EP0707188B1 - Support en SiC - Google Patents

Support en SiC Download PDF

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Publication number
EP0707188B1
EP0707188B1 EP95116102A EP95116102A EP0707188B1 EP 0707188 B1 EP0707188 B1 EP 0707188B1 EP 95116102 A EP95116102 A EP 95116102A EP 95116102 A EP95116102 A EP 95116102A EP 0707188 B1 EP0707188 B1 EP 0707188B1
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EP
European Patent Office
Prior art keywords
layer
sic
support according
support
thickness
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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.)
Expired - Lifetime
Application number
EP95116102A
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German (de)
English (en)
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EP0707188A1 (fr
Inventor
Andreas Dr. Sonntag
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Morgan Crucible Co PLC
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Morgan Crucible Co PLC
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Publication of EP0707188A1 publication Critical patent/EP0707188A1/fr
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D5/00—Supports, screens, or the like for the charge within the furnace
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/02—Skids or tracks for heavy objects

Definitions

  • the invention relates to support bodies in the form of rollers, Beams, plates, positioning supports or the like as a piece of equipment in heat treatment furnaces for heat treatment of metals consisting of SiC and are coated with a corrosion protection layer and a method for the heat treatment of metals with such a support body.
  • high-temperature-resistant ceramic carrier components offers the advantage over metals that they maintain their shape stability under (static or dynamic) mechanical stress at high operating temperatures and show no distortion after or during cooling.
  • the surface defects ("pittings") described above also disappear when using ceramic supports.
  • These ceramics are oxide-ceramic materials that are characterized by good creep resistance and resistance to temperature changes even at temperatures above 1,000 ° C. Nevertheless, the durability of oxide ceramic supports in the high temperature range is limited, since their typical compositions are not corrosion-resistant to the constituents of the metal material, in particular Fe.
  • oxide-ceramic supports are only possible to a limited extent. In the case of very high mechanical loads, such as those that can occur during the transport of steel blocks through roller hardening furnaces, or in the case of very abrupt temperature changes, such as those that occur when quenching in a discontinuously operating hardening furnace, the usability of the oxide-ceramic materials mentioned above is additionally restricted, since they have the required strength and cannot provide resistance to temperature changes.
  • a support body in the form of rollers is known as a piece of equipment in heat treatment furnaces.
  • the supporting body is made of SiC and has a protective layer against oxidation and abrasion at temperatures above 1000 ° C.
  • the protective layer consists of oxide ceramics such as Al 2 O 3 , ZnO 3 , TiO 2 or Cr 2 O 3 with a thickness between 0.03 and 20 mm.
  • the invention is characterized by the characteristic features of claim 1 solved.
  • the subclaims show advantageous further training.
  • thermally sprayed compensation layer with a thickness of 1 to 300 ⁇ m with a linear coefficient of thermal expansion ⁇ 20-1000 ° C ⁇ 6 x 10 -6 1 / K between the SiC support body and the corrosion protection layer, which an equalization or compensation of the different thermal expansion coefficients and / or elastic constants between the corrosion protection layer and the SiC carrier.
  • the SiC carrier bodies according to the invention are now compared more resilient to oxidic ceramics and also have an extraordinarily good one Resistance to temperature changes. So they can known for the oxide ceramic idlers Disadvantages as described above are overcome become.
  • the support body according to the invention show is also clear compared to the metallic consider, since now the typical appearance, the when two hot metal surfaces slide together ("Pitting") arises, no longer occur.
  • relevant SiC materials come according to the invention in particular recrystallized SiC (RSiC), the silicon infiltrated SiC (SiSiC), the nitridic or oxynitridic bonded SiC and the sintered SiC (SSiC) into consideration.
  • the inventive coating of the SiC material with a thermally sprayed corrosion protection layer prevents the elements contained in the steels, in particular iron, from reacting with the SiC.
  • SiC materials are not chemically resistant to the elements present in steel (in particular Fe or Ni), since these elements (Me) reduce the SiC at high temperatures under reducing or vacuum conditions according to the reaction equation decompose.
  • Analogous silicide formation reactions eg Cr, Mn, Co, Mo, Nb
  • Alloy elements such as V, Ti, Ta, W can, depending on the thermodynamic equilibrium conditions, after silicide formation or after carbide formation come in. For this reason, SiC grain is used, for example, in the processing of cast iron for carburizing and siliciding, and is used as a deoxidizer in the steel casting process.
  • Nitridic binding phases react similarly such as or excess metallic Si in the SiC material to form an alloy formation that may lower the melting point and thus increase the vapor pressure, which may result in an increase in the porosity at operating temperatures from approx. 1200 ° C:
  • the coating of SiC idlers with oxides is known from another area of application, namely on the heat treatment of oxidic ceramics (silicate and oxide ceramics). It is proposed to apply a suspension to the SiC support body in order to avoid sticking in high-temperature applications for oxidic materials.
  • the composition of the suspensions (engobes) is predominantly based on Al 2 O 3 and is preferably applied to plates made of recrystallized SiC, which serve as a base for fired goods in smooth porcelain firing at temperatures around 1,400 ° C.
  • the engobe layer is solidified by a fire in the area of the operating temperature, the adhesion to the SiC substrate is based on interlocking with the open-pored surface of the RSiC.
  • layers of engobes adhere to dense SiC surfaces, such as those found with SSiC or SiSiC, generally less well because the necessary mechanical interlocking of the engobe with the SiC does not occur.
  • G 91 10 703.2 describes the use of a plasma-sprayed Al 2 O 3 layer on SiC rolls or SiC base plates for high-temperature firing (1,400 ° C) from Hartsproellan.
  • the Al 2 O 3 layer applied to the SiC has the function of a separating layer in order to prevent the sticking between the roll and the plate, which often occurs in temperature ranges from 1,200 to 1,300 ° C.
  • Those in the Plasma coatings based on ZrO 2 -CaO or Al 2 O 3 -MgO, which are described in DE 31 26 062 A1, are sprayed onto ceramic support rollers and thus prevent sticking between glazed firing material and support roller in roller hearth furnaces.
  • G 93 07 308.9 are supporting rollers of high-purity sintered quartz and alumina-containing ceramics by means of thermal spraying processes bonding layers of Si, Cr, Ni or mixtures thereof and subsequent functional layer of MgAl 2 O 4, 3Al 2 O 3, 2SiO 2, Al 2 TiO 5, ZrO 2 , Y 2 O 3 , TiO 2 , BaO, MgO, SnO 2 or the oxides of rare earths.
  • the function of the oxide layers here is to prevent caking and adhesion reactions between the rollers and the firing material during transport in the furnace.
  • the coatings of ceramic support bodies described all have in common that sticking and thus wetting silicatic glass phase formation between the firing material and the support body should be avoided.
  • SiC ceramics When SiC ceramics are used, this is caused by their surface oxidation to SiO 2 in oxidizing high-temperature use; in the case of sintered quartz material or transport rollers containing aluminum oxide, the glass phase-forming SiO 2 component is incorporated in their composition from the outset. Rolls coated in this way are only used in the thermal treatment of oxidic materials, i.e. silicate and oxide ceramics, oxidic functional ceramics and glass.
  • SiC support body with a thermally sprayed corrosion protection layer also for heat treatment of metals in heat treatment furnaces at temperatures > 1000 ° C can be used.
  • the supporting body showed even in temperature ranges above 1,300 ° C an excellent resistance. That too treating metal did not react in any case with the SiC carrier.
  • disadvantages namely the ability to react the SiC with metals contained in the alloys, it was not to be expected that only through the thermally sprayed protective layer of this SiC support body compared to the known metallic or oxide ceramic have such superior properties.
  • the corrosion protection layers according to the invention serve thus for chemical bonding and / or diffusion hindrance the diffusing into the layer structure Metal ions and / or for rejection or slowdown penetration of metallic (partial) Melting in the layer structure.
  • the different compositions of the corrosion protection layers characterize their different Individual functions. These individual functions can through appropriate graded or graded Complete mixed compositions with each other, whereby the total thickness of the corrosion protection layer (s) Do not exceed 300 ⁇ m.
  • The is preferably 200 ⁇ m thick.
  • composition of the corrosion protection layer has a low wettability of metallic melting phases in a reduced or protective gas atmosphere or vacuum. This is achieved by means of corrosion protection layer compositions which consist partly or completely of spinels of the general formula AB 2 O 4 , partly or completely of chromium oxides, in particular Cr 2 O 3 aluminum oxide, titanium oxide or zirconium oxide or mixtures thereof.
  • spinels of the general formula AB 2 O 4
  • chromium oxides in particular Cr 2 O 3 aluminum oxide, titanium oxide or zirconium oxide or mixtures thereof.
  • A are divalent metals from the group Mg, Fe, Zn, Mn, Co, Ni, Cu or Cd and for B the metals Al, Fe, V, Cr or Ti.
  • Mg / Al spinels are particularly preferred.
  • the embodiment proposes to apply a so-called compensation layer with a layer thickness of up to 300 ⁇ m, preferably 200 ⁇ m, between the SiC support body and the corrosion protection layer.
  • These compensation layers are composed in such a way that they bring about an adjustment or compensation of the different coefficients of thermal expansion and / or different elastic constants between the corrosion protection layers and the SiC carrier body.
  • the compensation or equalization of the different coefficients of thermal expansion is achieved according to the invention in that the thermal expansion coefficients of the compensating layers are equalized or less than that of the SiC.
  • This group of compounds is described, inter alia, by the general formulas [(Al, Ti, Fe) 2 O 3 .TiO 2 ] and [(Mg, Ti, Fe) O. 2TiO 2 ].
  • Al 2 TiO 5 has a coefficient of thermal expansion of ⁇ 20-1,000 ° C ⁇ 1.5 10 -6 1 / K.
  • the compensation layers can be based on, for example, 3Al 2 O 3 .2SiO 2 , ZrO 2 .SiO 2 or Al 2 TiO 5 in a graded or stepped manner. For example, 10 individual layers of approx. 20 ⁇ m each with the mixing ratios 3Al 2 O 3 ⁇ 2SiO 2 : Cr 2 O 3 from 5:95, 10: 90, 20:80 etc. to 90:10 can be passed over and thus directly adapted to the outer corrosion protection layer become.
  • the leveling layers are characterized by certain crack or lamella structures in their structure.
  • Compensating layers with 3Al 2 O 3 .2SiO 3 and / or ZrO 2 .SiO 2 as a layer component are advantageously characterized in that they can form a crack structure or lamellar structure which is parallel to the base body surface by using thermal spraying technology.
  • These lamellar cracks with a lamellar structure within a typically approx. 200 ⁇ m thick compensation layer lead to a delayed or completely prevented progress of radially aligned cracks, which in turn have their origin due to thermally induced stresses within the corrosion protection layers.
  • Compensating layers that consist partly or completely of Al 2 TiO 5 have, due to the pronounced anisotropic thermal expansion behavior of the Al 2 TiO 5 single crystal, a material structure typically interspersed with the finest microcracks with a comparatively low modulus of elasticity of approximately 1.5 GPA (modulus of elasticity SiSiC is around 360 GPa). It is therefore characteristic of these compensating layers that thermally or mechanically induced stresses in the layer structure can be reduced or reduced within the compensating layer interspersed with microcracks, the structure giving in to the applied stresses relatively easily.
  • the use of a compensating layer consisting partly or entirely of Al 2 TiO 5 is the corrosion-inhibiting effect already described above.
  • an adhesive layer is primarily required for dense SiC materials, i.e. Materials without open porosity or smooth surface. These include the sintered SSiC and the silicium-filtered SiSiC.
  • Adhesive layers are in a total thickness of max. 50 ⁇ m, preferably 20 ⁇ m, directly on the previously cleaned and roughened, i.e. with e.g. Corundum grains blasted surface, sprayed on.
  • the function of the adhesive layers is one, fixed adhesive transition between compensation or corrosion protection layer under the SiC material surface to ensure. This is typically done by metallic Adhesive layer compositions of Si, Ti, Ni, Cr or mixtures or alloys of these elements or also by NiCrAlY, CoCrAlY or NiCo CrAlY alloys reached. Depending on the composition of the adhesive layer can be a vacuum or protective gas atmosphere have a positive influence on the adhesion properties of the layer.
  • metallic adhesive layers are capable mechanical stresses caused by reduce their ductility.
  • the adhesive coating is more open-porous SiC ceramics such as recrystallized SiC (RSiC) or nitridically or oxynitridically bound SiC also supports firm liability in this case the leveling layer and / or anti-corrosion layer to get on the SiC underground, though adhesion without mechanical layer due to mechanical Interlocking is given.
  • RSiC recrystallized SiC
  • nitridically or oxynitridically bound SiC also supports firm liability in this case the leveling layer and / or anti-corrosion layer to get on the SiC underground, though adhesion without mechanical layer due to mechanical Interlocking is given.
  • the invention Discrete layer structure provided from individual layers. But it is also possible that either in individual Layers, e.g. in a corrosion protection layer there is a graded structure or that just one layer in the form of a changing material composition is used.
  • the invention encompasses thus all layer variants, starting from one Corrosion protection layer with a uniform composition, one or more layers with graded Structure, like multiple layers with uniform compositions.
  • Figure 1 shows schematically a layer structure on the SiC support body 1.
  • an adhesive layer 2 with a layer thickness of 20 ⁇ m applied.
  • the leveling layer deposited on it 3 has a thickness of 200 microns.
  • 2 corrosion protection layers 4, 5 provided, each having a thickness of Have 50 microns.
  • the layer compositions can now be chosen so that the individual layers only materials of the respective layer type contain or have a graded structure. In this case the composition changes in one shift.
  • the layer structures described can be used with one applied in vacuum plasma spraying Ti adhesive layer as well as without any adhesive layer Apply to the open porous SiC carrier.
  • Radial cracks preferably occur with corrosion protection layers above 100 ⁇ m. Corrosion tests show no new mineral phase formation in Example I. A coloration of the spinel layer in the contact area could be determined by light microscopy. The layer combination in Example II shows a partial new phase formation in the corrosion protection layer from Al 2 O 3 to FeO Al 2 O 3 (Hercynit), combined with a densification of the layer close to the surface to the closed porosity.
  • Example No. III Base: nitride-bonded SiC Adhesive layer approx. 20 ⁇ m CrNi Leveling layer approx. 200 ⁇ m Al 2 TiO 5 Corrosion protection layer graded transition from 100% Al 2 O 3 to 100% ZrO 2 over a total thickness of approx.
  • Example No. IV Base: nitride-bonded SiC Adhesive layer approx. 20 ⁇ m NiCrAlY Leveling layer approx. 200 ⁇ m Al 2 TiO 5 1. Corrosion protection layer approx. 35 ⁇ m 25% ZrO 2 75% Al 2 O 3 2. Corrosion protection layer 35 ⁇ m 75% ZrO 2 25% Al 2 O 3
  • the adhesive layers of Examples III and IV are flushed with argon. ie O 2 exclusion sprayed.
  • the layer structures are characterized by a 10% or 75% ZrO 2 corrosion protection layer. Due to the relatively large difference in the thermal coefficients of thermal expansion from ZrO 2 to SiC with 12 x 10 -6 l / k and 4.5 10 -6 l / k (20-1000 ° C), a stronger radial crack formation after aging or Thermal shock tests by a max. Reduce the corrosion protection thickness by 70 ⁇ m. Al 2 TiO 5 compensation layers have proven to be particularly advantageous in these examples. The radial crack propagation can be effectively prevented with a compensation layer thickness from 200 ⁇ m.
  • Example No. V Base body: silicon infiltrated SiC (SiSiC) Adhesive layer approx. 20 ⁇ m Si Leveling layer approx. 150 ⁇ m Al 2 ⁇ TiO 5 1. Corrosion protection layer 50 ⁇ m 25% MgO ⁇ Al 2 O 3 75% 0.87Al 2 O 3 0.13TiO 2 2. Corrosion protection layer approx. 100 ⁇ m MgO ⁇ Al 2 O 3 Example No.
  • Base body silicon-infiltrated SiC (SiSiC) Adhesive layer approx. 20 ⁇ m Si Leveling layer approx. 150 ⁇ m 50% (Al, Ti, Fe) 2 O 3 ⁇ 2TiO 2 50% (Mg, Ti, Fe) O ⁇ 2TiO 2 1. Corrosion protection layer 50 ⁇ m 25% Cr 2 O 3 75% 0.97 Al 2 O 3 0.03TiO 2 2. Corrosion protection layer approx. 50 ⁇ m 75% Cr 2 O 3 25% 0.97 Al 2 O 3 0.03TiO 2
  • the Si adhesive layers were sprayed onto the SiSiC surfaces in atmospheric air.
  • the first layers of corrosion protection layer were partially sprayed with a TiO 2 -containing Al 2 O 3 mixture, which is characterized by a low-pore structure.
  • the corrosion protection layers in Example V. are more susceptible to thermal shock than in Example VI.
  • the anosovite layer prevents crack propagation on the SiC surface.
  • New phase formation after the corrosion tests could in Example VI. can be determined by the formation of hercynite, in Example V. a dark coloring of the spinel phase could be observed.
  • Example No. VII Base: sintered SiC (SSiC) Adhesive layer approx. 20 ⁇ m Si Leveling layer approx.
  • Examples VII. And VIII. Illustrate a three-layer structure.
  • the compensation layer thickness on the Anosovite was increased to approx. 250 ⁇ m, an approximately 70 ⁇ m thick ZrO 2 layer could be sprayed on directly.
  • Radial crack formation after aging or thermal shock could be restricted with this layer thickness ratio. Possibly. Cracks on the anosovite layer are prevented from progressing further.
  • Corrosion tests showed a dark discoloration of the ZrO 2 protective layer, a new phase formation could not be detected.
  • the Cr 2 O 3 protective layer variant likewise showed no new phase formation. A crack propagation from the Cr 2 O 3 layer after aging or after the thermal shock tests could already be prevented from a compensating layer thickness of about 100 ⁇ m.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
  • Ceramic Products (AREA)

Claims (11)

  1. Corps de support sous la forme de rouleaux, de poutres, de plaques, de supports de positionnement ou analogues. comme pièce d'équipement dans des fours de traitement thermique pour traiter à chaud des métaux, qui est constitué de SiC au moins dans la zone de contact, dans lequel on applique sur le SiC une couche anti-corrosion pulvérisée à chaud d'une épaisseur de 1 à 300 µm, caractérisé en ce qu'on applique entre le corps de support de SiC et la couche anti-corrosion une couche de compensation pulvérisée à chaud d'une épaisseur de 1 à 300 µm présentant un coefficient de dilatation thermique linéaire α20-1000°C < 6 x 10-6 1/K, qui permet une harmonisation ou compensation des différents coefficients de dilatation thermique et/ou des différentes constantes élastiques entre la couche anti-corrosion et le corps de support en SiC.
  2. Corps de support selon la revendication 1, caractérisé en ce que les matériaux de la couche anti-corrosion sont choisis parmi les spinelles de formule générale I : AB2O4 dans laquelle A est un métal bivalent choisi dans le groupe de métaux Mg, Fe, Zn, Mn, Co, Ni, Cu ou Cd, et B est un métal trivalent ou quadrivalent choisi dans le groupe des métaux Al, Fe, V, Cr ou Ti,
    et/ou les oxydes de chrome et/ou les oxydes d'aluminium,
    et/ou les oxydes de titane,
    et/ou l'oxyde de zirconium.
  3. Corps de support selon la revendication 2, caractérisé en ce que A est le magnésium et B l'aluminium.
  4. Corps de support selon au moins l'une des revendications 1 à 3, caractérisé en ce que la couche anti-corrosion est constituée de 2 à 20 couches individuelles de composition identique et/ou différente.
  5. Corps de support selon au moins l'une des revendications 1 à 4, caractérisé en ce que les matériaux de la couche de compensation sont choisis dans le groupe des Anosovite, Pseudobrookite, Karrooite, Tialite ou d'un de leurs mélanges,
    et/ou le silicate de zirconium,
    et/ou la Mullite.
  6. Corps de support selon la revendication 5, caractérisé en ce que le matériau est la Tialite (Al2TiO5).
  7. Corps de support selon au moins l'une des revendications 1 à 6, caractérisé en ce que la couche de compensation est constituée de 2 à 20 couches individuelles de composition identique et/ou différente.
  8. Corps de support selon au moins l'une des revendications 1 à 7, caractérisé en ce qu'on applique une couche adhésive pulvérisée à chaud d'une épaisseur de 1 à 50 µm entre la couche de compensation et le corps de support de SiC.
  9. Corps de support selon la revendication 8, caractérisé en ce que la couche adhésive est choisie parmi les métaux Si, Ti, Ni, Cr ou leurs mélanges ou leurs alliages et/ou des alliages NiCrAlY et/ou CoCrAlY et/ou NiCoCrAlY.
  10. Corps de support selon au moins l'une des revendications. 1 à 9, caractérisé en ce qu'on applique sur le corps de support de SiC une couche pulvérisée à chaud d'une épaisseur de 2-600 µm, dont la composition matérielle, dilatée de la surface de SiC, varie des matériaux de la couche de compensation aux matériaux de la couche anti-corrosion en continu.
  11. Procédé de traitement thermique de métaux dans des fours de traitement thermique, caractérisé en ce qu'on utilise un corps de support de SiC selon au moins l'une des revendications 1 à 10.
EP95116102A 1994-10-14 1995-10-12 Support en SiC Expired - Lifetime EP0707188B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4436823 1994-10-14
DE4436823A DE4436823C1 (de) 1994-10-14 1994-10-14 Tragkörper aus SiC und dessen Verwendung

Publications (2)

Publication Number Publication Date
EP0707188A1 EP0707188A1 (fr) 1996-04-17
EP0707188B1 true EP0707188B1 (fr) 2001-12-19

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EP95116102A Expired - Lifetime EP0707188B1 (fr) 1994-10-14 1995-10-12 Support en SiC

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Country Link
EP (1) EP0707188B1 (fr)
AT (1) ATE211252T1 (fr)
DE (2) DE4436823C1 (fr)

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DE19653483C2 (de) * 1996-12-20 2002-02-28 Morgan Crucible Company Plc Wi Hängevorrichtung für den Einsatz in Brennöfen zur Herstellung keramischer Bauteile
DE19854793B4 (de) * 1998-11-27 2004-04-01 Universität Stuttgart Institut für Fertigungstechnologie keramischer Bauteile Elektrode zur elektrochemischen Bearbeitung eines metallischen Werkstücks und Verfahren zur Herstellung einer solchen
US6296941B1 (en) * 1999-04-15 2001-10-02 General Electric Company Silicon based substrate with yttrium silicate environmental/thermal barrier layer
DE10307341B4 (de) * 2003-02-21 2006-02-02 Bayerische Motoren Werke Ag Tragplatte zur Aufnahme eines Tellerrades
DE102011051270A1 (de) * 2011-06-22 2012-12-27 Benteler Automobiltechnik Gmbh Rolle für einen Rollenofen sowie Rollenofen und Verfahren zur Herstellung einer Rolle für einen Rollenofen
DE102012003216B4 (de) 2012-02-17 2015-10-29 Audi Ag Wärmebehandlungsofen zum Erwärmen von härtbaren Blechplatinen
DE102015205807A1 (de) * 2015-03-31 2016-10-06 Siemens Aktiengesellschaft Beschichtungssystem für Gasturbinen

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BE894731A (fr) * 1982-10-19 1983-02-14 Plumat Emile Procede et dispositif de fabrication de materiaux refractaires par reaction hautement exothermique de carbures
JPS61127657A (ja) * 1984-11-22 1986-06-14 日本坩堝株式会社 誘導加熱炉用セラミツクチユ−ブの製造方法
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DE3707396A1 (de) * 1987-03-09 1988-09-22 Kalawrytinos Georg Verfahren zur herstellung eines keramischen werkstoffes und verfahren zur beschichtung von werkstuecken mit diesem werkstoff
JPH0628947B2 (ja) * 1987-03-16 1994-04-20 品川白煉瓦株式会社 道具れんが用二層構造耐熱板
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DE9307308U1 (de) * 1993-05-13 1993-09-16 Haldenwanger Tech Keramik Gmbh Transportrolle

Also Published As

Publication number Publication date
ATE211252T1 (de) 2002-01-15
DE59509964D1 (de) 2002-01-31
EP0707188A1 (fr) 1996-04-17
DE4436823C1 (de) 1996-05-02

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