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A History of Wireless Telegraphy (2nd edition, revised), J. J. Fahie, 1901, pages 292-304:

APPENDIX  C.

VARIATIONS  OF  CONDUCTIVITY  UNDER  ELECTRICAL  INFLUENCE.

    Substance of a paper by Prof. E. Branly, of the Catholic University of Paris. 1

    The object of this article is to describe the first results obtained in an investigation of the variation or resistance of a large number of conductors under various electrical influences. The substances which up to the present have presented the greatest variations in conductivity are the powders or filings of metals. The enormous resistance offered by metal in a state of powder is well known; indeed, if we take a somewhat long column of very fine metallic powder, the passage of the current is completely stopped. The increase in the electrical conductivity by pressure of powdered conducting substances is also well known, and has had various practical applications. The variations of conductivity, however, which occur on subjecting such bodies to various electrical influences have not been previously investigated.
    The Effect of Electric Sparks,--Let us take a circuit comprising a single cell, a galvanometer, and some powdered metal enclosed in an ebonite tube of one square centimetre cross section and a few centimetres long. Close the extremities of the tube with two cylindrical copper tubes pressing against the powdered metal and connected to the rest of the circuit. If the powder is sufficiently fine, even a very sensitive galvanometer does not show any evidence of a current passing. The resistance is of the order of millions of ohms, although the same metal melted or under pressure would only offer (the dimensions being the same) a resistance equal to a fraction of an ohm. There being, therefore, no current in the circuit, a Leyden jar is discharged at some little distance off, when the abrupt and permanent deflection of the galvanometer needle shows that an immediate and a permanent reduction of the resistance has been caused. The resistance of the metal is no longer to be measured in millions of ohms, but in hundreds. Its conductivity increases with the number and intensity of the sparks.
    Some 20 or 30 centimetres from a circuit comprising some metallic filings contained in an ebonite cup, let us place a hollow brass sphere, 15 to 20 centimetres in diameter, insulated by a vertical glass support. The filings offer an enormous resistance and the galvanometer needle remains at zero. But if we bring an electrified stick of resin near the sphere, a little spark will pass between the stick and the sphere, and immediately the needle of the galvanometer is violently jerked and then remains permanently deflected. On some fresh filings being placed in the ebonite cup, the resistance of the circuit will again keep the needle at zero. If now the charged brass sphere is touched with the finger, there is a minute discharge and the galvanometer needle is again deflected. With a few accumulators the experiment can easily be made without a galvanometer. The circuit consists of the battery, some metallic powder, a platinum wire, and a mercury cup. The resistance of the powder is so high that the interruption of the circuit takes place without any sparking of the mercury cup. If now a Leyden jar is discharged in the neighbourhood of the circuit the powder is rendered conducting, the platinum wire immediately becomes red hot, and a violent spark occurs on breaking the circuit.
    The influence of the spark decreases as the distance increases, but its influence is observable several metres away from the powder, even with a small Wimshurst machine. Repeating the spark increases the conductivity; in fact, with certain substances successive sparks produce successive jerks, and a gradually increasing and persistent deflection of the galvanometer needle.
    Influence of a Conductor traversed by condenser Discharges.--While using the Wimshurst machine it was noticed that the reduction in the resistance of the filings frequently took place before discharge. This led me to the following experiment: Take a long brass tube, one end of which is close to the circuit containing the metallic powder; its other end, several metres distant from the circuit, is fairly close to a charged Leyden jar. A spark takes place and the conductor is charged. At the same instant, the conductivity of the metallic powder is greatly increased. Fig. 1
    The following arrangement, owing to its efficacy, convenience, and regularity of action, was used by me in most of my researches, and I shall briefly call it the A arrangement (fig. 1).
    The source of electricity is a two-plate Holtz machine driven at from 100 to 400 revolutions. A sensitive substance is introduced into one of the arms of a Wheatstone bridge, or into the circuit of a single Daniell cell at a distance of some 10 metres from the Holtz machine. Between the discharge knobs of the machine and the Wheatstone bridge, and connected to the former, there are two insulated brass tubes, A A', running parallel to one another 40 centimetres apart. The Leyden jars usually attached to a Holtz machine may be dispensed with, the capacity of the long brass tubes being in some measure equivalent to them. The knobs S were 1 mm., ·5 mm., or ·1 mm. apart. When the plates were rotated, sparks rapidly succeeded each other. Experiments showed that these sparks had no direct effect at a distance of 10 metres. The two tubes A A' are not absolutely necessary; the diminution of resistance is easily produced if only one is employed, and in some cases, indeed, a single conductor is more efficacious. An increase in the speed of the machine increases its action to a marked extent. The sparks at S may be suppressed by drawing the knobs apart, but the conductor A will still continue to exert its influence, especially if there is a spark-gap anywhere about.
    Effects of Induced Currents.--The passage of induced currents through a sensitive substance produces similar effects to those described above. In one instance an induction coil was taken, having two similar wires. The circuit of the secondary wire was closed through a tube containing filings, the galvanometer being also in circuit. Care was taken to ascertain before introducing the filings into the circuit that the currents on make and break gave equal and opposite deflections. Filings were then introduced into the circuit, the primary being made and broken at regular intervals. The following table gives the results obtained in the case of zinc filings:--

ZINC  FILINGS.
Galvanometer throws.          Galvanometer throws.
1stclosing 1stopening18°
2nd"64° 2nd"100°
3rd"146° 3rd"140°

    Effects of passing Continuous Currents of High E.M.F.--If a continuous current of high E.M.F. is employed, it renders a sensitive substance conducting. The phenomenon may be shown in the following manner. A circuit is made up consisting of a battery, a sensitive substance, and a galvanometer. The E.M.F. of the battery is first 1 volt, then 100 volts, then 1 volt. Below I give the galvanometer deflections obtained with an E.M.F. of 1 volt for three different substances before and after the application of the E.M.F. of 100 volts:--

Before application
of current.
          
After application
of current.
16 100
  0   15
  1 500

    In the case of some measurements taken on a Wheatstone bridge, a prism of aluminium filings interposed between two copper electrodes offered a resistance of several million ohms before a high E.M.F. was applied, but only offered a resistance of 350 ohms after the application of this pressure for one minute. The time during which the powder should be interposed in the battery circuit should not be too short. Thus, in one instance the application for 10 seconds of 75 mercury sulphate cells produced no effect, but their application for 60 seconds resulted in the resistance being reduced from several megohms to 2500 ohms.
    It should be observed that the phenomenon of suddenly increased conductivity occurs even if the sensitive substance is not in circuit with a battery at the time it is influenced. Thus, the metallic filings, after having been placed in circuit with a Daniell cell, and their high resistance observed, may then be completely insulated and submitted in this condition to the action of a distant spark, or of a charged rod, or of induced currents. If, after this, the filings are replaced in their original circuit, the enormous increase in their conductivity is immediately apparent. Fig. 2    The conductivity produced by these various methods takes place throughout the whole mass of the metallic filings, and in every direction, as the following experiment will show. A vertical ebonite cup containing aluminium powder (fig. 2) is placed between two metal plates A, B; laterally the powder is in contact with two short rods C, D, which pass through the sides of the ebonite cylinder. A and B can be connected to two terminals of one of the arms of the Wheatstone bridge, C and D being free, and vice versâ. Whatever arrangement is adopted, if a battery of 100 cells is joined up for a few seconds with one or the other of the pairs of terminals, the increase in the conductivity is immediately visible in that direction, and is found to exist also in the direction at right angles.
    Substances in which Diminution of Resistance has been observed.--The substances in which the phenomenon of the sudden increase of conductivity is most easily observed are filings of iron, aluminium, copper, brass, antimony, tellurium, cadmium, zinc, bismuth, &c. The size of the grains and their nature are not the only elements to be considered, for grains of lead of the same size, but coming from different quarters, offer at the same temperature great differences in resistance (20,000 to 500,000 ohms). Extremely fine metallic powder, as a rule, offers almost perfect resistance to the passage of a current. But if we take a sufficiently short column and exert a sufficiently great pressure, a point is soon reached when the electrical influence will effect a sudden increase in the conductivity. Thus, a layer of copper reduced by hydrogen, which does not become conducting under the influence of the electric spark or otherwise, will become so on being submitted to a pressure of 500 grammes to the square centimetre (7 lb. per square inch). Instead of using pressure, I employed as a conductor in some experiments a very fine coating of powdered copper spread on a sheet of unpolished glass or ebonite E (fig. 3), 7 centimetres long and 2 centimetres broad. A layer of this kind, polished with a burnisher, has a very variable resistance. With a little care one can prepare sheets which are more or less sensitive to electrical action. Fig. 3
    Metal powders or metal filings are not the only sensitive substances, as powdered galena, which is slightly conducting under pressure, conducts much better after having been submitted to electrical influence. Powdered binoxide of manganese is not very sensitive unless mixed with powdered antimony and compressed.
    Making use of the A arrangement with very short sparks at S (fig. 1), the phenomenon of increased conductivity can be observed with platinised and silvered glass, also with glass covered with gold, silver, and aluminium foil. Some of the mixtures employed had the consistency of paste. These were mixtures of colza oil and iron, or antimony filings, and of ether or petroleum and aluminium, and plumbago, &c. Other mixtures were solid. If we make a mixture of iron filings and Canada balsam, melted in a water bath, and pour the paste into a little ebonite cup, the ends of which are closed by metallic rods, a substance is obtained which solidifies on cooling. The resistance of such a mixture is lowered from several megohms to a few hundred ohms by an electric spark. Similar results are obtained with a solid rod composed of fused flowers of sulphur and iron or aluminium filings, also by a mixture of melted resin and aluminium filings. In the preparation of these solid sensitive mixtures, care must be taken that the insulating substance should only form a small percentage of the whole.
    Some interesting results are also obtained with mixtures of sulphur and aluminium, and with resin and aluminium, when in a state of powder. When cold these mixtures, as a rule, do not conduct either directly or after they have been exposed to electrical influences, but they become conducting on combining pressure with electrical influences. Thus, a mixture of flowers-of-sulphur and aluminium filings in equal volumes was placed in a glass tube 24 mm. in diameter. The weight of the mixture was 20 grammes and the height of the column 22 mm., with a pressure of 186 grammes per square centimetre (2½ lb. per square inch). The mixture is not conducting, but after exposure to electrical influence, obtained by the A arrangement, the resistance falls to 90 ohms. In a similar manner a mixture of selenium and aluminium, placed in a tube 99 mm. long, was not conducting until after it was exposed to the combined influence of pressure and electricity.
    The following is one of the group of numerous experiments of a slightly different character. A mixture of flowers-of-sulphur and fine aluminium filings, containing two of sulphur to one of aluminium, is placed in a cylindrical glass tube 35 mm. long. By means of a piston, a pressure of 20 kilogrammes per square centimetre (284 lb. per square inch) was applied. It was only necessary to connect the column for 10 seconds to the poles of a 25-cell battery, for the resistance originally infinite to be reduced to 4000 ohms. Fig. 4
    The arrangement shown in fig. 4 illustrates another order of experiment. Two rods of copper were oxidised in the flame of a Bunsen burner, and were then arranged to lie across each other, as shown, and were connected to the terminals of the arm of a Wheatstone bridge, the high resistance of the circuit being due to the layers of oxide. Amongst the many measurements made, I found, in one case, a resistance of 80,000 ohms, which, after exposure to the influence of the electric spark, was reduced to 7 ohms. Analogous effects are obtained with oxidised steel rods. Another pretty experiment is to place a cylinder of copper, with an oxidised hemispherical head, on a sheet of oxidised copper. Before exposure to the influence of the electric spark, the oxide offers considerable resistance. The experiment can be repeated several times by merely moving the cylinder from one place to another on the oxidised sheet of copper, thus showing that the phenomenon only takes place at the point of contact of the two layers of oxide.
    It may be worth noting that, for most of the substances enumerated, an elevation of temperature diminishes the resistance, but the effect of a rise of tempera. ture is transient, and is incomparably less than the effect due to currents of high potential. For a few substances the two effects are opposed.
    Restoration of Original Resistance.--The conductivity caused by the various electrical influences lasts sometimes for a long period (twenty-four hours or more), but it is always possible to make it rapidly disappear, particularly by a shock.
    The majority of substances tested showed an increase of resistance on being shaken previous to being submitted to any special electrical influence, but after having been influenced the effect of shock is much more marked. The phenomenon is best seen with the metallic filings, but it can also be observed with metallised ebonite sheets with mixtures of liquid insulators and metallic powders, mixtures of metallic filings and insulating substances (compressed or not compressed), and finally with solid bodies.
    I observed the return to original resistance in the following manner:--
    The sensitive substance was placed at K (fig. 1), and formed part of a circuit which included a Daniell cell and galvanometer. At first no current passes. Sparks are then caused at S, and the needle of the galvanometer is permanently deflected. On smartly tapping the table supporting the ebonite cup in which the sensitive substance is contained, the original condition is completely restored. When the electric action has been of powerful character, violent blows are necessary. I employed for the purpose of these shocks a hammer fixed on the table, the blows of which could be regulated.
    With some substances, when feebly electrified, the return seemed to be spontaneous, although it was slower than the return of the galvanometer needle to equilibrium. This restoration of the original resistance is attributable to surrounding trepidations, as it was only necessary to walk about the room at a distance of a few metres, or to shake a distant wall. This spontaneous return to original resistance after weak electrical action was visible with a mixture of equal parts of fine selenium and tellurium powders. The restoration of resistance by shock was not observable so long as the electrical influence was at work.
    After having been submitted to powerful electric action, shock does not seem to entirely restore substances to their original state; in fact, the substances generally show greater sensitiveness to electric action. Thus, a mixture of colza oil and antimony powder being exposed to the influence of arrangement A, a spark of 5 mm. was at first necessary to break down the resistance; but after the conductivity had been made to disappear by means of blows, a spark of only 1 mm. was sufficient to again render the substance conducting. Finely powdered aluminium has an extremely high resistance. A vertical column of powdered aluminium 5 mm. long of 4 square cms. cross-section, submitted to considerable pressure, completely stopped the current from a Daniell cell. The influence of arrangement A produced no effect, but, by direct contact with a Leyden jar, the resistance was reduced to 50 ohms. The effect of shock was then tried, and after this the sparks produced by arrangement A were able to reduce the resistance.
    The following experiment is also of the same kind: Aluminium filings placed in a parallelipidic trough completely stopped the current from a Daniell cell, and the resistance offered to a single cell remained infinite after the trough had been placed in the circuit of 25 sulphate of mercury cells for 10 seconds. The aluminium was next placed in circuit with a battery of 75 cells; a single Daniell cell was then able to send a current through the substance. The original resistance was restored by shock, but not the original condition of things, since a single cell was able to send a current after the aluminium had been circuited for 10 seconds with a battery of only 25 cells. I may add that if the restoration of resistance was brought about by a violent shock, it was necessary to place the aluminium in circuit with 75 cells for one minute before the resistance was again broken down.
    It must be observed that electrical influence is not always necessary to restore conductivity after an apparent return to the original resistance, repeated feeble blows being sometimes successful in bringing this about. Both in the case of slow return by time and sudden return by shock, the original value of the resistance is often increased. Rods of Carré carbon, 1 metre long and 1 mm. in diameter, were particularly noticeable for this phenomenon.
    Return to Original Resistance by Temperature Elevation.--A plate of coppered ebonite rendered conducting by electricity, and placed close to a gas-jet, quickly regained its original resistance. A solid rod of resin and aluminium, or of sulphur and aluminium, rendered conducting by connection to the poles of a small battery, will regain its original resistance by shock; but if the conducting state has been caused by powerful means, such, for instance, as direct contact with a Leyden jar, shock no longer has any effect, at least such a shock as the fragile nature of the material can stand. A slight rise of temperature, however, has the desired result. By suitably regulating the electric action it is possible to get a substance into such a condition that the warmth of the fingers suffices to annul conductivity. Fig. 5
    Influence of Surroundings.--Electric action gives rise to no alteration of resistance when the substance is entirely within a closed metal box. The sensitive substance, in circuit with a Daniell cell and a galvanometer, is placed inside a brass box (fig. 5). The absence of current is ascertained, the circuit broken, and the box closed. A Wimshurst machine is then worked a little way off, and will be found to have had no effect. The same result will be obtained if the circuit is kept closed during the time the Wimshurst machine is in operation. If a wire connected at some point to the circuit is passed out through a hole in the box to a distance of 20 to 50 cms., the influence of the Wimshurst machine makes itself felt. On tapping the lid to restore resistance, the galvanometer needle remains deflected so long as the sparks continue to pass. If, however, the wires are pushed in so that they only project a few millimetres, the sparks still passing, a few taps suffice to bring back the needle to zero. On touching the end of the wire with the fingers or a piece of metal, conductivity is immediately restored. The movements of the galvanometer needle were rendered visible in these experiments by looking through a piece of wide-mesh wire-gauze with a telescope. The respective position of the things was reversed; that is to say, a Ruhmkorff coil and a periodically discharged Leyden jar were placed inside, and the sensitive substance outside, the box, with the same results.
    In some later experiments with a larger metallic case, and with the Daniell cell, sensitive substance, delicate galvanometer, and Wheatstone bridge placed inside, I found that a double casing was necessary in order to absolutely suppress all effects. A glass covering afforded no protection.
    Considerations on the Mechanism of the Ejects produced.--What conclusions are we to draw from the experiments described? The substances employed in these investigations were not conductors, since the metallic particles composing them were separated from each other in the midst of an insulating medium. It was not surprising that currents of high potential, and especially currents induced by discharges, should spark across the insulating intervals. But as the conductivity persisted afterwards, even for the weakest thermo electric currents, there is some ground for supposing that the insulating medium is transformed by the passage of the current, and that certain actions, such as shock and rise of temperature, bring about a modification of this new state of the insulating body. Actual movement of the metallic particles cannot be imagined in experiments where the particles in a layer a few millimetres thick were fixed in an invariable relative position by extreme pressures, reaching at times to more than 100 kilogrammes per square cm. (1420 lb. to the square inch). Moreover, in the case of solid mixtures, in which the same variations of resistance were produced, displacement seems out of the question. To explain the persistence of the conductivity after the cessation of the electrical influence, are we to suppose in the case of metallic filings a partial volatilisation of the particles creating a conducting medium between the grains of metal? In the case of mixtures of metallic powders and insulating substances agglomerated by fusion, are we to suppose that the thin insulating layers are pierced by the passage of very small sparks, and that the holes left behind are coated with conducting material? If this explication is admissible for induced currents, it must hold good for continuous currents. If so, we must conclude that these mechanical actions may be produced by batteries of only 10 to 20 volts electromotive force, and which only cause an insignificant current to pass. The following experiment is worth quoting in this connection:--
    A circuit was formed by a Daniell cell, a sensitive galvanometer, and some aluminium filings in an ebonite cup. The galvanometer needle remained at zero. The filings were cut out of this circuit, and switched for one minute into circuit with a battery of 43 sulphate of mercury cells. On being replaced in the first circuit, the filings exhibited high conductivity. The result was the same when 10 or 20 cells were employed, or when the current was diminished by interposing in the circuit a column of distilled water, 40 cm. long and 20 mm. in diameter. The cells used (platinum, sulphate of mercury, sulphate of zinc, zinc) had a high internal resistance. Thus, 43 cells (60 volts), when short circuited, only gave a current of 5 milliampères. The same battery, with the column of distilled water in circuit only, caused a deflection of 100 mm. on a scale one metre off, with an astatic galvanometer wound with 50,000 turns. We can, therefore, see how infinitesimally small the initial current must have been when the filings were added to the circuit. The battery acted, therefore, essentially by virtue of its electro-motive force.
    If mechanical displacement of particles or transportation of conducting bodies seem inadmissible, it is probable that there is a modification of the insulator itself, the modification persisting for some time by virtue of a sort of "coercive force." An electric current of high potential, which would be completely stopped by a thick insulating sheet, may be supposed to gradually traverse the very thin dielectric layers between the conducting particles, the passage being effected very rapidly if the electric pressure is great, and more slowly if the pressure is less.
    Increase of Resistance.--An increase of resistance was observed in these investigations less often than a diminution; nevertheless, a number of frequently repeated experiments enable me to say that increase of resistance is not exceptional, and that the conditions under which it takes place are well defined. Short columns of antimony or aluminium powder, when subjected to a pressure of about 1 kilogramme per square cm. (14·2 lb. per square inch), and offering but a low resistance, exhibited an increase of resistance under the influence of a powerful electrification. Peroxide of lead, a fairly good conductor, always exhibited an increase, so also did some kinds of platinised glass, while others showed alternate effects. For instance, a sheet of platinised glass, which offered a resistance of 700 ohms, became highly conducting after 150 sulphate of mercury cells had been applied to it for 10 seconds. This condition of conductivity was annulled by contact with a charged Leyden jar, and reappeared after again applying 150 cells for 10 seconds, and so on. Similar effects were obtained with a thin layer of a mixture of selenium and tellurium poured, when fused, into a groove in a sheet of mica placed between two copper plates. These alternations were always observed several times in succession, and at intervals of several days.
    These augmentations and alternations are in no way incompatible with the hypothesis of a physical modification of the insulator by electrical influence.

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    1 Based on reports in the (London) 'Electrician,' June 26 and August 21, 1891.
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