

By J. D. Verhoeven

In a recent study1 this author has investigated the effect of an electric field upon the solute redistribution accompanying solidification of Sn-Bi alloys. It was concluded that the primary effect of the electric current upon the solute redistribution resulted from electrotransport within the liquid boundary layer at the solid-liquid interface. In order to maximize the electrotransport effect all of the experiments were conducted at the highest current densities experimentally attainable. It was found that these high current densities produced considerable convective mixing within the liquid metal. This mixing reduces the boundary layer thickness and consequently reduces the effectiveness of the electric field in producing solute redistribution. Consequently, it is quite possible that the condition of maximum achievable current density would not correspond to maximum solute redistribution. It may be that, as the field intensity is increased, a point is reached where the additional solute redistribution from the increased electrotransport is more than offset by the decrease in solute redistribution resulting from the increased mixing in the liquid. In order to check this possibility the effective distribution coefficient has been determined as a function of current density in a series of experiments. The experiments were conducted on 6.6 at. pct Bi

Jan 1, 1968

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968

By N. R. Adsit

THE B-Ni system was chosen for this study because of the great interest being shown in boron-fiber-strengthened composite materials. Boron fibers were obtained from Texaco Experiment, Inc. They average 4.2 mils in diam with a 0.5-mil tungsten wire in the center. In order to make the diffusion couple, the fibers were included in the nickel matrix by electroforming. The samples were placed in a preheated furnace for the desired temperature and length of time. Sectioning and polishing the samples revealed concentric rings as shown in Fig. 1. The average penetration distance, X, was calculated by measuring the radius of the second phase (the white shell in Fig. 1) and subtracting the original radius. The second phase was identified as NiB by X-ray diffraction. This allows the kinetics of the formation of the phase NiB to be calculated by Eq. [I], which is taken from offman:"

Jan 1, 1967