CN1149354A - Telecommunications gas tube apparatus and composition for use therewith - Google Patents

Telecommunications gas tube apparatus and composition for use therewith Download PDF

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Publication number
CN1149354A
CN1149354A CN95193320A CN95193320A CN1149354A CN 1149354 A CN1149354 A CN 1149354A CN 95193320 A CN95193320 A CN 95193320A CN 95193320 A CN95193320 A CN 95193320A CN 1149354 A CN1149354 A CN 1149354A
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China
Prior art keywords
composition
colloid
ohm
flue
voltage
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CN95193320A
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Chinese (zh)
Inventor
W·H·塞门迪格二世
R·E·莫顿
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Raychem Corp
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Raychem Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J17/00—Gas-filled discharge tubes with solid cathode
    • H01J17/38—Cold-cathode tubes
    • H01J17/40—Cold-cathode tubes with one cathode and one anode, e.g. glow tubes, tuning-indicator glow tubes, voltage-stabiliser tubes, voltage-indicator tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/12—Overvoltage protection resistors
    • H01C7/126—Means for protecting against excessive pressure or for disconnecting in case of failure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/12—Overvoltage protection resistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01T—SPARK GAPS; OVERVOLTAGE ARRESTERS USING SPARK GAPS; SPARKING PLUGS; CORONA DEVICES; GENERATING IONS TO BE INTRODUCED INTO NON-ENCLOSED GASES
    • H01T1/00—Details of spark gaps
    • H01T1/14—Means structurally associated with spark gap for protecting it against overload or for disconnecting it in case of failure

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • External Artificial Organs (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Organic Insulating Materials (AREA)

Abstract

A telecommunications gas tube apparatus (40) which is suitable for connection to a gas discharge tube (12) and which comprises an electrically non-linear resistive element (45) prepared from an electrically non-linear composition which comprises a polymeric component and a particulate filler. The composition has an initial resistivity rho i at 25 DEG C of at least 10<9> ohm-cm, and is such that a standard device containing the composition has an initial breakdown voltage VSi, and after the standard device has been exposed to a standard impulse breakdown test, the device has a final breakdown voltage VSf which is from 0.7VSi to 1.3VSi. In addition, the composition in the device has a final resistivity rho f at 25 DEG C of at least 10<9> ohm-cm. Such compositions are useful in providing both vent-safe and fail-safe protection to a gas discharge tube.

Description

The composition of telecommunications flue device and use thereof
Invention scope
The present invention relates to be used for the gas discharge pipe unit and the composition that uses at this device of telecommunication apparatus.The present invention introduces
Gas discharge tube generally is used to protect telecommunication apparatus and circuit, suffers damage under electrical Interference or high-tension electricity flash pulsing avoiding.The flue of this purposes is called the flue protector usually.This pipe contains a kind of gas, and it under high pressure is ionized, and makes the direct ground connection of current impulse, thereby it is minimum that the infringement that causes because of pulse is reduced to.If when having a lasting high electric current overload to take place, for example the power line accident is bumped and connect, these pipes are just kept limited ionization so.
In order to prevent during continuing overcurrent will to guarantee simultaneously that because of the overheated fault that causes ionizable gas does not overflow this pipe, the flue protector has " error protection " and " ventilate and protect " mechanism usually." error protection " refers to the protection of heat damage, normally provided by a kind of fusible metal or plastics.If plastics are heated because of the energy of current overload, it can be subjected to bias voltage short circuit member shadow to and around flue, provide a permanent current along separate routes.This can by fusion place two between the electrode thermoplastic film and cause, thereby allow the contact of two electrodes make current bypass ground connection." ventilate to protection " refers to standby overvoltage protection, and it works in that gas " overflows " or when elapsing atmosphere.The protection of ventilating is normally provided by an air gap, and this air gap is the part of this pipe external structure.Choosing of air gap ratio is to exceed an igniting potential energy in fact, for example is the twice of the normal ignition potential energy of flue own, makes under normal circumstances flue can prevent that air gap from lighting.So choose the damage chance that can make air gap reduce to minimum, although, may hurt the air gap that is used as safeguard protection because the igniting the during flue of overvoltage pulse by a normal operation is normally harmless.
In order to improve the ventilate reliability of protection design of air gap, from environment, air gap is completely cut off usually, to prevent by moisture, air pollution, insects or infringement that other environmental factors were caused.Yet its effectiveness is limited usually for encapsulant such as package agent, sealed compound, conformal coating and colloid etc., because they generally all can't limit moisture and enter, they self can see through air gap and change the voltage discharge potential and/or be directed at corrosion simultaneously.Short circuit current when the attenuating of discharge voltage current potential may cause low voltage potential; The rising of discharge voltage current potential then can make the air gap protection lose efficacy.
Proposed to substitute air gap with one deck solid material at some problem in these problems, this solid material has special nonlinear resistance coefficient feature.An air gap like this proposes in No. the 08/046th, 059, the U.S. patent application case of common pending trial people such as (, application on April 10th, 1993) Debbaut, and this application case content is incorporated in this paper for your guidance.Though this solid material is stable to environment, puncture voltage is reduced, and in fact in the normal work period of an electrion, high energy pulse such as lighting can cause the breaking-up of solid material itself.What is more, is not that all these class air gaps can both provide the effect that destroys protection.Brief summary of the invention
Find; if a non-linear electric component is made by a nonlinear electrical material; and this material has special electrical property through the voltage breakdown test; then use the alternative U.S. patent application case the 08/046th of this electric component; solid material gap disclosed in No. 059, and can make a flue device and make it to have simultaneously ventilate protection and error protection characteristic.In addition because the characteristic of this nonlinear material with and physics and electric stability during the continuous electric gaseity, this device can intensify and this non-linear element of unlikely destruction under general telecommunications service condition repeatedly.Reduce owing to replace the demand of this element, so the reliability of telecommunication system increases maintenance cost decline.In a preferred embodiment, this material comprises a kind of colloid, and this colloid can cooperate the flue protective device, reduces moisture and invades chance, and allow bigger manufacturing tolerance.In addition, colloid and colloid encapsulating material can be compatible, thereby help environmental sealing.
At first, the invention provides a kind of telecommunications flue device, it comprises:
(1) first electrode, power supply is connected to first terminal on the gas discharge tube;
(2) second electrodes, power supply is connected to second terminal on this flue; And
(3) nonlinear resistive elements, it separates first and second electrodes, and this element comprises
A kind of non-linear electric composition, its
(a) comprise (i) a kind of polymer composition, and (ii) a kind of particular fillers,
(b) has an initial resistance coefficient ρ i, it is 10 in the time of 25 ℃ at least 9Ohm-
Centimetre, and
(c) has an initial breakdown voltage when a normal component that comprises said composition
V Si, and after this normal component is subjected to a calibration pulse puncture test, this device
Part has a scope 0.7 to 1.3V SiBetween final puncture voltage V Sf,
The final resistance coefficient ρ of the composition in this device simultaneously fIn the time of 25 ℃ at least
Be 10 9Ohm-cm.
Secondly, the invention provides a kind of telecommunications flue device, it comprises:
(1) first electrode, power supply is connected to first terminal on the gas discharge tube;
(2) second electrodes, power supply is connected to second terminal on this flue; And
(3) nonlinear resistive elements, it separates first and second electrodes, and this element comprises
A kind of non-linear electric composition, its
(a) colloid that comprises (i) whole composition volume 30 to 95%, and (ii) whole combination
The special conductive filler of object long-pending 5 to 70%; And
(b) has an initial resistance coefficient ρ i, it is 10 in the time of 25 ℃ at least 9Ohm-
Centimetre.
The 3rd, the invention provides a kind of assembly, it comprises:
(A) retaining element; And
(B) the present invention's first telecommunications flue device that is proposed above is inserted in the said fixing element.
The 4th, the invention provides a kind of nonlinear resistance composition on electric.Its pattern such as the present invention be the explanation in first above.
Brief description
Fig. 1 is that typical three element gas discharge tube joins the schematic diagram in a pair of telecommunication line;
Fig. 2 is the cutaway view of Fig. 1 flue;
Fig. 3 is the exploded view of flue device of the present invention;
Fig. 4 is the cutaway view of the flue device in the inclosure colloid of the present invention;
Fig. 5 is the exploded view of assembly of the present invention;
Fig. 6 is the cutaway view of Fig. 5 assembly;
Fig. 7 is the schematic diagram for the normal component of testing composition of the present invention;
Fig. 8 is a pulse breakdown curve, with the function representation of volt as the pulse test cycle;
Fig. 9 and Figure 10 are the pulse breakdown curves, the function representation of the interelectrode distance of using as each composition of the present invention with volt; And
The curve chart of Figure 11 interelectrode distance function that to be dc breakdown voltage and pulse breakdown voltage use as each composition of the present invention.
Detailed description of the present invention
Flue device of the present invention and assembly all comprise a nonlinear resistive element, and this nonlinear resistive element comprises a kind of non-linear electric composition.In the present invention, " non-linear " one language refers to that said composition belongs to electrical insulator basically on electric property, just has greater than 10 during less than its pulse breakdown voltage when applied voltage 9The resistance coefficient of ohm-cm, but just become electric conductor subsequently, that is when applied voltage is equal to or greater than pulse breakdown voltage, have less than 10 9The resistance coefficient of ohm-cm.This non-linear electric composition comprises a polymer composition and a particular fillers.This polymer composition can be any suitable polymers, the thermoplastic of polyolefin or fluoropolymer for example, or such as thermosets, synthetic rubber, lubricating grease or the colloid of epoxy resin.30 to 95% of the normally whole composition volume of polymer component content, preferably 35 to 90%, particularly 40 to 95%.
In many application, the polymer composition preferably comprises a kind of polymeric colloid, just a kind of crosslinker solution that has diluted basically, and this solution is immobilising under stable state.Its cross-bond provides a kind of continuity network configuration, and this structure is formed by entity or chemical bond, crystallinity or other connected modes, and must be kept perfectly under the colloid operating position.Most of colloid comprises a kind of polymer of mobile expansion, and wherein the fluid of oil and so on for example can be inserted the space in the network.The colloid that is suitable for comprises the material that contains silicone, for example poly organo methane series, polyamine base Ethyl formate, polyureas, Styrene-Butadiene, styrene-isoprene copolymer, styrene-(commodity are called Septon to (ethylene/propene)-styrene (SEPS) block copolymer TM, by the supply of Kuraray company), styrene-(commodity are called Septon to (ethylene-propylene/ethene-butylene)-styrene block copolymer TM, by the supply of Kuraray company), and/or styrene-(commodity are called Kraton to (ethylene/butylene)-styrene (SEBS) block copolymer TM, by the supply of Shell Oil company).The expansion fluid that is suitable for comprises for example for example three beeswax esters or above various mixture of paraffin oil, silicone oil, plasticizer of mineral oil, vegetable oil, and general content is 30 to 90% of whole colloid weight.Colloid can be thermosetting cement style such as silicone colloid, and wherein the formation of cross-bond is to reach by the crosslinking agent that uses many effects; Or the thermoplasticity colloid, wherein interregional microphase-separated point is as tie point.Disclosed the colloid that can be used as polymer composition in the composition and be found in United States Patent (USP) the 4th, 600, No. 261 (Debbaut), the 4th, 690, No. 831 (people such as Uken), the 4th, 716, No. 183 (people such as Gamarra), the 4th, 777, No. 063 (people such as Dubrow), the 4th, 864, No. 725 (people such as Dubbaut), the 4th, 865, No. 905 (people such as Uken), the 5th, 079, No. 300 (people such as Dubrow), the 5th, 104, No. 930 (people such as Rinde), and the 5th, 149, No. 736 (Gamarra); Also have international monopoly to announce people such as () Toy WO86/01634 number, WO88/00603 number people such as () Francis, WO90/05166 number (Sutherland), WO91/05014 number (Sutherland) and WO93/23472 number people such as () Hammond.More than the content of each patent and bulletin all to be incorporated in this paper for reference.
The Voland hardness of colloid is preferably 1 to 50 gram, more preferably 5 to 25 grams, preferably 6 to 20 grams; Stress relaxation is 1 to 45%, more preferably 15 to 40%; And viscosity is 5 to 40 grams, more preferably 9 to 35 grams; Best ductility is at least 50%, and more preferably at least 100%, be that at least 400%, at least 1000% is better well again, be preferably at least 1500%.Ductility is measured according to ASTM D217, and this explanation is also for reference in this paper.Voland hardness, stress relaxation and viscosity are to use a kind of fabric analysis instrument of Voland-Stevens LFRA type to measure, it has one 1000 gram load container, the starter of one 5 gram, and the spherical probes of 0.25 inch (6.35 millimeters), as (people such as Dubrow) United States Patent (USP) the 5th, 079, No. 300 described, and its content is also for reference in this paper.In order to measure the hardness of colloid, one 20 milliliters glass scintillation bottle includes the colloids of 10 grams, be placed in the analyzer, and the stainless steel ball probe is pressed into colloid with the speed of 0.20 mm/second, to penetration range be 4.0 millimeters.The Voland hardness number is to drive the required power with the gram expression of 4.0 millimeters distances that spherical probes is gone to penetrate colloid surface with above-mentioned speed or made it deformation characteristic.The Voland hardness of a specific colloid directly and use the ASTM D217 cone penetration hardness of the 4th, 852, No. 646 described programs of United States Patent (USP) such as (Dittmer people) relevant, it illustrates also and is for reference in this paper.
In composition, except the polymer composition, also comprise a kind of particular fillers.This filler can be conductivity, semiconduction, non-conductive filler or above two or more mixture, as long as make final composition have suitable non-linear electrical properties.It is good generally with filler conductivity or semiconduction being arranged.Though resistance coefficient is the function of dopant material, temperature and other factors, and its value may be higher than 10 in fact 3Ohm-cm, but the resistance coefficient that electroconductive stuffing generally has is at most 10 -3Ohm-cm; The semiconduction filler then generally has 10 at the most 3Ohm-cm.Appropriate filler comprises metal dust, such as aluminium, nickel, silver, silver-plated nickel, platinum, copper, tantalum, tungsten, gold and cobalt; Metal oxide powder is such as iron oxide, add the iron oxide of doping, the zinc oxide that adds the titanium dioxide of doping and add doping; Metal carbide powders is as carborundum, titanium carbide and ramet; The metal nitride powder; The metal boride powder; Carbon black or graphite; Also has alloy, such as brass and bronze.Good especially filler has aluminium, iron oxide (Fe 3O 4), be doped with iron oxide, carborundum and the silver-plated nickel of titanium dioxide.If the polymer composition is a colloid, the most important thing is that then selected filler can not cause interference with colloid crosslinked, does not just make colloid " poisoning ".Amount of filler generally accounts for 5 to 70% of whole composition volume, with 10 to 65% preferable, and preferably 15 to 60%
The volume load of filler, shape and size have influence on the non-linear electrical characteristic of composition, in part because have due to the space between particle.The particle of Any shape can use, for example spherical, sheet, fibrous or weldering shape.The composition that share can be 0.010 to 100 micron particle manufacturing with mean size, with 0.1 to 75 micron preferable, better, and best with 0.5 to 50 micron with 1 to 20 micron.The granulate mixture of different sizes, shape and/or kind also can use.Particle can carrying magnetic or carrying magnetic not.
Except particular fillers, said composition also can comprise other known additives, comprises stabilizer, pigment, crosslinking agent, catalyst and retardant.
Composition of the present invention can be made with any suitable method, for example metal fusion, solvent mix or intensive mixing; And can be shaped with known method, comprise extrusion modling, calendering formation, casting and compression molded.If component of polymer is a kind of colloid, then colloid can mix to stir with filler, and said composition can be watered or cast on substrate or solidified in the mould again, carries out with mode of heating usually.
Composition among the present invention has splendid stability, and it is measured with resistance coefficient and puncture voltage.These compositions are electric on-insulated, its initial resistance coefficient ρ iIn the time of 25 ℃, be at least 10 9Ohm-cm is with 10 10Ohm-cm is preferable, and 10 11Ohm-cm is better, and with 10 12Ohm-cm the best.Initial resistance coefficient value ρ iBe when said composition forms hereinafter described normal component, should make initial insulation resistance R iBe at least 10 9Ohm is with at least 10 10Ohm is preferable, and at least 10 11ρ when ohm is better iValue.When composition of the present invention is used for telecommunication installation, R iValue at least 10 9Ohm is good.When carrying out calibration pulse puncture test as described below, final resistance coefficient ρ fIn the time of 25 ℃, be 10 at least 9Ohm-cm, and ρ fTo ρ iRatio be 1 * 10 at the most 3, with at the most 5 * 10 2For good, at the most 1 * 10 2Better, at the most 5 * 10 1Better again, and at the most 1 * 10 1Best.To a normal component, final insulation resistance R fBe subjected to being at least 10 when calibration pulse punctures test 9Ohm, at least 10 10Ohm is preferable, and with at least 10 11Ohm is best.
When composition of the present invention was subjected to calibration pulse puncture test by a following narration normal component of formation, this device had an initial breakdown voltage (V Si) and a final puncture voltage (V Sf), V SfBe 0.7V SiTo 1.3V Si, with 0.80V SiTo 1.20V SfFor good, and 0.85V SiTo 1.15V SiBetter, 0.90V SiTo 1.10V SiThen best.Breakdown voltage value mainly be subjected to particular fillers percent volume to volume, granular size, grain spacing from etc. factor affecting.Usually, puncture voltage increases when particle size reduces.
Some composition can " breech lock (latch) " among the present invention, and just after the primary voltage discharge, its resistance coefficient is less than 10 6Ohm-cm and remain on conduction state.If this breech lock device is to be made by the composition that comprises colloid, then this device can " reset " a high resistivity state, just at least 10 9A resistance coefficient of ohm-cm, this resets is by means of the entity distortion, for example deflection, distortion, compression or the realization that stretches.The breech lock action is the function of granular size, intergranular space and grain shape.In colloid, generally be little spherical particle, as 1 to 5 micron, have little intergranular space, as less than 4 microns, understand breech lock.
Under some electric condition, composition of the present invention particularly contains the composition of aluminium, and failure protection function can be provided.If be subjected to an enough high-octane influence, for example 30 amperes and 1,000 volt are lasted 2 seconds to 30 minutes, then this particular fillers may merge and provide a permanent conductive path between electrode, thereby producing a final resistance, it is worth less than 10 ohm, for example 1 to 10 milliohm.This action has its needs when the power line short, and causes a permanent short circuit.
The present invention is to illustrate, and wherein Fig. 1 is the schematic diagram of a known telecommunication circuit 10, and this circuit has comprised flue 12 on a telecommunication line.This pipe represents with cutaway view that in Fig. 2 one first terminal 16 and one second terminal 17 are wherein arranged, for top margin 13 that is connected to telecommunication circuit respectively and ring limit 14.In addition, flue 12 has a centre-point earth terminal 18.A ceramic package 19 is sealed ionizable gas 20, the ionization and form discharge plasma under certain voltage of this gas.
Fig. 3 is an exploded view of a flue device 40 of the present invention.In the present embodiment, first terminal 16 of flue 12 and second terminal 17 also play a part first and second electrodes in the flue device 40 respectively.Though (be not shown among the figure, this flue can comprise one the 3rd terminal, and it can be connected on the third electrode of flue device.One of electrode can be a grounding electrode.) position of nonlinear resistive element 45 contacts with first terminal 16 and second terminal 17.Grounding electrode 55 contacts with resistive element 45 entities and the grounding terminals 18 of flue 12 is and electrically contacts.In a preferred embodiment, the nonlinear combination thing that comprises this resistive element has enough flexibilities, to adapt to the shape of flue 12.
Fig. 4 is flue device 40 cutaway view of colloid after enclosing in the agent 50 of packing into.This inclosure agent can be for example sealed compound, a kind of conformal coating agent or a kind of colloid, and it provides the environmental protection of blocks moisture or other pollutants.In addition, this inclosure agent can be got rid of the plasma discharge of oxygen, and as a radiator heat energy is shed from hot localised points.Preferably this resistive element has chemical stability to enclosing agent.
Fig. 5 is the exploded view of assembly 70 of the present invention, and Fig. 6 then is the cutaway view of this assembly.Retaining element 72 is designed to be used for air inclusion pipe 12, resistive element 45 and a grounding electrode 55 '.Though resistive element 45 can be as shown laminar, for strengthening and the contacting of flue 12, this element can be bending or be other shapes. Spring guide card 76 and 78 is attached on the flue 12, is used for substituting with each insulation that the connector (not shown) is electric to be contacted.Flue 12 keeps suitably location by retaining element 72, fixed cap 74 and ground connection pin 80 with resistive element 45 and grounding electrode 55 ', in ground connection pin 80 grooves or hole that can insert on the fixed cap 74.Fixed cap 74 can weld with ultrasonic waves, bonding or other modes are fused on the retaining element 72.In order to keep that suitable distance is arranged between flue 12 and grounding electrode 55 ', at grounding electrode 55 ' upper process spacer 56, it highly can be chosen to reach the voltage breakdown of varying level.Retaining element 72 usefulness are enclosed agent and are filled with around its inclusion.
The present invention can illustrate with following example: example 1 to 14
The listed composition of table 1 is mixed with a tongue piece button disperses particular fillers, removes gas 1 minute then in a vacuum furnace, pours into a slice again and scribbles on the separating plate of polytetrafluoroethylene (PTFE) and harden.A normal component as described below has 1 millimeter electrode spacing.Each sample all stands in three tests once, although wherein some sample will be accepted the calibration pulse in 5 to 100 cycles and punctures test.Its result is presented on Fig. 8 to Figure 11, and the result points out, when above, has splendid stability and reproducibility for pulse breakdown and insulation resistance 100 cycles based on the composition of silicone colloid 1 and thermoplasticity colloid.Based on the composition of silicone colloid 2, its insulation resistance is reduced to less than 10 to about 41 cycles the time 5Ohm.Compositions display based on the silicone grease has the similarly reduction (Fig. 8) to 4 cycles the time.Example 5 is based on a kind of epoxy resin, is pulverized under the pulse test condition, and insulation resistance reduces to 15 cycles the time but demonstrate in the dc breakdown test.Fig. 9 and 10 demonstrates the influence of particle size and filler load paired pulses puncture voltage, and each sample thickness is from 0.25 to 1.0 millimeter.Figure 11 demonstrates under certain particle size and load, and pulse breakdown and dc breakdown voltage are suitable.Normal component
The circular sample that 11.2 millimeters (about 1 square centimeter of surface area) thickness of a diameter are 1 millimeter is to cut out from the composition of sclerosis, and puts into testing equipment, and the section of this equipment is shown in Fig. 7.The composition sample 90 of being tested is placed between two circular aluminium electrodes 91 and 92, and the diameter of each electrode all is about 11.2 millimeters, about 100 square millimeters of the contact area of its surface and composition 90.The slightly larger in diameter of polycarbonate cannula 93 is in 11.2 millimeters, be placed on the electrode and composition after the assembling, and this assembly put into the equipment 94 that comprises support component 95 and 96.It is 1 millimeter that adjustment micrometer 97 makes the distance between electrode 91 and 92.(for the pulse breakdown test of following correction, adjust micrometer and make it from 0.25 to 1.00 millimeter to change electrode spacing, this spacing is sample thickness just.As for each colloid sample, its initial thickness is 1 millimeter.When adjusting micrometer and reduce thickness of sample, the surplus composition opening 98 in the electrode 94 of flowing through, and flow between electrode 91,92 and the Merlon sleeve 93.) calibration pulse puncture test
Volume is that 1 square centimeter * 1 millimeter normal component is put into testing apparatus as shown in Figure 7.The insulated electro group R of this device before the test iUnder 25 ℃ and 50 volts of bias voltages, utilize the test of a Genrad 1863 megohm testers, and calculate its initial resistance coefficient ρ iThis of device insertion is had in the circuit of pulse generator, and all there is a high energy pulse in each cycle, and its waveform is 10 * 1, (time that promptly is raised to maximum voltage is 10 microseconds to 000 microsecond, and the time that rises to half height be 1,000 microsecond), to add electric current be at most 1 ampere in institute.Measured crest voltage on this device during puncture, that is the voltage when electric current begins to flow through colloid write down as pulse breakdown voltage.Puncture test for calibration pulse, then carry out the test in 5 cycles.The final insulated electro group R of 5 all after dates of measurement standard test f, and calculate its final electricity group coefficient ρ fThe pulse breakdown test of revising
Prepare sample, after calibration pulse punctures the program of test, make variation from 0.25 to 1 millimeter of the electrode spacing and test.The dc breakdown test
A normal component is put into circuit and apply a voltage (Hipot M1000 type DC test device) that increases with 200 volts/seconds speed.When 5 milliamperes of electric currents begin to flow through this device, the volt of record dc breakdown.
Table I
Example Polymer Al filler Test ??R i??(Ω) ??R f??(Ω) Test period
Size (μ m) Volume %
??1 Silicone colloid 1 ????20 ??40.0 ??I1 ??10 12 ????10 12 ????100
??2 The thermoplasticity colloid ????20 ??35.1 ??I1 ??10 12 ????10 12 ????100
??3 Silicone oil ????20 ??26.4 ??I1 ??10 12 ??＜10 5 ????4
??4 Silicone colloid 2 ????20 ??40.0 ??I1 ??10 10 ??＜10 5 ????46
??5 Epoxy resin ????20 ??26.4 ??D * ??10 10 ??＜10 5 ????15
??6 Silicone colloid 1 ????1-5 ??45.6 ??I2.D
??7 Silicone colloid 1 ????1-5 ??40.0 ??I2
??8 Silicone colloid 1 ????1-5 ??35.1 ??I2
??9 Silicone colloid 1 ????1-5 ??26.4 ??I2
??10 Silicone colloid 1 ????20 ??45.6 ??I2.D
??11 Silicone colloid 1 ????20 ??35.1 ??I2
??12 Silicone colloid 1 ????20 ??26.4 ??I2
??13 Silicone colloid 1 ????20 ??19.3 ??I2
??14 Silicone colloid 1 ????20 ??13.3 ??I2 **
The explanation of Table I:
Silicone colloid 1 is a mixture, and 0.8 part first composition is wherein arranged, and first composition is 26% Nusil Ply by percentage by weight TMThe dimethyl silicone polymer of the divinyl terminal of 7520 CS 170 (by the McGhan-Nusil supply), 73.88% Carbide L45/50 CS dimethyl silicone polymer silicone fluid diluent (by Union Carbide supply), 0.1% Nusil Cat TM50 catalyst (3 to 4% platinum is placed in the silicone oil, by the McGhan-Nusil supply) and 0.02%T2160 inhibitor (1,3,5,7-tetrem thiazolinyl tetramethyl-ring tetrasiloxane is by the Huls supply) are formed; Other has 1.0 parts second composition, and second composition is 26% Nusil Ply by percentage by weight TM7520 CS, 170 dimethyl silicone polymers, 73.91%CarbideL45/50 CS silicone fluid diluent and 0.9%T1915 four dimethyl silica silane crosslinkers (by the Huls supply) are formed.
It is 10% Septon that the thermoplasticity colloid comprises percentage by weight TM4055 styrene-(ethylene/propene)-styrene block copolymer, it has the mid-block of an ethylene/propene and 308,000 molecular weight (by the Kuraray supply), 87.5% Witco TM380 expand the Irganox of oil (by the Witco supply) and 1% TMB900 antioxidant (by the Ciba-Geigy supply).
Silicone oil is the mixture of the silicone oil of silicon dioxide and 50cst, wherein SiO 2Be added to silicone oil till no longer flowing under its deadweight always.
Silicone colloid 2 is SylGard TMThe silicone dielectric colloid of Q3-6636 (by Dow Corning supply).
Epoxy resin is ACE TM18612 5-divide epoxy resin (by Ace Hardware Stores supply).
The mean particle size of aluminium powder is 20 microns, is roughly spherically, and its product type is 26651, is supplied by Aldrich Chemicals.
The mean particle size of aluminium powder is 1 to 5 micron (by 325 purpose nets), is roughly spherically, and its product type is 11067, is supplied by Johnson Mathey.
The accurate pulse breakdown test of I1 index.
I2 refers to that corrected impulse punctures test.
D refers to the dc breakdown test.Example 15 to 18
Determine whether each composition remains conduction state among the present invention after the voltage discharge, must preparation have the normal component of listing in these compositions in the table 2.The measurement of its initial resistance is to carry out before this device is subjected to the primary voltage discharge of aforesaid standards pulse breakdown test-types.Then measure final resistance after the discharge.If final resistance is less than 10 5Ohm, then device is regarded as by breech lock.Intergranular about space utilizes formula λ=4 (1-f) r/ (3f) to calculate, and wherein going into is mean free path (being the particle interval), and f is a particle volume percentage, and r is a particle radius.Whether composition is that the breech lock attitude was both relevant with granular size, also relevant with particle load.20 microns aluminium is breech lock when having higher particle at interval.Clearly, though particle is roughly sphere on average, be not that all particles are all spherical in shape fully.
Table II
Example Polymer Al filler Breech lock The particle interbody spacer is gone into (μ m)
Size (μ m) Volume %
??15 The silicone colloid ????1-5 ????26.4 Not ????5.6
??16 The silicone colloid ????1-5 ????35.1 Be ????3.7
??17 The silicone colloid ????20 ????35.1 Not ????24.6
??18 The silicone colloid ????20 ????45.6 Be ????15.9

Claims (10)

1. nonlinear resistance composition, its
(a) comprise (i) a kind of polymer composition, and (ii) a kind of particular fillers,
(b) has an initial resistance coefficient ρ i, it is 10 in the time of 25 ℃ at least 9Ohm-cm, and
(c) has an initial breakdown voltage V when a normal component that comprises said composition Si, and after this normal component was subjected to a calibration pulse puncture test, this device had a scope at 0.7V SiTo 1.3V SiBetween final puncture voltage V Sf, the final resistance coefficient ρ of the composition in this device simultaneously fIn the time of 25 ℃, be 10 at least 9Ohm-cm.
2. according to the composition of claim 1, polymer composition wherein comprises colloid.
3. according to the composition of claim 2, colloid wherein is a kind of thermosetting colloid or a kind of thermoplasticity colloid.
4. according to the composition of claim 1, particular fillers wherein comprises conductivity or semiconduction colloid.
5. according to the composition of claim 4, particular fillers wherein is by choosing in the group that comprises metal dust, metal oxide powder, metal carbide powders, metal nitride powder and metal boride powder.
6. according to the composition of claim 5, particular fillers wherein comprises aluminium, nickel, silver, silver-plated nickel, platinum, copper, tantalum, tungsten, iron oxide, the iron oxide that adds doping, the zinc oxide that adds doping, carborundum, titanium carbide or ramet.
7. according to the composition of claim 1 or 2, V wherein SfBe 0.8V SiTo 1.2V Si
8. according to the composition of claim 1 or 2, ρ wherein iTo ρ fRatio be at most 10 3
9. according to the composition of claim 1 or 2, initial resistance coefficient ρ wherein iAt least be 10 11Ohm-cm.
10. according to the composition of claim 1 or 2, particular fillers wherein is roughly sphere.
CN95193320A 1994-06-01 1995-05-30 Telecommunications gas tube apparatus and composition for use therewith Pending CN1149354A (en)

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CN101958540A (en) * 2009-07-20 2011-01-26 奥宝贝特曼股份有限两合公司 Surge arrester
CN105762762A (en) * 2016-05-13 2016-07-13 深圳市槟城电子有限公司 Circuit protection device

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ES2133124B1 (en) * 1994-05-04 2000-04-01 Cymem S A IMPROVEMENTS INTRODUCED IN THE PATENT OF INVENTION P-9400938/4, BY: EXTERNAL SHORT CIRCUIT DEVICE FOR PROTECTION MODULES OF TELEPHONE AND SIMILAR EQUIPMENT.
IL117529A0 (en) * 1995-03-22 1996-07-23 Raychem Corp Button protection device
US6251513B1 (en) * 1997-11-08 2001-06-26 Littlefuse, Inc. Polymer composites for overvoltage protection
SE9704824D0 (en) * 1997-12-22 1997-12-22 Asea Brown Boveri Fiber composite articles and method for making such composite articles
US7258819B2 (en) 2001-10-11 2007-08-21 Littelfuse, Inc. Voltage variable substrate material
JP2006012492A (en) * 2004-06-23 2006-01-12 Shinko Electric Ind Co Ltd Discharge tube
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TW211079B (en) * 1992-06-30 1993-08-11 Raychem Corp Gas tube vent-safe device

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Publication number Priority date Publication date Assignee Title
CN101958540A (en) * 2009-07-20 2011-01-26 奥宝贝特曼股份有限两合公司 Surge arrester
CN101958540B (en) * 2009-07-20 2014-10-22 奥宝贝特曼股份有限两合公司 Surge arrester
CN105762762A (en) * 2016-05-13 2016-07-13 深圳市槟城电子有限公司 Circuit protection device
CN105762762B (en) * 2016-05-13 2024-05-03 深圳市槟城电子股份有限公司 Circuit protection device

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FI964764A0 (en) 1996-11-29

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