EP0694627A1 - Coating for driving elements - Google Patents
Coating for driving elements Download PDFInfo
- Publication number
- EP0694627A1 EP0694627A1 EP95111213A EP95111213A EP0694627A1 EP 0694627 A1 EP0694627 A1 EP 0694627A1 EP 95111213 A EP95111213 A EP 95111213A EP 95111213 A EP95111213 A EP 95111213A EP 0694627 A1 EP0694627 A1 EP 0694627A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- covering
- powder
- mixed
- abradable
- 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- Withdrawn
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 46
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 239000003082 abrasive agent Substances 0.000 claims abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 19
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 17
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910010293 ceramic material Inorganic materials 0.000 claims description 7
- 230000003628 erosive effect Effects 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 5
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
- 238000005494 tarnishing Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 238000010285 flame spraying Methods 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 238000007750 plasma spraying Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 241000264877 Hippospongia communis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
Definitions
- the present invention relates to a rub-on coating for engine components with an abradable or an abrasive material component in the form of particles and a material component connecting them.
- Rubbing surfaces are widely used in engine construction to optimize gap seals.
- the efficiency of engines depends to a large extent on the gaps between the rotor and stator.
- a gap seal usually consists of two abradable coverings, a run-in covering that can be rubbed off and is partially rubbed off when it is rubbed, and a run-on covering that has an abrasive effect and is incorporated into the run-in covering when it is rubbed. Consequently, it is known that abradable coverings as inlet coverings usually consist of a material component that can be rubbed off in the form of particles and a connecting material component made of metal.
- This metal can also be structured as a support matrix in the form of honeycombs or other networks, the interstices being filled with ceramic and / or metal layers.
- rub-on coverings as run-in coverings in addition to abradable material components and connecting metals or ceramics can still contain plastic materials.
- Such three-phase run-in coatings have the disadvantage that the production of a wettable powder from these components in preparation for the application of the coating is extremely complex and cost-intensive. In addition, the production of the coverings is very complicated and there is a risk of incorrect coatings. Finally, a metallic support matrix is exposed to the risk of oxidation and damage to the lining at the operating temperatures of turbines and the aggressive media in turbines.
- Temperatures of 600 ° C are reached in the high-pressure compressor range, with approx. 700 ° C being aimed for in the future.
- Covering materials based on Ni or NiCrAl are mainly used for the temperature range between approx. 400 ° C and 700 ° C.
- Brushed rubbers based on pure Ni are characterized by a temperature resistance of up to 450 ° C and show good running-in properties up to these operating temperatures.
- NiCrAl base materials show somewhat less favorable running-in behavior, but they can be used up to 800 ° C.
- the support matrix or networks made of metal or ceramic usually show insufficient rubbing behavior, so that it is an object of the invention to avoid such networks.
- Another object of the invention is to overcome the disadvantages in the prior art and to provide a surface which is capable of being rubbed for high-temperature applications.
- This solution has the advantage that the covering is much easier and cheaper to manufacture, since there is no need for complex soldering or welding techniques for attaching a supporting network.
- the rubbing behavior improves at the same time, since no disruptive support matrix hinders the rubbing process. Damage to the abradable coating caused by the oxidation of metallic components is excluded.
- An adaptation of the layer properties from abrasion to abrasion is possible by adapting the composition of the mixed particles, by adding or replacing components in the mixed particles and / or by changing the manufacturing parameters when applying the coverings. Additional solid lubricants such as plastic can also be dispensed with.
- the ceramic materials for the brush coating according to the invention are materials based on magnesium oxide, zinc oxide, calcium fluoride, barium fluoride or magnesium fluoride and are present in the brush coating as mixed and / or individual phases. This limited selection has the advantage that the inventory can be kept small. It also contains substances that allow a high degree of heat penetration. Thermal penetration is the square root of the product of thermal conductivity, density and isobaric heat capacity. This parameter should achieve the highest possible value in order to be excellent in addition to high temperature resistance Ensure brushability. In the case of abradable coverings, it has been shown that the rapid degradation and the rapid distribution of local overheating at operating temperatures are decisive for the success of a abradable covering. The above materials show a clear superiority particularly in this regard at the high operating temperatures mentioned above compared to blade base materials such as titanium and Ni, Co and Fe base alloys.
- the covering has zinc oxide as the connecting material component to form mixed phases with the other components.
- This material forms mixed phases with the other components such as magnesium oxide in micro areas and at grain boundaries, which advantageously favors the connecting effect.
- the abradable material component consists of zinc oxide, calcium fluoride, barium fluoride or mixtures thereof, preferably of zinc oxide and calcium fluoride.
- These fluorides and zinc oxide can be used particularly advantageously as abradable components because, due to their high melting point and their crystalline structure, they do not melt like a metallic support matrix or are kneaded into a doughy mass when they are touched, but instead break down in layers or granules into the finest dust, which the gases in the flow channel of an engine are blown out.
- the splitting energy that is to be used thereby reduces the frictional or thermal energy that occurs during the rubbing process, so that local overheating can advantageously be avoided and the scraping component can work into the rubbing-on pad, which acts as a running-in pad, without its own abrasive removal.
- the abradable covering preferably additionally has an erosion-resistant ceramic material which forms mixed phases at its grain boundaries with the other ceramic components.
- Magnesium oxide has proven to be the preferred component for this.
- the magnesium oxide has the further advantage that it forms large-grain mixed phases with zinc oxide, which, with the appropriate composition and thermal treatment, can grow into abrasive, deposit-hardening crystallites.
- the abradable covering should preferably result in a running-in covering, it is composed at least of an erosion-resistant and connecting ceramic material and an abradable ceramic material. If one starts from the oxides and fluorides disclosed here, magnesium oxide has emerged as the connecting and erosion-resistant component, while all the other ceramics mentioned above can be used as abradable components.
- the streak is preferably a tarnish, it is composed predominantly (greater than 50% by weight) of magnesium oxide and zinc oxide, since these two components form large-grain and hard to abrasive mixed phases and mixed crystals.
- These mixed phases can advantageously already be formed during the production of the mixed particles, so that with the production of mixed particles a preselection can be made to form an inlet coating with low growth of mixed phases or a start-up coating with high growth of mixed phases.
- an inlet coating indicates a high porosity, which decreases towards the component, while a startup coating indicates a consistently lower porosity.
- the porosity can be adjusted by the parameters during the application of the covering to a component. Therefore, the abradable coating according to the invention is preferably a plasma or flame spraying layer, since in plasma or flame spraying the porosity can be easily controlled via the spraying parameters.
- a brush-on coating according to the invention on a purely ceramic basis which essentially consists of ZnO, MgO and CaF2, proves to be an ideal solution both for run-in and for run-in coatings at high operating temperatures, the production parameters and the compositions being adapted to the operational requirements of the coatings can.
- a ceramic powder is mixed in powder form by mixing the components required for the coating. Sintering the powder mixture and crushing the sintered mass produces a mixed powder so that the components of the abradable coating are contained in each powder particle, and then the coating powder is plasma or flame sprayed directly onto the component surface or onto an adhesive layer.
- the sintered mass is comminuted into coating powder with an average particle size of 5 ⁇ m to 150 ⁇ m.
- the sintered mass contains all the components involved according to the invention.
- the following ceramic powders are preferably mixed to produce the coating powder: CaF2 30 to 40% by weight MgO 3 to 20% by weight ZnO rest.
- the powder mixture is sintered.
- the hardness and abrasiveness of the subsequent coating is set at the same time.
- the hardness increases with increasing sintering time and sintering temperature because an increasingly hard mixed phase of magnesium oxide and zinc oxide forms.
- Calcium fluoride essentially adjusts the abradability of the abradable coating and at the same time provides protection against local overheating.
- Another preferred mixture for producing the coating powder consists of the following ceramic powders: CaF2 30 to 32% by weight MgO 10 to 20% by weight ZnO rest.
- the proportion of magnesium oxide is in the upper range, which promotes the formation of an abrasive tarnish.
- the following composition of the mixed particles is included CaF2 35 to 40% by weight MgO 3 to 10% by weight ZnO rest. suitable for abradable inlet coverings, for which the proportion of magnesium oxide is reduced.
- magnesium fluoride or barium fluoride or mixtures of these fluorides can also be used instead of the calcium fluoride.
- the following ceramic powders are mixed to produce a abradable coating for engine components with an abradable or an abrasive material component in the form of particles and a connecting material component: CaF2 30 to 40 wt.%, MgO 3 to 20 wt.% Rest ZnO.
- This powder mixture is then sintered into a ceramic mass. After cooling to room temperature, this ceramic sintered mass is ground into mixed particles, for example in a drum mill, down to a particle size between 5 and 150 ⁇ m.
- a high CaF2 content of up to 40% by weight with a low MgO content of 5% by weight is used.
- a lower CaF2 content below 35% by weight with a high MgO content of up to 20% by weight is used.
- a brush coating is produced by plasma spraying with a plasma spray gun under a voltage of 50 to 60 V at a current of 300 to 400 A, a primary gas stream of nitrogen of 60 to 80 liters per minute and a secondary gas stream of hydrogen of 70 up to 80 liters per minute.
- a component gas surface is plasma sprayed with a nitrogen gas flow of 20 to 40 liters per minute until a thickness of several millimeters is reached.
- the porosity can be varied and adjusted essentially by the spraying distance and by the propellant gas flow.
- the mixed particles are produced depending on the requirements of the abradable coating and then applied using a flame spraying process.
- a fuel gas flow of 30 to 40 liters per minute from acetylene with a secondary gas flow from oxygen of 30 to 40 liters per minute is maintained with a flame spray burner.
- the component surface is flame-sprayed several times with a nitrogen gas flow of 30 to 45 liters per minute until a sufficient covering thickness of several millimeters is reached.
- the porosity can be varied and adjusted essentially by the spraying distance and by the propellant gas flow.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Cylinder Crankcases Of Internal Combustion Engines (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft einen Anstreifbelag für Triebwerksbauteile mit einer abreibbaren oder einer abrasiven Materialkomponente in Form von Partikeln und einer diese verbindenden Materialkomponente.The present invention relates to a rub-on coating for engine components with an abradable or an abrasive material component in the form of particles and a material component connecting them.
Anstreifbeläge sind im Triebwerksbau weit verbreitet, um Spaltdichtungen zu optimieren. Der Wirkungsgrad von Triebwerken hängt in hohem Maße von den Spalten zwischen Rotor und Stator ab. Dabei besteht eine Spaltdichtung üblicherweise aus zwei Anstreifbelägen, einem Einlaufbelag, der abreibbar ist und beim Anstreifen teilweise abgerieben wird und einem Anlaufbelag, der abrasiv wirkt und sich beim Anstreifen in den Einlaufbelag einarbeitet. Folglich ist bekannt, daß Anstreifbeläge als Einlaufbeläge aus einer abreibbaren Materialkomponente in Form von Partikeln und einer verbindenden Materialkomponente üblicherweise aus Metall bestehen. Dieses Metall kann auch struturiert als Stützmatrix in Form von Waben oder anderen Netzwerken vorliegen, wobei die Zwischenräume mit Keramik- und/oder Metallschichten aufgefüllt sind. Aus EP-PS-0 487 273 ist darüberhinaus bekannt, daß Anstreifbeläge als Einlaufbeläge neben abreibbaren Materialkomponenten und verbindenden Metallen oder Keramiken zusätzlich noch Kunststoffmaterialien enthalten können. Derartige dreiphasige Einlaufbeläge haben den Nachteil, daß die Herstellung eines Spritzpulvers aus diesen Komponenten zur Vorbereitung der Aufbringung des Belages äußerst aufwendig und kostenintensiv ist. Außerdem ist die Fertigung der Beläge sehr kompliziert, und es besteht die Gefahr von Fehlbeschichtungen. Schließlich ist eine metallische Stützmatrix bei den Betriebstemperaturen von Turbinen und den aggressiven Medien in Turbinen der Oxidationsgefahr und der Schädigung des Belages ausgesetzt.Rubbing surfaces are widely used in engine construction to optimize gap seals. The efficiency of engines depends to a large extent on the gaps between the rotor and stator. In this case, a gap seal usually consists of two abradable coverings, a run-in covering that can be rubbed off and is partially rubbed off when it is rubbed, and a run-on covering that has an abrasive effect and is incorporated into the run-in covering when it is rubbed. Consequently, it is known that abradable coverings as inlet coverings usually consist of a material component that can be rubbed off in the form of particles and a connecting material component made of metal. This metal can also be structured as a support matrix in the form of honeycombs or other networks, the interstices being filled with ceramic and / or metal layers. From EP-PS-0 487 273 it is also known that rub-on coverings as run-in coverings in addition to abradable material components and connecting metals or ceramics can still contain plastic materials. Such three-phase run-in coatings have the disadvantage that the production of a wettable powder from these components in preparation for the application of the coating is extremely complex and cost-intensive. In addition, the production of the coverings is very complicated and there is a risk of incorrect coatings. Finally, a metallic support matrix is exposed to the risk of oxidation and damage to the lining at the operating temperatures of turbines and the aggressive media in turbines.
Im Hochdruckverdichterbereich werden Temperaturen von 600 °C erreicht, wobei für die Zukunft ca. 700 °C angestrebt werden. Für den Temperaturbereich zwischen ca. 400 °C und 700 °C sind im wesentlichen Belagwerkstoffe auf Ni- oder NiCrAl-Basis im Einsatz. Anstreifbeläge auf der Basis von reinem Ni sind durch eine Temperaturbeständigkeit von bis zu 450 °C gekennzeichnet und zeigen bis zu diesen Betriebstemperaturen gute Einlaufeigenschaften. Ein etwas ungünstigeres Einlaufverhalten zeigen dagegen NiCrAl-Basiswerkstoffe, die aber bis 800 °C einsetzbar sind.Temperatures of 600 ° C are reached in the high-pressure compressor range, with approx. 700 ° C being aimed for in the future. Covering materials based on Ni or NiCrAl are mainly used for the temperature range between approx. 400 ° C and 700 ° C. Brushed rubbers based on pure Ni are characterized by a temperature resistance of up to 450 ° C and show good running-in properties up to these operating temperatures. NiCrAl base materials, on the other hand, show somewhat less favorable running-in behavior, but they can be used up to 800 ° C.
Die Stützmatrix oder Netzwerke aus Metall oder Keramik zeigen üblicherweise ein ungenügendes Anstreifverhalten, so daß es eine Aufgabe der Erfindung ist, derartige Netzwerke zu vermeiden.The support matrix or networks made of metal or ceramic usually show insufficient rubbing behavior, so that it is an object of the invention to avoid such networks.
Eine weitere Aufgabe der Erfindung ist es, die Nachteile im Stand der Technik zu überwinden und einen anstreiffähigen Belag für Hochtemperaturanwendungen anzugeben.Another object of the invention is to overcome the disadvantages in the prior art and to provide a surface which is capable of being rubbed for high-temperature applications.
Gelöst wir diese Aufgabe dadurch, daß der Anstreifbelag ausschließlich aus keramischen Komponenten aufgebaut ist, und damit sowohl die Partikel als auch die verbindende Materialkomponente aus Keramik bestehen, die vor dem Aufbringen des Belages in Mischpartikeln vorliegen, wobei jedes Partikel sämtliche Komponenten für den Anstreifbelag umfaßt.We solved this task by the fact that the brushing surface exclusively is made up of ceramic components, so that both the particles and the connecting material component consist of ceramic, which are present in mixed particles before the coating is applied, each particle comprising all components for the abradable coating.
Diese Lösung hat den Vorteil, daß der Belag wesentlich einfacher und kostengünstiger herzustellen ist, da aufwendige Löt- oder Schweißtechniken zur Anbringung eines stützenden Netzwerkes entfallen. Durch den Wegfall der Stützmatrix verbessert sich gleichzeitig das Anstreifverhalten, da keine störende Stützmatrix den Anstreifvorgang behindert. Schäden des Anstreifbelages, die durch Oxidation metallischer Komponenten verursacht werden, sind ausgeschlossen. Eine Anpassung der Schichteigenschaften von der Abreibbarkeit bis hin zur Abrasion ist durch Anpassung der Zusammensetzung der Mischpartikel, durch Zugabe oder Ersatz von Komponenten in den Mischpartikeln und/oder durch Änderung der Herstellungsparameter beim Aufbringen der Beläge möglich. Auf zusätzliche Festschmierstoffe wie Plastik kann ebenfalls verzichtet werden.This solution has the advantage that the covering is much easier and cheaper to manufacture, since there is no need for complex soldering or welding techniques for attaching a supporting network. By eliminating the support matrix, the rubbing behavior improves at the same time, since no disruptive support matrix hinders the rubbing process. Damage to the abradable coating caused by the oxidation of metallic components is excluded. An adaptation of the layer properties from abrasion to abrasion is possible by adapting the composition of the mixed particles, by adding or replacing components in the mixed particles and / or by changing the manufacturing parameters when applying the coverings. Additional solid lubricants such as plastic can also be dispensed with.
Die keramischen Materialien für den erfindungsgemäßen Anstreifbelag sind Werkstoffe auf der Basis Magnesiumoxid, Zinkoxid, Kalziumfluorid, Bariumfluorid oder Magnesiumfluorid und liegen im Anstreifbelag als Misch- und/oder Einzelphasen vor. Diese begrenzte Auswahl hat den Vorteil, daß die Lagerbevorratung klein gehalten werden kann. Außerdem enthält sie Stoffe, die eine hohe Wärmeeindringfähigkeit zulassen. Unter Wärmeeindringfähigkeit wird die Quadratwurzel aus dem Produkt von Wärmeleitfähigkeit, Dichte und isobarer Wärmekapazität verstanden. Diese Kenngröße soll einen möglichst hohen Wert erreichen, um neben einer hohen Temperaturbeständigkeit eine hervorragende Anstreiffähigkeit zu gewährleisten. Bei Anstreifbelägen hat es sich nämlich gezeigt, daß der schnelle Abbau und die schnelle Verteilung lokaler Überhitzungen bei Betriebstemperaturen entscheidend für den Erfolg eines Anstreifbelages ist. Die obigen Materialien zeigen besonders in dieser Hinsicht bei den oben erwähnten hohen Betriebstemperaturen gegenüber Schaufelgrundwerkstoffen wie Titan und Ni-, Co- und Fe-Basislegierungen eine eindeutige Überlegenheit.The ceramic materials for the brush coating according to the invention are materials based on magnesium oxide, zinc oxide, calcium fluoride, barium fluoride or magnesium fluoride and are present in the brush coating as mixed and / or individual phases. This limited selection has the advantage that the inventory can be kept small. It also contains substances that allow a high degree of heat penetration. Thermal penetration is the square root of the product of thermal conductivity, density and isobaric heat capacity. This parameter should achieve the highest possible value in order to be excellent in addition to high temperature resistance Ensure brushability. In the case of abradable coverings, it has been shown that the rapid degradation and the rapid distribution of local overheating at operating temperatures are decisive for the success of a abradable covering. The above materials show a clear superiority particularly in this regard at the high operating temperatures mentioned above compared to blade base materials such as titanium and Ni, Co and Fe base alloys.
In einer bevorzugten Ausführungsform der Erfindung weist der Belag als verbindende Materialkomponente Zinkoxid zur Bildung von Mischphasen mit den übrigen Komponenten auf. Dieses Material bildet mit den übrigen Komponenten wie Magnesiumoxid in Mikrobereichen und an Korngrenzen Mischphasen aus, was vorteilhaft den verbindenden Effekt begünstigt.In a preferred embodiment of the invention, the covering has zinc oxide as the connecting material component to form mixed phases with the other components. This material forms mixed phases with the other components such as magnesium oxide in micro areas and at grain boundaries, which advantageously favors the connecting effect.
Bei einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung besteht die abreibbare Materialkomponente aus Zinkoxid, Kalziumfluorid, Bariumfluorid oder Mischungen derselben, vorzugsweise aus Zinkoxid und Kalziumfluorid. Diese Fluoride und das Zinkoxid sind besonders vorteilhaft als abreibbare Komponenten einsetzbar, weil sie aufgrund ihres hohen Schmelzpunktes und ihrer kristallinen Struktur nicht wie eine metallische Stützmatrix angeschmolzen oder zu einer teigigen Masse beim Anstreifen geknetet werden, sondern schichtweise oder körnchenweise zu feinstem Staub spalten, der mit den Gasen im Strömungskanal eines Triebwerks ausgeblasen wird. Die Spalternergie, die dabei aufzuwenden ist, vermindert die beim Anstreifvorgang auftretende Reib- oder Wärmeenergie, so daß vorteilhaft lokale Überhitzungen vermieden werden und sich das anstreifende Bauteil ohne eigenen abrasiven Abtrag in den als Einlaufbelag wirkenden Anstreifbelag einarbeiten kann.In a further preferred embodiment of the present invention, the abradable material component consists of zinc oxide, calcium fluoride, barium fluoride or mixtures thereof, preferably of zinc oxide and calcium fluoride. These fluorides and zinc oxide can be used particularly advantageously as abradable components because, due to their high melting point and their crystalline structure, they do not melt like a metallic support matrix or are kneaded into a doughy mass when they are touched, but instead break down in layers or granules into the finest dust, which the gases in the flow channel of an engine are blown out. The splitting energy that is to be used thereby reduces the frictional or thermal energy that occurs during the rubbing process, so that local overheating can advantageously be avoided and the scraping component can work into the rubbing-on pad, which acts as a running-in pad, without its own abrasive removal.
Die Erosionsbeständigkeit dieser Fluoride ist entsprechend ihrer leichten Spaltbarkeit gering. Deshalb weist der Anstreifbelag vorzugsweise zusätzlich ein erosionsbeständiges keramisches Material auf, das an seinen Korngrenzen mit den übrigen keramischen Komponenten Mischphasen bildet. Als bevorzugte Komponente hat sich dafür Magnesiumoxid bewährt. Das Magnesiumoxid hat weiterhin den Vorteil, daß es mit Zinkoxid großkörnige Mischphasen bildet, die bei entsprechender Zusammensetzung und thermischer Behandlung zu abrasiven, den Belag härtenden Kristalliten anwachsen können.The resistance to erosion of these fluorides is low due to their easy cleavage. For this reason, the abradable covering preferably additionally has an erosion-resistant ceramic material which forms mixed phases at its grain boundaries with the other ceramic components. Magnesium oxide has proven to be the preferred component for this. The magnesium oxide has the further advantage that it forms large-grain mixed phases with zinc oxide, which, with the appropriate composition and thermal treatment, can grow into abrasive, deposit-hardening crystallites.
Soll der Anstreifbelag vorzugsweise einen Einlaufbelag ergeben, so setzt er sich mindestens aus einem erosionsbeständigen und verbindenden keramischen Material und einem abreibbaren keramischen Material zusammen. Wird von den hier offenbarten Oxiden und Fluoriden ausgegangen, so hat sich als verbindende und erosionsbeständige Komponente das Magnesiumoxid herausgestellt, während alle übrigen oben genannten Keramiken als abreibbare Komponenten einsetzbar sind.If the abradable covering should preferably result in a running-in covering, it is composed at least of an erosion-resistant and connecting ceramic material and an abradable ceramic material. If one starts from the oxides and fluorides disclosed here, magnesium oxide has emerged as the connecting and erosion-resistant component, while all the other ceramics mentioned above can be used as abradable components.
Soll der Antreifbelag vorzugsweise einen Anlaufbelag ergeben, so setzt er sich zum überwiegenden Teil (größer 50 Gew.%) aus Magnesiumoxid und Zinkoxid zusammen, da diese beiden Komponenten großkörnige und harte bis abrasive Mischphasen und Mischkristalle bilden. Diese Mischphasen können vorteilhaft schon bei der Herstellung der Mischpartikel ausgebildet werden, so daß mit der Herstellung von Mischpartikeln eine Vorauswahl zur Bildung eines Einlaufbelages mit geringem Wachstum von Mischphasen oder eines Anlaufbelages mit hohem Wachstum von Mischphasen erfolgen kann.If the streak is preferably a tarnish, it is composed predominantly (greater than 50% by weight) of magnesium oxide and zinc oxide, since these two components form large-grain and hard to abrasive mixed phases and mixed crystals. These mixed phases can advantageously already be formed during the production of the mixed particles, so that with the production of mixed particles a preselection can be made to form an inlet coating with low growth of mixed phases or a start-up coating with high growth of mixed phases.
Neben der Einstellung der Härte des erfindungsgemäßen Anstreifbelages über die obige Magnesiumoxid-Zinkoxid-Mischphasenbildung kennzeichnet einen Einlaufbelag eine hohe Porosität, die zum Bauteil hin abnimmt, während einen Anlaufbelag eine durchgehend geringere Porosität kennzeichnet. Die Porosität ist dabei durch die Parameter während der Aufbringung des Belages auf ein Bauteil einstellbar. Deshalb ist der erfindungsgemäße Anstreifbelag vorzugsweise eine Plasma- oder Flammspritzschicht, da beim Plasma- oder Flammspritzen die Porosität über die Spritzparameter leicht steuerbar ist.In addition to adjusting the hardness of the abradable coating according to the invention by means of the above magnesium oxide-zinc oxide mixed phase formation, an inlet coating indicates a high porosity, which decreases towards the component, while a startup coating indicates a consistently lower porosity. The porosity can be adjusted by the parameters during the application of the covering to a component. Therefore, the abradable coating according to the invention is preferably a plasma or flame spraying layer, since in plasma or flame spraying the porosity can be easily controlled via the spraying parameters.
Ein erfindungsgemäßer Anstreifbelag auf rein keramischer Basis, der im wesentlichen aus ZnO, MgO und CaF2 besteht, erweist sich als eine ideale Lösung sowohl für Einlauf als auch für Anlaufbeläge bei hohen Betriebstemperaturen, wobei die Herstellungsparameter und die Zusammensetzungen den betrieblichen Anforderungen an die Beläge angepaßt werden können.A brush-on coating according to the invention on a purely ceramic basis, which essentially consists of ZnO, MgO and CaF2, proves to be an ideal solution both for run-in and for run-in coatings at high operating temperatures, the production parameters and the compositions being adapted to the operational requirements of the coatings can.
Die Aufgabe, ein Verfahren zur Herstellung eines Anstreifbelages für Triebwerksbauteile mit einer abreibbaren oder einer abrasiven Materialkomponente in Form von Partikeln und einer diese verbindenden Materialkomponente anzugeben wird mit den folgenden Verfahrensschritten gelöst: zunächst wird ein Keramikpulver durch Mischen der für den Anstreifbelag erforderlichen Komponenten in Pulverform, Sintern der Pulvermischung und Zerkleinern der gesinterten Masse ein Mischpulver hergestellt, so daß in jedem Pulverpartikel die Komponenten des Anstreifbelages enthalten sind, und anschließend wird das Beschichtungspulver direkt auf die Bauteiloberfläche oder auf eine Haftschicht plasma- oder flammgespritzt.The task of specifying a method for producing a rub-on coating for engine components with an abradable or an abrasive material component in the form of particles and a material component connecting them is solved with the following process steps: First, a ceramic powder is mixed in powder form by mixing the components required for the coating. Sintering the powder mixture and crushing the sintered mass produces a mixed powder so that the components of the abradable coating are contained in each powder particle, and then the coating powder is plasma or flame sprayed directly onto the component surface or onto an adhesive layer.
Bei einer bevorzugten Durchführung des Verfahrens wird die Sintermasse zu Beschichtungspulver mit einer mittleren Teilchengröße von 5 µm bis 150 µm zerkleinert. Die Sintermasse enthält alle beteiligten erfindungsgemäßen Komponenten. Bevorzugt werden zur Herstellung des Beschichtungspulvers folgende Keramikpulver gemischt:
CaF₂ 30 bis 40 Gew.%
MgO 3 bis 20 Gew.%
ZnO Rest.In a preferred implementation of the method, the sintered mass is comminuted into coating powder with an average particle size of 5 μm to 150 μm. The sintered mass contains all the components involved according to the invention. The following ceramic powders are preferably mixed to produce the coating powder:
CaF₂ 30 to 40% by weight
MgO 3 to 20% by weight
ZnO rest.
Nach der Mischung wird die Pulvermischung gesintert. Mit der Sinterzeit und Sintertemperatur wird gleichzeitig die Härte und Abrasivität des späteren Belages eingestellt. Wobei mit zunehmender Sinterzeit und Sintertemperatur die Härte steigt, weil sich zunehmend eine harte Mischphase aus Magnesiumoxid und Zinkoxid ausbildet. Mit dem Kalziumfluorid wird im wesentlichen eine Abreibbarkeit des Anstreifbelages eingestellt und gleichzeitig ein Schutz gegen örtliche Überhitzungen geschaffen.After the mixing, the powder mixture is sintered. With the sintering time and sintering temperature, the hardness and abrasiveness of the subsequent coating is set at the same time. The hardness increases with increasing sintering time and sintering temperature because an increasingly hard mixed phase of magnesium oxide and zinc oxide forms. Calcium fluoride essentially adjusts the abradability of the abradable coating and at the same time provides protection against local overheating.
Eine weitere bevorzugte Mischung zur Herstellung des Beschichtungspulvers besteht aus folgenden Keramikpulvern:
CaF₂ 30 bis 32 Gew.%
MgO 10 bis 20 Gew.%
ZnO Rest.Another preferred mixture for producing the coating powder consists of the following ceramic powders:
CaF₂ 30 to 32% by weight
MgO 10 to 20% by weight
ZnO rest.
Dabei ist der Anteil an Magnesiumoxid im oberen Bereich, was die Ausbildung eines abrasiven Anlaufbelages fördert. Im Gegensatz dazu ist die folgende Zusammensetzung der Mischpartikel mit
CaF₂ 35 bis 40 Gew.%
MgO 3 bis 10 Gew.%
ZnO Rest.
für abreibbare Einlaufbeläge geeignet, wozu der Anteil an Magnesiumoxid erniedrigt wird. In diesem Fall können anstelle des Kalziumfluorids auch Magnesiumfluorid oder Bariumfluorid oder Mischungen dieser Fluoride eingesetzt werden.The proportion of magnesium oxide is in the upper range, which promotes the formation of an abrasive tarnish. In contrast, the following composition of the mixed particles is included
CaF₂ 35 to 40% by weight
MgO 3 to 10% by weight
ZnO rest.
suitable for abradable inlet coverings, for which the proportion of magnesium oxide is reduced. In this case, magnesium fluoride or barium fluoride or mixtures of these fluorides can also be used instead of the calcium fluoride.
Die folgenden Ausführungsbeispiele sollen die Erfindung erläutern.The following exemplary embodiments are intended to explain the invention.
Zur Herstellung eines Anstreifbelags für Triebwerksbauteile mit einer abreibbaren oder einer abrasiven Materialkomponente in Form von Partikeln und einer verbindenden Materialkomponente werden folgende keramische Pulver gemischt: CaF₂ 30 bis 40 Gew.%, MgO 3 bis 20 Gew.% Rest ZnO. Diese Pulvermischung wird anschließend zu einer keramischen Masse gesintert. Diese keramische Sintermasse wird nach Abkühlung auf Raumtemperatur in Mischpartikel zermahlen, beispielsweise in einer Trommelmühle, bis auf eine Teilchengröße zwischen 5 und 150 µm.The following ceramic powders are mixed to produce a abradable coating for engine components with an abradable or an abrasive material component in the form of particles and a connecting material component: CaF₂ 30 to 40 wt.%, MgO 3 to 20 wt.% Rest ZnO. This powder mixture is then sintered into a ceramic mass. After cooling to room temperature, this ceramic sintered mass is ground into mixed particles, for example in a drum mill, down to a particle size between 5 and 150 μm.
Für Anstreifbeläge, die vorzugsweise als Einlaufbeläge eingesetzt werden, wird dabei ein hoher CaF₂-Anteil bis 40 Gew. % bei niedrigem MgO-Anteil um 5 Gew. % gefahren. Für Anstreifbeläge, die vorzugsweise als Anlaufbeläge eingesetzt werden, wird dabei ein geringerer CaF₂-Anteil unter 35 Gew. % bei hohem MgO-Anteil bis 20 Gew. % gefahren.For abradable coverings, which are preferably used as run-in coverings, a high CaF₂ content of up to 40% by weight with a low MgO content of 5% by weight is used. For abradable coverings, which are preferably used as tarnishing coverings, a lower CaF₂ content below 35% by weight with a high MgO content of up to 20% by weight is used.
Aus den derartig hergestellten Mischpartikeln wird ein Anstreifbelag durch Plasmaspritzen mit einem Plasmaspritzbrenner unter einer Spannung von 50 bis 60 V bei einem Strom von 300 bis 400 A hergestellt, wobei ein Primärgasstrom aus Stickstoff von 60 bis 80 Liter pro Minute und ein Sekundärgasstrom aus Wasserstoff von 70 bis 80 Liter pro Minute eingehalten wird. Bei einem Spritzabstand von 75 bis 225 mm wird mit einem Treibgasstrom aus Stickstoff von 20 bis 40 Liter pro Minute eine Bauteiloberfläche plasmagespritzt, bis eine Dicke von mehreren Millimetern erreicht ist. Die Porosität kann dabei im wesentlichen durch den Spritzabstand und durch den Treibgasstrom variiert und eingestellt werden.From the mixed particles produced in this way, a brush coating is produced by plasma spraying with a plasma spray gun under a voltage of 50 to 60 V at a current of 300 to 400 A, a primary gas stream of nitrogen of 60 to 80 liters per minute and a secondary gas stream of hydrogen of 70 up to 80 liters per minute. At a spraying distance of 75 to 225 mm, a component gas surface is plasma sprayed with a nitrogen gas flow of 20 to 40 liters per minute until a thickness of several millimeters is reached. The porosity can be varied and adjusted essentially by the spraying distance and by the propellant gas flow.
Wie in Beispiel 1 werden je nach Anforderung an den Anstreifbelag die Mischpartikel hergestellt und anschließend mit einem Flammspritzverfahren aufgebracht. Dazu wird mit einem Flammspritzbrenner ein Brenngasstrom von 30 bis 40 Liter pro Minute aus Azetylen mit einem Sekundärgasstrom aus Sauerstoff von 30 bis 40 Liter pro Minute eingehalten. Bei einem Spritzabstand von 75 bis 225 mm wird mit einem Treibgasstrom aus Stickstoff von 30 bis 45 Liter pro Minute die Bauteiloberfläche mehrfach flammgespritzt bis eine ausreichende Belagdicke von mehreren Millimetern erreicht ist. Die Porosität kann dabei im wesentlichen durch den Spritzabstand und durch den Treibgasstrom variiert und eingestellt werden.As in Example 1, the mixed particles are produced depending on the requirements of the abradable coating and then applied using a flame spraying process. For this purpose, a fuel gas flow of 30 to 40 liters per minute from acetylene with a secondary gas flow from oxygen of 30 to 40 liters per minute is maintained with a flame spray burner. At a spraying distance of 75 to 225 mm, the component surface is flame-sprayed several times with a nitrogen gas flow of 30 to 45 liters per minute until a sufficient covering thickness of several millimeters is reached. The porosity can be varied and adjusted essentially by the spraying distance and by the propellant gas flow.
Claims (13)
CaF₂ 30 bis 40 Gew.%
MgO 3 bis 20 Gew.%
ZnO Rest.A method according to claim 9 or 10, characterized in that the following ceramic powders are mixed to produce the coating powder
CaF₂ 30 to 40% by weight
MgO 3 to 20% by weight
ZnO rest.
CaF₂ 30 bis 32 Gew.%
MgO 10 bis 20 Gew.%
ZnO Rest.A method according to claim 9 or 10, characterized in that the following ceramic powders are mixed to produce the coating powder
CaF₂ 30 to 32% by weight
MgO 10 to 20% by weight
ZnO rest.
CaF₂ 35 bis 40 Gew.%
MgO 3 bis 10 Gew.%
ZnO Rest.A method according to claim 9 or 10, characterized in that the following ceramic powders are mixed to produce the coating powder
CaF₂ 35 to 40% by weight
MgO 3 to 10% by weight
ZnO rest.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4427264A DE4427264C2 (en) | 1994-07-30 | 1994-07-30 | Brushing surface for engine components and method for its production |
| DE4427264 | 1994-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0694627A1 true EP0694627A1 (en) | 1996-01-31 |
Family
ID=6524685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95111213A Withdrawn EP0694627A1 (en) | 1994-07-30 | 1995-07-18 | Coating for driving elements |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0694627A1 (en) |
| JP (1) | JPH08114150A (en) |
| DE (1) | DE4427264C2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1375696A2 (en) * | 2002-06-10 | 2004-01-02 | MTU Aero Engines GmbH | Coatingsystem for the rotor/stator sealing of a turbo machine |
| DE102012217617A1 (en) * | 2012-09-27 | 2014-03-27 | Siemens Aktiengesellschaft | Component used in e.g. oxygen lance, has zinc oxide-containing layer provided on substrate and having surface layer consisting of zinc oxide crystals, and intermediate layer consisting of specific intermetallic compound |
| EP2752393A1 (en) * | 2013-01-02 | 2014-07-09 | IPGR International Partners in Glass Research | Device for handling hot melted glass and method for making such a device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007019476A1 (en) | 2007-04-25 | 2008-11-06 | Mtu Aero Engines Gmbh | Method of producing a scuffing pad |
| EP2330228B1 (en) * | 2009-12-03 | 2017-09-27 | Oerlikon Metco AG, Wohlen | Spray material, thermal spray layer and cylinder with a thermal spray layer |
| DE102014008922A1 (en) * | 2014-06-17 | 2015-12-17 | Mtu Friedrichshafen Gmbh | Method for treating a surface |
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| EP1375696A2 (en) * | 2002-06-10 | 2004-01-02 | MTU Aero Engines GmbH | Coatingsystem for the rotor/stator sealing of a turbo machine |
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| DE102012217617A1 (en) * | 2012-09-27 | 2014-03-27 | Siemens Aktiengesellschaft | Component used in e.g. oxygen lance, has zinc oxide-containing layer provided on substrate and having surface layer consisting of zinc oxide crystals, and intermediate layer consisting of specific intermetallic compound |
| EP2752393A1 (en) * | 2013-01-02 | 2014-07-09 | IPGR International Partners in Glass Research | Device for handling hot melted glass and method for making such a device |
| WO2014106613A1 (en) * | 2013-01-02 | 2014-07-10 | Ipgr International Partners In Glass Research | Device for handling hot melted glass and method for making such a device |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4427264C2 (en) | 1996-09-26 |
| DE4427264A1 (en) | 1996-02-01 |
| JPH08114150A (en) | 1996-05-07 |
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