DE4032062A1 - Prodn. of voltage-dependent ceramic composite - using self-hardening reactive monomer binder, pref. isocyanate - Google Patents

Prodn. of voltage-dependent ceramic composite - using self-hardening reactive monomer binder, pref. isocyanate

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Publication number
DE4032062A1
DE4032062A1 DE4032062A DE4032062A DE4032062A1 DE 4032062 A1 DE4032062 A1 DE 4032062A1 DE 4032062 A DE4032062 A DE 4032062A DE 4032062 A DE4032062 A DE 4032062A DE 4032062 A1 DE4032062 A1 DE 4032062A1
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DE
Germany
Prior art keywords
voltage
pref
mixed
self
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
DE4032062A
Other languages
German (de)
Inventor
Claus Thomas
Walter Kleinsteuber
Thomas Fleischmann
Gunter Opelt
Birgit Serfling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HERMSDORF KERAMIK VEB
Original Assignee
HERMSDORF KERAMIK VEB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HERMSDORF KERAMIK VEB filed Critical HERMSDORF KERAMIK VEB
Priority to DE4032062A priority Critical patent/DE4032062A1/en
Publication of DE4032062A1 publication Critical patent/DE4032062A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63456—Polyurethanes; Polyisocyanates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)

Abstract

A voltage-dependent ceramic composite material (I) is produced using a self-hardening reactive monomer binder, pref. isocyanate. Specifically, the reactive monomers are mixed with dry, finely powdered multilayer minerals, pref. kaolinite or mixed-layer to a bonding mass. Amts. of the basic substance, pref. SiC are mixed with amts. of the bonding mass in a ratio of 4-1:1-10. USE/ADVANTAGE - (I) are used as components in overvoltage protection devices and semiconductors. (I) has high dimensional stability, high temp. stability (greater than 220 deg.C), high voltage strength, tracking resistance, good mechanical load-bearing capacity. (0/0)

Description

Anwendungsgebiet der ErfindungField of application of the invention

Die Erfindung bezieht sich auf ein Verfahren zur Herstellung eines spannungsabhängigen Verbundwerkstoffes mit chemischer Bindung der Werkstoffkomponenten unter Einsatz eines selbsthärtenden Bindemittels. Vorrangig wird dieser Werkstoff zur Herstellung von Bauteilen der Überspannungsschutztechnik sowie der Halbleitertechnik eingesetzt.The invention relates to a process for the preparation a voltage-dependent composite with chemical Bonding of the material components using a self-curing binder. This material is primarily used for Production of components of surge protection technology and the semiconductor technology used.

Charakteristik des bekannten Standes der TechnikCharacteristic of the known state of the art

Es ist bekannt, spannungsabhängige Werkstoffe durch herkömmliche Formgebungsverfahren, sowie anschließendes Sintern bei Temperaturen über 1000°C, aber auch durch Mischen von Kunstharzen oder anderen Polymeren, entsprechender Formgebung und anschließendem Aushärten herzustellenden beziehungsweise zu verarbeiten (DE 21 56 700).It is known, voltage-dependent materials by conventional Shaping process, followed by sintering at Temperatures over 1000 ° C, but also by mixing of synthetic resins or other polymers, appropriate shaping and subsequent hardening to produce or to process (DE 21 56 700).

Nachteile der keramischen Sinterverfahren sind der hohe technische Aufwand, insbesondere die hohen Energiekosten, eine begrenzte Maßhaltigkeit, sowie die Sprödigkeit der hergestellten Endprodukte. Die Verwendung von Polymeren als Bindemittel erfordert einen hohen Aufwand zur Realisierung der Forderungen des Gesundheits-, Arbeits- und Umweltschutzes, hohe materielle Aufwendungen (Kosten der Polymere, Ausrüstungen) und gewährleistet im allgemeinen keine ausreichende Hochspannungsfestigkeit und ausreichende thermische Dauerbelastbarkeit. Darüber hinaus treten aufgrund langer Aushärtezeiten Sedimentationserscheinungen des SiC im Kunstharz auf, die zu inhomogenen elektrischen und mechanischen Eigenschaften führen. Schließlich ist es auch bekannt, daß die Bindung des spannungsabhängigen Widerstandsmaterials durch Wasserglas erfolgen kann (DE-PS 8 98 267). Dieser Werkstoff ist jedoch nicht feuchteresistent.Disadvantages of the ceramic sintering process are the high technical effort, especially the high energy costs, a limited dimensional stability, as well as the brittleness of the manufactured End products. The use of polymers as binders requires a lot of effort to realize the demands of health, labor and environmental protection, high material Expenses (costs of polymers, equipment) and generally does not guarantee sufficient High voltage resistance and adequate thermal Continuous load. In addition, due to long occur Curing times Sedimentation phenomena of SiC in synthetic resin on, leading to inhomogeneous electrical and mechanical Properties lead. Finally, it is also known that the Binding of the voltage-dependent resistor material by Water glass can be done (DE-PS 8 98 267). This material is but not moisture resistant.

Ziel der ErfindungObject of the invention

Das Ziel der Erfindung besteht darin, einen spannungsabhängigen, nicht entflammbaren keramischen Verbundwerkstoff mit minimalem Aufwand herzustellen, welcher sich auszeichnet durch:The object of the invention is to provide a voltage-dependent, non-flammable ceramic composite with minimal Effort to produce, which is characterized by:

  • - hohe Maßhaltigkeit durch schwindungsloses Herstellungsverfahren,high dimensional stability due to shrinkless production process,
  • - minimaler Energieaufwand des Herstellungsverfahrens,- minimal energy consumption of the manufacturing process,
  • - hohe Dauertemperaturbeständigkeit (<220°C),high high temperature resistance (<220 ° C),
  • - Feuchtebeständigkeit, - moisture resistance,  
  • - Hochspannungsfestigkeit, Kriechstromfestigkeit,- high voltage strength, creepage resistance,
  • - gute mechanische Belastbarkeit.- good mechanical strength.
Darlegung des Wesens der ErfindungExplanation of the essence of the invention

Der Erfindung liegt deshalb die Aufgabe zugrunde, ein Verfahren zur Herstellung eines spannungsabhängigen keramischen Verbundwerkstoffes mit chemischer Bindung der Werkstoffkomponenten unter Einsatz eines selbsthärtenden Bindemittels zu entwickeln, das die üblichen Formgebungsverfahren ohne nachfolgende Sinterung ermöglicht. Der Werkstoff soll eine Dauertemperaturbelastbarkeit bis zu 250°C, eine Hochspannungsfestigkeit bis 5 kV und eine Maßtoleranz bei der Herstellung von maximal ±0,1% aufweisen.The invention is therefore the object of a method for producing a voltage-dependent ceramic Composite with chemical bonding of the Material components using a self-curing Bindemittels to develop the usual molding processes without subsequent sintering possible. The material should be a Continuous operating temperature up to 250 ° C, one High voltage resistance up to 5 kV and a dimensional tolerance in the Production of a maximum of ± 0.1%.

Erfindungsgemäß erfolgt dies, indem als Bindemittel reaktive Monomere verwendet werden.According to the invention, this is done by reacting as a binder Monomers can be used.

Besonders gute Werte für die Dauertemperaturbelastbarkeit und der Hochspannungsfestigkeit lassen sich erzielen, wenn als reaktive Monomere Isocyanate eingesetzt werden.Particularly good values for the continuous temperature load capacity and the High voltage resistance can be achieved when as reactive Monomeric isocyanates are used.

Vorteilhaft ist es weiter, die reaktiven Monomere mit trockenen, feinpulverisierten Mehrschichtmineralien, vorzugsweise Kaolinit bzw. Mixed-Layer zu einer Bindemasse zu mischen. Der Anteil der spannungsabhängigen Grundsubstanz, vorzugsweise SiC sollte mit dem Anteil der Bindemasse im Verhältnis von 4,0 : 1 bis 1 : 10 gemischt werden.It is also advantageous to use the reactive monomers with dry, finely pulverized multi-layer minerals, preferably kaolinite or mixed layer to a binding mass to mix. The share of voltage-dependent ground substance, preferably SiC should with the proportion of binder in the ratio of 4.0: 1 to 1:10 be mixed.

Der so hergestellte Werkstoff läßt sich nach dem üblichen Verfahren weiterverarbeiten. Auf die Formgebung folgt das Trocknen der Rohlinge bei Temperaturen bis zu 120°C über 1 bis 24 Stunden. Der so hergestellte Werkstoff mit spannungsabhängigem Widerstand ist schwindungsfrei und läßt sich mit hoher Maßhaltigkeit und minimalem technologischen Aufwand weiterverarbeiten.The material thus prepared can be according to the usual Process further. This is followed by the shaping Dry the blanks at temperatures up to 120 ° C over 1 to 24 Hours. The material thus produced with voltage-dependent Resistance is shrinkage free and can be with high Dimensional accuracy and minimal technological effort processed.

Ausführungsbeispielembodiment

An einigen Beispielen soll die Erfindung näher erläutert werden. Zunächst werden die Ausgangsstoffe im Schnellmischer homogen gemischt. Nach dem Trockenpressen erfolgt das Tempern der Formlinge im Trockenschrank.By some examples, the invention will be explained in more detail. First, the starting materials in the high-speed mixer are homogeneous mixed. After dry pressing, the tempering of the Moldings in the drying oven.

Die nachstehenden Werkstoffzusammensetzungen mit Isocyanaten als reaktives Monomer brachten jeweils eine Hochspannungsfestigkeit bis zu 5 kV und eine Dauertemperaturbelastbarkeit bis zu 250°C.The following material compositions with isocyanates as reactive monomer each brought high-voltage strength up to 5 kV and a continuous temperature rating of up to 250 ° C.

Beispiel 1example 1 SiC Kempten, F 320|50%SiC Kempten, F 320 | 50% Ton GuttauTon Guttau 30%30% Isocyanatisocyanate 20%20%

Aufbereitung durch Trockenmischen:
Trockenpressen, spezif. Preßdruck: 800 kp/qcm
Tempern bei 100°C; 3 h
Rohdichte: 2,3 g/ccm
Biegebruchfestigkeit: 54 MPaPreparation by dry mixing:
Dry pressing, specif. Pressing pressure: 800 kp / qcm
Annealing at 100 ° C; 3 h
Bulk density: 2.3 g / cc
Bending strength: 54 MPa

U-I-Kennlinie:U-I characteristic:

1 µA|90 V1 μA | 90V 10 µA10 μA 175 V175 v 100 µA100 μA 290 V290 V 1 mA1 mA 450 V450V 10 mA10 mA 630 V630 V

Beispiel 2Example 2 SiC Norton, F 800|70%SiC Norton, F 800 | 70% Kaolin SeilitzKaolin rope seat 21%21% Isocyanatisocyanate 9%9%

Aufbereitung durch Trockenmischen:
Trockenpressen, spezif. Preßdruck: 100 kp/qcm
Tempern bei 120°; 2 h
Rohdichte: 2,25 g/ccmPreparation by dry mixing:
Dry pressing, specif. Pressing pressure: 100 kp / qcm
Annealing at 120 °; 2 h
Bulk density: 2.25 g / cc

U-I-Kennlinie:U-I characteristic:

1 µA|820 V1 μA | 820 V 10 µA10 μA 1500 V1500 V 100 µA100 μA 2800 V2800 V 1 mA1 mA 4400 V4400 V 10 mA10 mA 6300 V6300V

Beispiel 3Example 3 SiC Kempten extra F 180|20%SiC Kempten extra F 180 | 20% Kaolin SeilitzKaolin rope seat 56%56% Isocyanatisocyanate 24%24%

Aufbereitung durch Trockenmischen:
Trockenpressen, spezif. Preßdruck: 800 kp/qcm
Tempern bei 220°C; 2 h
Rohdichte: 2,1 g/ccmPreparation by dry mixing:
Dry pressing, specif. Pressing pressure: 800 kp / qcm
Annealing at 220 ° C; 2 h
Bulk density: 2.1 g / cc

U-I-Kennlinie:U-I characteristic:

1 µA|2500 V1 μA | 2500V 10 µA10 μA 3600 V3600 V 100 µA100 μA 4850 V4850V 1 mA1 mA 6900 V6900 V

Rechercheberichtresearch report

C 04 B, 35/56
DD 1 38 061 . . . 2 77 668
DE 26 37 634 . . . 38 36 392
WO 84/01 369 . . . 90/03 348
EP 93 532 . . . 3 68 535
FR 21 80 701 . . . 25 28 823
GB 13 26 812 . . . 20 82 165
SU 6 29 200 . . . 10 60 597
US 45 22 666 . . . 46 93 988
JP 58-33 192 . . . 62-20 149C 04 B, 35/56
DD 1 38 061. , , 2 77 668
DE 26 37 634. , , 38 36 392
WO 84/01 369. , , 90/03 348
EP 93,532. , , 3 68,535
FR 21 80 701. , , 25 28 823
GB 13 26 812. , , 20 82 165
SU 6 29 200. , , 10 60 597
US 45 22 666. , , 46 93 988
JP 58-33 192. , , 62-20 149

H 01 C, 7/10
DD 1 32 376 . . . 2 65 024
DE 26 33 566 . . . 38 41 131
GM 87 17 303
WO 84/03 171 . . . 89/1 209
EP 66 333 . . . 3 57 113
FR 21 72 134 . . . 25 71 537
GB 13 29 750 . . . 21 11 748
SU 5 88 563 . . . 13 36 124
US 37 45 505 . . . 47 86 888
JP 48-6 755 . . . 63-47 125H 01 C, 7/10
DD 1 32 376. , , 2 65 024
DE 26 33 566. , , 38 41 131
GM 87 17 303
WO 84/03 171. , , 89/1 209
EP 66 333. , , 3 57 113
FR 21 72 134. , , 25 71 537
GB 13 29 750. , , 21 11 748
SU 5 88 563. , , 13 36 124
US 37 45 505. , , 47 86 888
JP 48-6755. , , 63-47 125

Claims (4)

1. Verfahren zur Herstellung eines spannungsabhängigen keramischen Verbundwerkstoffes unter Einsatz eines selbsthärtenden Bindemittels, dadurch gekennzeichnet, daß als Bindemittel reaktive Monomere verwendet werden.1. A process for preparing a voltage-dependent ceramic composite material using a self-curing binder, characterized in that reactive monomers are used as the binder. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als reaktive Monomere Isocyanate eingesetzt werden.2. The method according to claim 1, characterized in that as reactive monomers isocyanates are used. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die reaktiven Monomere mit trockenen, feinpulverisierten Mehrschichtmineralien, vorzugsweise Kaolinit bzw. Mixed-Layer zu einer Bindemasse gemischt werden.3. The method according to claim 1, characterized in that the reactive monomers with dry, finely pulverized Multilayered minerals, preferably kaolinite or mixed layer be mixed into a binding mass. 4. Verfahren nach Anspruch 1 und 3, dadurch gekennzeichnet, daß die Anteile der spannungsabhängigen Grundsubstanz, vorzugsweise SiC mit den Anteilen der Bindemasse im Verhältnis von 4,0 : 1 bis 1 : 10 gemischt werden.4. The method according to claim 1 and 3, characterized in that the proportions of the voltage-dependent ground substance, preferably SiC with the proportions of the binder in the Ratio of 4.0: 1 to 1: 10 mixed.
DE4032062A 1990-10-05 1990-10-05 Prodn. of voltage-dependent ceramic composite - using self-hardening reactive monomer binder, pref. isocyanate Withdrawn DE4032062A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE4032062A DE4032062A1 (en) 1990-10-05 1990-10-05 Prodn. of voltage-dependent ceramic composite - using self-hardening reactive monomer binder, pref. isocyanate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE4032062A DE4032062A1 (en) 1990-10-05 1990-10-05 Prodn. of voltage-dependent ceramic composite - using self-hardening reactive monomer binder, pref. isocyanate

Publications (1)

Publication Number Publication Date
DE4032062A1 true DE4032062A1 (en) 1992-04-09

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4120835A1 (en) * 1991-06-24 1993-01-07 Tridelta Ag Polymer-ceramic composite prepn. - by mixing dried, finely ground mineral supports with organic dimers or oligomers
DE19821239C2 (en) * 1998-05-12 2003-04-17 Epcos Ag Composite material for deriving overvoltage pulses and method for its production

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4120835A1 (en) * 1991-06-24 1993-01-07 Tridelta Ag Polymer-ceramic composite prepn. - by mixing dried, finely ground mineral supports with organic dimers or oligomers
DE4120835C2 (en) * 1991-06-24 2001-03-08 Cera System Verschleisschutz G Process for producing a polymer-ceramic composite
DE19821239C2 (en) * 1998-05-12 2003-04-17 Epcos Ag Composite material for deriving overvoltage pulses and method for its production
DE19821239C5 (en) * 1998-05-12 2006-01-05 Epcos Ag Composite material for dissipation of overvoltage pulses and method for its production

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