GB2159144A - Method of manufacturing refractory bodies or compositions - Google Patents
Method of manufacturing refractory bodies or compositions Download PDFInfo
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- GB2159144A GB2159144A GB08512942A GB8512942A GB2159144A GB 2159144 A GB2159144 A GB 2159144A GB 08512942 A GB08512942 A GB 08512942A GB 8512942 A GB8512942 A GB 8512942A GB 2159144 A GB2159144 A GB 2159144A
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 9
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001597 celsian Inorganic materials 0.000 claims abstract description 7
- 238000010304 firing Methods 0.000 claims abstract description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 5
- 239000007767 bonding agent Substances 0.000 claims abstract description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 11
- 239000010431 corundum Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 2
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 230000035939 shock Effects 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000274 aluminium melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 229910052849 andalusite Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- -1 corundum Chemical compound 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/105—Refractories from grain sized mixtures containing chromium oxide or chrome ore
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
A method of manufacturing refractory bodies or compositions includes forming a starting mixture containing one or more of an aluminosilicate, aluminium oxide, silicon dioxide, zirconium silicate and silicon carbide, Al2O3 and SiO2 and also containing a bonding agent. 0.5 to 40% by weight barium sulphate with respect to the starting mixture, 2 to 20% by weight chromium (III) oxide with respect to the starting mixture and 3 to 25 parts by weight calcium fluoride, with respect to 100 parts by weight of the added barium sulphate, are also added to the mixture. The mixture is fired at 1100 to 1600 DEG C and Celsian is formed during the firing.
Description
SPECIFICATION
Method of manufacturing refractory bodies or compositions.
The invention relates to a method of manufacturing refractory bodies or compositions, particularly for the lining of furnances or vessels for molten metals, and to bodies and compositions made by such a method.
British Patent Specification No. 2147893A of the present appli cants discloses such a method which includes forming a starting mixture containing one or more of an aluminosilicate, aluminium oxide, silicon dioxide, zirconium silicate and silicon carbide, Awl203 and SiO2 and the mixture also containing a bonding agent, adding 0.5 to 40% by weight barium sulphate with respect to the starting mixture, and 3 to 25 parts by weight calcium fluoride, with respect to 100 parts by weight of the added barium sulphate, and firing the mixture at 100 to 1600"C whereby Celsian (BaO.AI203.2 SiO2) is formed during the firing.
The refractory bodies or compositions made in accordance with the prior specification contain Celsian and attain a high cold compression strength at relatively low firing temperatures and have a high resistance to molten metals and/or slags and to corrosive gases and vapours. The refractory bodies or compositions are therefore suitable for use in aluminium smelting furnaces, rotary tubular cement furnaces, refuse combustion furnaces, in the lining of glass bath furnaces and in blast furnaces.
It has now been found that the refractory bodies and compositions made in accordance with the prior patent specification, in particular their properties at high temperatures, such as refractoriness under load measured in accordance with DIN 51064 (ta value) and the maximum temperature at which they may be used and also their thermal shock resistance can be improved by adding 2 to 20% and preferably 2 to 14% by weight chromium (III) oxide, preferably in fine grained form, to the starting mixture during their manufacture.
The refractory bodies and compositions made by the method in accordance with the invention have a high maximum use temperature as evidenced by the increased value for the refractoriness under load measured in accordance with DIN 51064 (ta value) and a high resistance to infiltration and corrosion by gases, slags and metal melts. An increase in the thermal shock resistance measured in accordance with
DIN 51068 (water quenching) is also exhibited by comparison with refractory bodies and compositions containing no chromium oxide.
In one embodiment of the invention the starting mixture is based on aluminium oxide, e.g. corundum, and/or aluminosilicate and contains 1 to 15%, preferably 2 to 10%, by weight zirconium oxide and optionally also 1 to 15%, preferably 2 to 10%, by weight silicon carbide. Refractory bodies or compositions made from this starting mixture are characterised by a further improved corrosion resistance to slags.
Further features and advantages of the invention will be apparent from examples 1 to 4 of which details are set forth in the table. Example 1 is merely a comparative example.
In all the examples the starting mixture includes the alumina-rich materials Corundum, Andalusite and calcined aluminia and the mixture of example 4 also includes zirconium oxide and silicon carbide.
The fired refractory bodies produced by the method of example 1 do not contain Celsian and the Al2O.Cr2O mixed crystal which is produced in the firing process resulted in strong infiltration by an aggressive aluminium melt (aluminium/ silicon/zinc alloy) at satisfactory values for the strength and the thermal shock resistance as measured by the Tiegel test at 800"C for 72 hours. The bodies produced in example 2 which is in accordance with the earlier patent specification referred to above exhibited no tendency to infiltration by aluminium in the Tiegel test with the same aluminium melt but had a markedly reduced refractoriness under load and thermal shock resistance.The refractory bodies produced by a method in accordance with the invention of examples 3 and 4 are, by contrast, characterised by a resistance to infiltration by aluminium melt, high refractoriness under load and high thermal shock resistance.
Examples
1 2 3 4
Corundum 0 -3 mm Wt.% 70 80 80 80
Andalusite 0 -3 mm Wt.% 25 15 15 10 calc.A12O3 -0.09 mm Wt.% 5 5 5
Zirconium oxide -0.1 mm Wt% 5
Silicon carbide 0.1 -1 mm Wt% 5
Chromium (III) -0.04 mm Wt.% +6 +14
oxide
Barium sulphate -0.04 mm Wt% +10 +10
Calcium fluoride -0.04 mm Wt% +1 +1
Barium sulphate (F) -0.04 mm Wt.% +10
Monoaluminium
phosphate
50% solution Litres 15 15 15 30
Phosphoric acid Litres 20 20 20 10
(80% by Vol)
Firing "C 1440 1440 1440 1450
Bulk density g/cm3 3.06 3.14 3.17 3.30
Open porosity % by Vol. 13.5 10.7 14.8 16.0
Cold compression N/mm2 140 300 170 190
strength
Refractoriness under "C ta value > 1740 1440 1710 > 1740
load
Temperature change > 30 15 > 28 > 25
(water)
Mineral component: K,M K,C,M K,C,M, K,C
Corundum, Celsian, Mul- trace M
lite (K,C,M) Al2O3Cr2O Mixed crystal AC AC
(AC)
Claims (8)
1. A method of manufacturing refractory bodies or compositions including forming a starting mixture containing one or more of an aluminosilicate, aluminium oxide, silicon dioxide, zirconium silicate and silicon carbide, Altos and SiO2 and also containing a bonding agent, adding 0.5 to 40% by weight barium sulphate with respect to the starting mixture, 2 to 20% by weight chromium (III) oxide with respect to the starting mixture and 3 to 25 parts by weight calcium fluoride, with respect to 100 parts by weight of the added barium sulphate, and fixing the mixture at 1100 to 1600"C whereby Celsian (BaO-AI203-2 SiO2) is formed during the firing.
2. A method as claimed in claim 1 in which 2 to 14% by weight chromium (Ill) oxide is added to the starting mixture.
3. A method as claimed in claim 1 or claim 2 in which the starting mixture is based on corundum and/or aluminosilicate and contains 1 to 15% by weight zirconium oxide.
4. A method as claimed in claim 3 in which the starting mixture contains 2 to 10% by weight zirconium oxide.
5. A method as claimed in claim 3 or claim 4 in which the starting mixture contains 1 to 15% by weight silicon carbide.
6. A method as claimed in claim 5 in which the starting mixture contains 2 to 10% by weight silicon carbide.
7. A method of manufacturing refractory bodies or compositions substantially as specifically herein described with reference to Example 3 or Example 4.
8. A composition comprising a mixture of one or more of an aluminosilicate, aluminium oxide, silicon dioxide, zirconium silicate and silicon carbide, the said material or materials containing Awl203 and SiO2, a bonding agent, 0.5 to 40% by weight barium sulphate, 2 to 20% by weight chromium (III) oxide and 3 to 25 parts by weight calcium fluoride, with respect to 100 parts by weight of the barium sulphate, whereby when the composition is fired Celsian is formed.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843419199 DE3419199A1 (en) | 1984-05-23 | 1984-05-23 | FIRE RESISTANT BODIES OR MEASURES, ESPECIALLY FOR THE LINING OF OEFENS OR CASES FOR MELTED METALS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8512942D0 GB8512942D0 (en) | 1985-06-26 |
| GB2159144A true GB2159144A (en) | 1985-11-27 |
| GB2159144B GB2159144B (en) | 1987-10-21 |
Family
ID=6236652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08512942A Expired GB2159144B (en) | 1984-05-23 | 1985-05-22 | Method of manufacturing refractory bodies or compositions |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE902361A (en) |
| DE (1) | DE3419199A1 (en) |
| ES (1) | ES8607892A1 (en) |
| FR (1) | FR2564825A1 (en) |
| GB (1) | GB2159144B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2593805A1 (en) * | 1986-02-04 | 1987-08-07 | Olifan Sa | Refractory composition intended especially for the manufacture of a crucible or tank furnace |
| GB2326120A (en) * | 1997-06-13 | 1998-12-16 | Ishikawajima Harima Heavy Ind | Continuous casting and refractory nozzle therefor |
| EP1739356A1 (en) * | 2005-07-01 | 2007-01-03 | Siemens Aktiengesellschaft | Moulding composition for making a refractory lining |
| EP1840101A2 (en) | 2006-03-31 | 2007-10-03 | Nichias Corporation | Fused siliceous refractory and production method thereof |
| US7531476B2 (en) | 2001-01-26 | 2009-05-12 | Pedro Fajardo Sola | Refractory material for cement industry kilns and use thereof |
| WO2009087111A1 (en) * | 2008-01-09 | 2009-07-16 | Refratechnik Steel Gmbh | Additive for forming a corrosion-protection layer on a refractory cladding of a melt furnace containing an aluminium alloy melt |
| FR3075785A1 (en) * | 2017-12-22 | 2019-06-28 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | PRODUCT CONTAINING CHROMIUM OXIDE 3 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3700895A1 (en) * | 1987-01-14 | 1988-07-28 | Intracon Handel | Closure for bottom tapping holes, and closing material suitable for this purpose |
| WO2002059057A1 (en) * | 2001-01-26 | 2002-08-01 | Pedro Fajardo Sola | Refractory material for cement industry kilns and use thereof |
| CN112194471A (en) * | 2020-10-23 | 2021-01-08 | 中钢洛耐科技股份有限公司 | Ultralow-porosity high-alumina brick and preparation process thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB527470A (en) * | 1939-04-13 | 1940-10-09 | Gilbert Edward Seil | Chromite refractory materials |
| FR2312468A1 (en) * | 1975-05-29 | 1976-12-24 | Ucpi | REFRACTORY MATERIAL, USEFUL IN PARTICULAR FOR THE PREPARATION AND TRANSPORT OF ALUMINUM |
| US4126474A (en) * | 1977-08-19 | 1978-11-21 | General Refractories Company | Refractory for aluminum-melting furnaces |
| GB2098198B (en) * | 1981-05-08 | 1984-12-05 | Flogates Ltd | Zircon-containing refractories |
| BE900761A (en) * | 1983-10-13 | 1985-02-01 | Didier Werke Ag | MASSES OR REFRACTORY BODIES IN PARTICULAR, FOR THE FURNISHING OF OVENS OR CONTAINERS FOR MOLTEN METALS. |
-
1984
- 1984-05-23 DE DE19843419199 patent/DE3419199A1/en active Granted
-
1985
- 1985-05-07 BE BE0/214969A patent/BE902361A/en not_active IP Right Cessation
- 1985-05-22 GB GB08512942A patent/GB2159144B/en not_active Expired
- 1985-05-22 ES ES543384A patent/ES8607892A1/en not_active Expired
- 1985-05-22 FR FR8507740A patent/FR2564825A1/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2593805A1 (en) * | 1986-02-04 | 1987-08-07 | Olifan Sa | Refractory composition intended especially for the manufacture of a crucible or tank furnace |
| GB2326120A (en) * | 1997-06-13 | 1998-12-16 | Ishikawajima Harima Heavy Ind | Continuous casting and refractory nozzle therefor |
| GB2326120B (en) * | 1997-06-13 | 2002-04-10 | Ishikawajima Harima Heavy Ind | Casting steel strip |
| US7531476B2 (en) | 2001-01-26 | 2009-05-12 | Pedro Fajardo Sola | Refractory material for cement industry kilns and use thereof |
| EP1739356A1 (en) * | 2005-07-01 | 2007-01-03 | Siemens Aktiengesellschaft | Moulding composition for making a refractory lining |
| WO2007003587A3 (en) * | 2005-07-01 | 2007-04-12 | Siemens Ag | Molding compound for producing a refractory lining |
| EP1840101A2 (en) | 2006-03-31 | 2007-10-03 | Nichias Corporation | Fused siliceous refractory and production method thereof |
| EP1840101A3 (en) * | 2006-03-31 | 2010-09-22 | Nichias Corporation | Fused siliceous refractory and production method thereof |
| WO2009087111A1 (en) * | 2008-01-09 | 2009-07-16 | Refratechnik Steel Gmbh | Additive for forming a corrosion-protection layer on a refractory cladding of a melt furnace containing an aluminium alloy melt |
| FR3075785A1 (en) * | 2017-12-22 | 2019-06-28 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | PRODUCT CONTAINING CHROMIUM OXIDE 3 |
Also Published As
| Publication number | Publication date |
|---|---|
| BE902361A (en) | 1985-09-02 |
| GB8512942D0 (en) | 1985-06-26 |
| GB2159144B (en) | 1987-10-21 |
| DE3419199C2 (en) | 1990-03-29 |
| ES8607892A1 (en) | 1986-06-01 |
| DE3419199A1 (en) | 1985-12-19 |
| FR2564825A1 (en) | 1985-11-29 |
| ES543384A0 (en) | 1986-06-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |