EP2222885B1 - Kobaltlegierung, faserbildende platte und verfahren zur herstellung von mineralwolle - Google Patents
Kobaltlegierung, faserbildende platte und verfahren zur herstellung von mineralwolle Download PDFInfo
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- EP2222885B1 EP2222885B1 EP08856969.4A EP08856969A EP2222885B1 EP 2222885 B1 EP2222885 B1 EP 2222885B1 EP 08856969 A EP08856969 A EP 08856969A EP 2222885 B1 EP2222885 B1 EP 2222885B1
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- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000011490 mineral wool Substances 0.000 title claims description 10
- 229910000531 Co alloy Inorganic materials 0.000 title description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 88
- 239000000956 alloy Substances 0.000 claims description 88
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 26
- 239000011651 chromium Substances 0.000 claims description 24
- 229910052715 tantalum Inorganic materials 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 15
- 239000011707 mineral Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 3
- 210000002268 wool Anatomy 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 230000002238 attenuated effect Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- 150000001247 metal acetylides Chemical class 0.000 description 19
- 239000011521 glass Substances 0.000 description 17
- 238000012681 fiber drawing Methods 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000000470 constituent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 229910003468 tantalcarbide Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- -1 chromium carbides Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910000753 refractory alloy Inorganic materials 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
Definitions
- the present invention relates to a metal alloy for use at a very high temperature, particularly used in a process for manufacturing mineral wool by fiberizing a molten mineral composition, or more generally for the constitution of tools having high temperature strength. in an oxidizing medium such as molten glass, and cobalt-based alloys that can be used at high temperature, in particular for the production of articles for producing and / or heat-transforming glass or other mineral material, such as of mineral wool making machinery.
- a fiber drawing technique consists in continuously dropping liquid glass inside a set of revolution parts rotating at a very high speed of rotation about their vertical axis.
- a centerpiece called “plate”, more often referred to in the art as the “spinner”, receives the glass against a so-called “band” wall pierced with holes, which the glass passes under the effect of centrifugal force for to escape from all parts in the form of melted filaments.
- An annular burner located above the outside of the plate, producing a downward gas flow along the outer wall of the strip, deflects these filaments downwardly by stretching them. These then “solidify” in the form of glass wool.
- the plate is a fiber-drawing tool that is very thermally stressed (thermal shocks during start-ups and shutdowns, and establishment in stabilized use of a temperature gradient along the part), mechanically (centrifugal force, erosion due to the passage of the glass) and chemically (oxidation and corrosion by the molten glass, and by the hot gases coming out of the burner around the plate). Its main modes of deterioration are: the deformation by hot creep of the vertical walls, the appearance of horizontal or vertical cracks, the erosion wear of the fiberizing orifices, which require the pure and simple replacement of the organs. Their constituent material must therefore withstand during a production time long enough to remain compatible with the technical and economic constraints of the process. For this purpose, materials with a certain ductility, creep resistance and resistance to corrosion and / or oxidation are sought.
- refractory alloys are based on chromium, cobalt (refractory element which brings to the matrix of the alloy an intrinsic strength at high temperature improved) and nickel (to stabilize the face-centered cubic crystal lattice of the Co).
- WO-A-99/16919 a cobalt-based alloy having improved mechanical properties at high temperature, comprising the following elements (in weight percent of the alloy): Cr 26 to 34% Or 6 to 12% W 4 to 8% Your 2-4% VS 0.2 to 0.5% Fe less than 3% Yes less than 1% mn less than 0.5% Zr less than 0.1% the remainder being constituted by cobalt and unavoidable impurities, the molar ratio of tantalum with respect to carbon being of the order of 0.4 to 1.
- the alloys described in the previous patent applications may especially be used in industrial conditions for the fibering of new glass compositions, in particular basaltic, whose melting temperature is higher than that of the compositions conventionally used in processes for obtaining wool of glass.
- Such compositions are described in the following description.
- a fibering plate made from the alloy described in Example 6 of WO 2005/052208 can withstand, over relatively long periods, melting glass temperatures in the range of 1200 to 1240 ° C., corresponding to a metal temperature of between 1160 and 1210 ° C., depending on the profile of the plate.
- the present invention aims at providing still improved alloys whose high temperature mechanical resistance is increased, making it possible to work at a temperature (for the metal) of up to 1200 ° C., or even at higher temperatures, and having a duration improved life under such fiber drawing conditions.
- the subject of the present invention is a cobalt-based alloy, further comprising chromium, and carbon, which contains the following elements (the proportions being indicated in percentage by weight of the alloy): Cr 23 to 34% Ti 0.2 to 5% Your 0.5 to 7% VS 0.2 to 1.2% Or less than 5% Fe less than 3% Yes less than 1% mn less than 0.5% the rest being cobalt and unavoidable impurities.
- the alloy according to the present invention differs from the alloys incorporating carbides of Ti and Ta described in the application WO 2005/052208 (See in particular Examples 6 and 7), in that the nickel content is substantially lower than those described in this publication (8.7% by weight for the alloys of Examples 6 and 7).
- the presence of such a quantity of nickel was necessary to extend the temperature stability domain of the face-centered cubic crystal structure of the cobalt matrix (see for example page 7 lines 18-21 of W02005 / 052208 or page 8 lines 29-32 and page 17 lines 25-30 of WO 2001/90429 ).
- tests conducted on alloys demand WO99 / 16919 have shown that the presence of a substantial amount of nickel appears preferable to limit the oxidation of such alloys when used in a high temperature fiber drawing process.
- the properties of the alloy compositions according to the present invention appeared to be greater than those of the previously described alloys.
- the lifetimes of the plates obtained from the alloys according to the invention during a high temperature fiber drawing process appeared very substantially improved.
- Carbon is an essential constituent of the alloy, necessary for the formation of metal carbide precipitates.
- the carbon content directly determines the amount of carbides present in the alloy. It is at least 0.2% by weight to obtain the minimum reinforcement desired, preferably at least 0.6% by weight, but preferably limited to at most 1.2% by weight to prevent the alloy from becoming hard and difficult to machine because of too high density of reinforcements.
- the lack of ductility of the alloy at such levels prevents it from accommodating without breaking an imposed deformation (for example of thermal origin) and withstanding sufficiently the propagation of cracks.
- chromium contributes to the intrinsic mechanical strength of the matrix in which it is present in part in solid solution, and in some cases also in the form of carbides essentially Cr 23 C 6 type in fine dispersion inside grains where they provide resistance to intragranular creep or in the form of Cr 7 C 3 or Cr 23 C 6 type carbides present at the grain boundaries, which prevent grain-on-grain slippage thereby contributing. also to the intergranular reinforcement of the alloy.
- Chromium contributes to the corrosion resistance as a chromium oxide precursor forming a protective layer on the surface exposed to the oxidizing medium. A minimal amount of chromium is required for the formation and maintenance of this protective layer. Too high a chromium content, however, is detrimental to strength and toughness at elevated temperatures, as it leads to too high rigidity and too low stress elongation that is incompatible with high temperature stresses.
- the chromium content of an alloy which can be used according to the invention is 23 to 34% by weight, preferably of the order of 26 to 32% by weight, advantageously of approximately 27 to 30% by weight. .
- the nickel, present in the alloy in the form of a solid solution with cobalt, is present in an amount of less than 5% by weight of the alloy.
- the amount of nickel present in the alloy is less than 4%, or even less than 3% or even less than 2% by weight of the alloy.
- the threshold at which the Ni is present only in the form of unavoidable impurities, excellent life values of plates, not yet observed so far, have also been obtained.
- unavoidable impurities is meant within the meaning of the present invention that the nickel is not present intentionally in the composition of the alloy but that it is introduced in the form of impurities contained in at least one of the main elements of the alloy (or in at least one of the precursors of said main elements).
- nickel was almost always present in the form of unavoidable impurities of at least 0.3% by weight and most often at least 0.5% by weight. or at least 0.7% by weight.
- percentages of nickel in the alloy less than 0.3% by weight must also be considered as part of the invention, but the cost generated by such purity would then make the cost of the alloy too expensive to allow the commercial viability of the fiber drawing process.
- Titanium is a more common element and less expensive than tantalum, so it penalizes less the final cost of the alloy.
- the fact that this element is light can also be an advantage.
- a minimum amount of titanium of 0.2 to 5% by weight of the alloy appeared preferable to produce a sufficient amount of TiC carbides, certainly due to the solubility of titanium in the cobalt cfc matrix.
- a titanium content of the order of 0.5 to 4% seems advantageous, especially 0.6 to 3%. Excellent results have been obtained for alloys comprising Ti contents between 0.8 and 2%.
- the tantalum present in the alloy is partly in solid solution in the cobalt matrix of which this heavy atom locally distorts the crystal lattice and hinders or even blocks the progression of the dislocations when the material is subjected to mechanical stress, thus contributing to the intrinsic strength of the matrix.
- the minimum content of tantalum for the formation of mixed carbides with the Ti according to the invention is of the order of 0.5%, preferably of the order of 1% and very preferably of the order of 1, 5% or even 2%.
- the upper limit of the tantalum content can be chosen to be about 7%.
- the tantalum content is preferably of the order of 2 to 6%, in particular of 1.5 to 5%.
- the tantalum content is very preferably less than 5%, even 4.5% or even 4% and advantageously close to 3.
- a small amount of tantalum has the double advantage of substantially reducing the overall cost of the alloy but also to allow easy machining of said alloy. The higher the content of tantalum, the harder the alloy is, that is to say difficult to form.
- the alloys according to the invention are preferably free of Ce, La, B, Y, Dy, Re and other rare earths.
- the alloys that can be used according to the invention which contain highly reactive elements, can be shaped by casting, in particular by inductive melting in at least partially inert atmosphere and casting in a sand mold.
- the casting may optionally be followed by a heat treatment at a temperature that may go beyond the fiberizing temperature.
- the invention also relates to a method of manufacturing an article by casting from the alloys described above as an object of the invention.
- the process may comprise at least one cooling stage, after casting and / or after or during a heat treatment, for example by cooling in air, in particular with a return to ambient temperature.
- the alloys that are the subject of the invention can be used to manufacture all kinds of parts mechanically stressed at high temperature and / or made to work in an oxidizing or corrosive medium.
- the invention also relates to such articles made from an alloy according to the invention, in particular by foundry.
- Such applications include the manufacture of articles used for the development or hot processing of glass, for example fiber plates for the manufacture of mineral wool.
- the subject of the invention is also a process for the manufacture of mineral wool by internal centrifugation, in which a flow of molten mineral matter is poured into a fiber-drawing plate whose peripheral band is pierced with a multitude of orifices through which filaments of molten mineral material escape, which are then drawn into wool by the action of a gas, the temperature of the mineral material in the plate being at least 1200 ° C. and the fibering plate being made of an alloy as defined above.
- the alloys according to the invention thus make it possible to fiberize glass or a similar molten mineral composition having a liquidus temperature T liq of the order of 1130 ° C or more, for example from 1130 to 1200 ° C, in particular 1170 ° C or more.
- the fiberization of these molten mineral compositions can be carried out in a temperature range (for the melt composition reaching the plate) between T liq and T log2,5 where T log2,5 is the temperature at which the composition
- T log2,5 is the temperature at which the composition
- the fondue has a viscosity of 2.5 poise (dPa.s), typically of the order of 1200 ° C or higher, e.g. 1240-1250 ° C or higher.
- compositions of mineral material it may be preferred compositions containing a significant amount of iron, which are less corrosive vis-à-vis the constituent metal of the fiberizing members.
- the process according to the invention advantageously uses a composition of oxidizing mineral material, in particular with respect to chromium, capable of repairing or reconstituting the protective layer of Cr 2 O 3 oxide which is established on the surface.
- compositions containing iron essentially in ferric form may be preferred, in particular with a molar ratio of the degrees oxidation II and III, expressed in the ratio FeO FeO + Fe 2 ⁇ O 3 on the order of 0.1 to 0.3, especially 0.15 to 0.20.
- the mineral material composition contains a high iron content allowing rapid kinetics of reconstitution of chromium oxide with a level of iron oxide (so-called "total iron” rate, corresponding to the total content of iron expressed conventionally in the form of Fe 2 O 3 equivalent) of at least 3%, preferably at least 4%, in particular of the order of 4 to 12%, in particular of at least 5%.
- total iron a level of iron oxide
- this corresponds to a ferric iron content Fe 2 O 3 alone of at least 2.7%, preferably at least 3.6%
- compositions are known in particular from WO 99/56525 and advantageously comprise the following constituents: SiO 2 38-52%, preferably 40-48% Al 2 O 3 17-23% SiO 2 + Al 2 O 3 56-75%, preferably 62-72% RO (CaO + MgO) 9-26%, preferably 12-25% MgO 4-20%, preferably 7-16% MgO / CaO ⁇ 0.8, preferably ⁇ 1.0 or ⁇ 1.15 R 2 O (Na 2 O + K 2 O) ⁇ 2% P 2 O 5 0-5% Total iron (Fe 2 O 3 ) ⁇ 1.7%, preferably ⁇ 2% B 2 O 3 0-5% MnO 0-4% TO 2 0-3%
- compositions of WO-00/17117 are particularly suitable for the process according to the invention.
- SiO 2 39-35% preferably 40-52% Al 2 O 3 16-27% - 16-25%
- the compositions have iron oxide levels of between 5 and 12%, especially between 5 and 8%, which can make it possible to obtain a fire resistance of the mineral wool mattresses.
- the invention can be applied to the manufacture of very diverse articles, when they must have a high mechanical strength in an oxidizing and / or corrosive medium, particularly at high temperature.
- these alloys can be used to make any type of refractory alloy fixed or moving parts for operating or operating a high temperature heat treatment furnace (above 1200 ° C.), a heat exchanger or reactor of the chemical industry. It can thus be for example hot fan blades, cooking support, charging material, etc. They can also be used to produce any type of heating resistor intended to operate in a hot oxidizing atmosphere, and to realize Turbine components, used in land, sea or air vehicle engines or in any other application that does not target vehicles, eg power plants.
- a high temperature heat treatment furnace above 1200 ° C.
- a heat exchanger or reactor of the chemical industry. It can thus be for example hot fan blades, cooking support, charging material, etc.
- They can also be used to produce any type of heating resistor intended to operate in a hot oxidizing atmosphere, and to realize Turbine components, used in land, sea or air vehicle engines or in any other application that does not target vehicles, eg power plants.
- the invention thus relates to the use in an oxidizing atmosphere at a temperature of at least 1200 ° C of an article consisting of an alloy as defined above.
- a molten charge is prepared for the following composition which is then formed by simply casting into a mold of sand: Cr 27.83% Or 1.33% VS 0.36% Your 3.08% Ti 1.34% Fe 2.00% mn ⁇ 0.5% Yes ⁇ 0.3% Zr ⁇ 0,1% sum other impurities ⁇ 1%, the rest being cobalt.
- the casting is followed by a heat treatment comprising a solution phase for 2 hours at 1200 ° C. and a secondary carbide precipitation phase for 10 hours at 1000 ° C., each of these stages ending with air cooling. to room temperature.
- a second fibering plate 400 mm in diameter and having the same characteristics is prepared from a melted filler of the following composition: Cr 28.84% Or 0.78% VS 0.41% Your 2.95% Ti 1.21% Fe 0.66% mn ⁇ 0.5% Yes ⁇ 0.3% Zr ⁇ 0,1% sum other impurities ⁇ 1%, the rest being cobalt.
- the capacity of the plates thus formed was evaluated in the fiberglass fiber application. More specifically the plates were placed on a industrial fiber drawing line of a basaltic glass composition: SiO 2 Al 2 O 3 Total iron (Fe 2 O 3 ) CaO MgO Na 2 O K 2 O Various 45.7 19 7.7 12.6 0.3 8 5.1 1
- the plates are used with two different shots of 10 and 12,5 tons per day until their decision is decided following the ruin of the plate, declared by a visible deterioration or by a quality of fiber produced become insufficiently good .
- the temperature of the mineral composition arriving in the plate is of the order of 1200 to 1240 ° C.
- the temperature of the metal according to the profile of the plate is between 1160 and 1210 ° C.
- the solidus temperature of the alloy constituting the plates is then measured according to conventional differential thermal analysis (DTA) techniques, after their use in the preceding fiberizing process.
- DTA differential thermal analysis
- solidus temperature is meant in the sense of your present description, the melting temperature of the alloys in equilibrium. Due to a different method of analysis, it should be noted that the values obtained from the solidus temperatures reported in Table 2 differ somewhat from the values previously obtained in WO 2005/052208 . However, the relative differences in melting temperature between the alloys according to the invention and the reference alloy remain identical, whatever the method used.
- the solidus temperature of the alloys according to the invention is approximately 10 ° C. higher than the alloys of the prior art in all cases, which reflects a greater refractoriness. Because of the relative proximity between the operating temperature of the plate in the fiberizing process and the melting temperature of the alloy constituting the plate, such an improvement is extremely significant and could alone justify your superior properties. of high temperature strength, as observed on the present alloys.
- Example 1 The high temperature strength properties of the alloys of Example 1 according to the invention and of Example 3 according to the prior art were evaluated in tests of resistance to three-point bending at 1250 ° C. load of 31 MPa for a period of 200 hours. The tests were carried out for each alloy on a series of parallelepipedic specimens of 30 mm wide and 3 mm thick, the load being exerted in the middle of a center distance of 37 mm. The results are shown in Table 3. Table 3 shows the slope of the three-point creep curves obtained for each alloy, said slope illustrating the rate of deformation (in ⁇ m.h -1 ) of the specimen by creep.
- Table 3 summarizes all the results obtained, giving for each alloy the average creep rates, as well as the maximum and minimum values observed over the entire set of test pieces.
- Table 3 Creep velocity in three-point bending ( ⁇ m.h -1 ) Average value Minimum value Maximum value Alloy example 1 (according to the invention) 4.1 2.8 5.7 Alloy example 3 (comparative) 17.7 3.5 30.8
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Continuous Casting (AREA)
- Glass Compositions (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Claims (11)
- Legierung, dadurch gekennzeichnet, dass sie die folgenden Bestandteile enthält, (die Anteile sind als Gewichtsprozente der Legierung angegeben):
Cr 23 bis 34 % Ti 0,2 bis 5 % Ta 0,5 bis 7 % C 0,2 bis 1,2 % Ni weniger als 5 % Fe weniger als 3 % Si weniger als 1 % Mn weniger als 0,5 % - Legierung nach Anspruch 1, dadurch gekennzeichnet, dass sie weniger als 4 Gewichts-% Ni, bevorzugt weniger als 3 Gewichts-% Ni und besonders bevorzugt weniger als 2 Gewichts-% Ni enthält.
- Legierung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass sie wenigstens 0,2 % und bevorzugt wenigstens 0,6 Gewichts-% Kohlenstoff enthält.
- Legierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass sie die Metalle Ti und Ta in einem Molverhältnis zu Kohlenstoff (Ti + Ta)/C von etwa 0,9 bis 2, insbesondere von 0,9 bis 1,5, enthält.
- Legierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass sie 0,5 bis 4 Gewichts-% Ti, bevorzugt von etwa 0,6 bis 3 Gewichts-% Ti enthält.
- Legierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Gehalt an Tantal im Bereich von 1 bis 7 %, insbesondere von etwa 2 bis 6 % ist.
- Legierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Gehalt an Chrom im Bereich von 26 bis 32 %, insbesondere von etwa 27 bis 30 % ist.
- Erzeugnis für die Herstellung von Mineralwolle gefertigt aus einer Legierung nach einem der Ansprüche 1 bis 7, insbesondere durch Gießtechnik.
- Spinnteller für die Herstellung von Mineralwolle gefertigt aus einer Legierung nach einem der Ansprüche 1 bis 8, insbesondere durch Gießtechnik.
- Verfahren zur Herstellung von Mineralwolle durch innere Zentrifugation, bei der man einen Durchfluss geschmolzener mineralischer Materie durch einen Spinnteller nach Anspruch 9 abfliessen lässt, dessen äußere Wand von einer Vielzahl von Öffnungen durchbohrt ist, durch die Filamente aus geschmolzenem Material austreten, die anschließend unter Einwirkung eines Gases zu Wolle ausgezogen werden, wobei die Temperatur der mineralischen Materie im Spinnteller mindestens 1200°C ist.
- Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die geschmolzene mineralische Materie eine Liquidustemperatur von etwa 1130°C oder mehr, insbesondere 1170°C oder mehr, hat.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL08856969T PL2222885T3 (pl) | 2007-11-30 | 2008-11-27 | Stop kobaltowy, tarcza do formowania włókien i sposób wytwarzania wełny mineralnej |
SI200831173T SI2222885T1 (sl) | 2007-11-30 | 2008-11-27 | Kobaltova zlitina, predilni kroĹľnik in postopek za pripravo mineralne volne |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0759451A FR2924442B1 (fr) | 2007-11-30 | 2007-11-30 | Alliage refractaire, assiette de fibrage et procede de fabrication de laine minerale |
PCT/FR2008/052140 WO2009071847A1 (fr) | 2007-11-30 | 2008-11-27 | Alliage refractaire, assiette de fibrage et procede de fabrication de laine minerale |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2222885A1 EP2222885A1 (de) | 2010-09-01 |
EP2222885B1 true EP2222885B1 (de) | 2014-01-01 |
Family
ID=39758463
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP08856969.4A Active EP2222885B1 (de) | 2007-11-30 | 2008-11-27 | Kobaltlegierung, faserbildende platte und verfahren zur herstellung von mineralwolle |
Country Status (20)
Country | Link |
---|---|
US (1) | US8262964B2 (de) |
EP (1) | EP2222885B1 (de) |
JP (1) | JP5461418B2 (de) |
KR (1) | KR101571143B1 (de) |
CN (1) | CN101878318B (de) |
BR (1) | BRPI0819639B8 (de) |
CA (1) | CA2706450C (de) |
CL (1) | CL2010000574A1 (de) |
CO (1) | CO6210750A2 (de) |
DK (1) | DK2222885T3 (de) |
EA (1) | EA017210B1 (de) |
EG (1) | EG26118A (de) |
ES (1) | ES2453499T3 (de) |
FR (1) | FR2924442B1 (de) |
HR (1) | HRP20140302T1 (de) |
PL (1) | PL2222885T3 (de) |
SI (1) | SI2222885T1 (de) |
UA (1) | UA98183C2 (de) |
WO (1) | WO2009071847A1 (de) |
ZA (1) | ZA201003834B (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH709112A8 (de) | 2014-01-14 | 2015-09-15 | Sager Ag | Mineralfaserkomposition. |
WO2018158509A1 (fr) * | 2017-02-28 | 2018-09-07 | Saint-Gobain Seva | Alliage pour assiette de fibrageid50000077372917 pub copy null |
ES2913751T3 (es) | 2017-11-20 | 2022-06-06 | Stm Tech S R L | Aleación a base de cobalto con una alta resistencia a altas temperaturas, hiladora para la producción de fibras minerales que comprende dicha aleación y procedimiento para la producción de fibras minerales que usa una hiladora de este tipo |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3881918A (en) * | 1974-05-09 | 1975-05-06 | Owens Corning Fiberglass Corp | Cobalt-base superalloy |
US4820324A (en) * | 1987-05-18 | 1989-04-11 | Owens-Corning Fiberglas Corporation | Glass corrosion resistant cobalt-based alloy having high strength |
US20030221756A1 (en) | 1997-09-29 | 2003-12-04 | Isover Saint Gobain | Cobalt based alloy, article made from said alloy and method for making same |
US6266979B1 (en) * | 1999-09-02 | 2001-07-31 | Johns Manville International, Inc. | Spinner disc alloy |
US6361836B1 (en) * | 1999-12-09 | 2002-03-26 | Johns Manville International, Inc. | Method of making spinner discs for rotary fiberization processes |
FR2809387B1 (fr) | 2000-05-23 | 2002-12-20 | Saint Gobain Isover | Procede de fabrication de laine minerale, alliages a base de cobalt pour le procede et autres utilisations |
JP4032654B2 (ja) * | 2001-03-06 | 2008-01-16 | Jfeスチール株式会社 | 耐ピックアップ性・耐高温摩耗特性に優れた表面被覆材料 |
JP4128832B2 (ja) * | 2002-09-09 | 2008-07-30 | 大平洋特殊鋳造株式会社 | ガラス繊維成形スピナ−用耐熱合金およびスピナ− |
FR2862662B1 (fr) * | 2003-11-26 | 2007-01-12 | Saint Gobain Isover | Alliage refractaire et procede de fabrication de laine minerale |
-
2007
- 2007-11-30 FR FR0759451A patent/FR2924442B1/fr not_active Expired - Fee Related
-
2008
- 2008-11-27 EP EP08856969.4A patent/EP2222885B1/de active Active
- 2008-11-27 CN CN200880118426.XA patent/CN101878318B/zh active Active
- 2008-11-27 BR BRPI0819639A patent/BRPI0819639B8/pt not_active IP Right Cessation
- 2008-11-27 CA CA2706450A patent/CA2706450C/fr not_active Expired - Fee Related
- 2008-11-27 PL PL08856969T patent/PL2222885T3/pl unknown
- 2008-11-27 ES ES08856969.4T patent/ES2453499T3/es active Active
- 2008-11-27 WO PCT/FR2008/052140 patent/WO2009071847A1/fr active Application Filing
- 2008-11-27 US US12/744,496 patent/US8262964B2/en active Active
- 2008-11-27 UA UAA201008139A patent/UA98183C2/uk unknown
- 2008-11-27 DK DK08856969.4T patent/DK2222885T3/da active
- 2008-11-27 JP JP2010535433A patent/JP5461418B2/ja active Active
- 2008-11-27 EA EA201000913A patent/EA017210B1/ru not_active IP Right Cessation
- 2008-11-27 KR KR1020107011637A patent/KR101571143B1/ko not_active IP Right Cessation
- 2008-11-27 SI SI200831173T patent/SI2222885T1/sl unknown
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2010
- 2010-05-17 EG EG2010050806A patent/EG26118A/en active
- 2010-05-26 CO CO10063134A patent/CO6210750A2/es active IP Right Grant
- 2010-05-28 ZA ZA2010/03834A patent/ZA201003834B/en unknown
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2014
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Also Published As
Publication number | Publication date |
---|---|
US20100244310A1 (en) | 2010-09-30 |
EG26118A (en) | 2013-03-05 |
WO2009071847A1 (fr) | 2009-06-11 |
FR2924442A1 (fr) | 2009-06-05 |
HRP20140302T1 (en) | 2014-05-23 |
EA201000913A1 (ru) | 2010-10-29 |
KR20100090783A (ko) | 2010-08-17 |
PL2222885T3 (pl) | 2014-05-30 |
UA98183C2 (uk) | 2012-04-25 |
CN101878318B (zh) | 2014-02-19 |
BRPI0819639A2 (pt) | 2015-05-05 |
CN101878318A (zh) | 2010-11-03 |
CA2706450C (fr) | 2016-10-04 |
KR101571143B1 (ko) | 2015-11-23 |
JP5461418B2 (ja) | 2014-04-02 |
SI2222885T1 (sl) | 2014-05-30 |
CL2010000574A1 (es) | 2010-12-10 |
DK2222885T3 (da) | 2014-04-07 |
EA017210B1 (ru) | 2012-10-30 |
CA2706450A1 (fr) | 2009-06-11 |
ZA201003834B (en) | 2011-02-23 |
CO6210750A2 (es) | 2010-10-20 |
AU2008333024A1 (en) | 2009-06-11 |
EP2222885A1 (de) | 2010-09-01 |
ES2453499T3 (es) | 2014-04-08 |
US8262964B2 (en) | 2012-09-11 |
FR2924442B1 (fr) | 2010-02-26 |
BRPI0819639B8 (pt) | 2018-02-27 |
JP2011504969A (ja) | 2011-02-17 |
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