WO1991006513A1 - Process for producing an active fine aggregate for the preparation of concrete - Google Patents
Process for producing an active fine aggregate for the preparation of concrete Download PDFInfo
- Publication number
- WO1991006513A1 WO1991006513A1 PCT/FI1990/000250 FI9000250W WO9106513A1 WO 1991006513 A1 WO1991006513 A1 WO 1991006513A1 FI 9000250 W FI9000250 W FI 9000250W WO 9106513 A1 WO9106513 A1 WO 9106513A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silica
- concrete
- fine
- weight
- inactive
- Prior art date
Links
- 239000004567 concrete Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000002360 preparation method 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 71
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000002893 slag Substances 0.000 claims abstract description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims 1
- 239000004117 Lignosulphonate Substances 0.000 claims 1
- 235000019357 lignosulphonate Nutrition 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011149 active material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1066—Oxides, Hydroxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- binders in addition to cement and cement binders, also various fine aggregates, as for example so-called so-called pozzolanic substances, are used as binders in con ⁇ crete. These substances are characterized therein that they contain glass-like silicon oxide, which re ⁇ acts with the calcium hydroxide generated at a hydra- tation of cement and forms compounds giving strength to the concrete.
- pozzolanas belong fly ash produced from the combustion of coal and peat and silica produced from the preparation of silicon.
- the reactivity of a pozzolana in concrete is influ- enced except by the chemical composition, also by the grain size thereof.
- the grain size of silica is con ⁇ siderably smaller than that of fly ash.
- the Finnish concrete standard always presupposes a use of a plasticizer when silica is used.
- the object of the present invention is to eli ⁇ minate the drawbacks described above and to provide a process by means of which it is possible to produce in an entirely new manner an active fine aggregate considerably more efficient than the previous ones, the use of which aggregate makes it always possible to achieve the final result desired.
- This object is achieved by means of the process of the invention characterized in that a raw material mixture is made containing substantially dry inactive and/or weakly active components selected from a group consisting of e.g.
- the silica or the other substance containing an abundance of fine amorphous silicon oxide is thus ground in a mill to ⁇ gether with the inactive and/or only weakly active materials.
- the silica preferably pelletized, then decomposes into very small particles, and according to research, a large part of these particles adheres to the surface of the rest ⁇ of the material ground and changes the surface of the inactive and/or weakly active material to react very easily with the calcium hydroxide.
- Another advantage of the process is that the need for water in concrete does not increase at all even though silica is used.
- the silica added to the grinding can also be unpelletized. This kind of silica changes during grinding in such a way that it can be used for the preparation of concrete.
- the share of the pozzolanic substances is some percentages by weight, as practical upper limit can be considered 50 % by weight.
- the average grain size of this product which can, for instance, be called an active filler, is larger than the average grain size of cement and smaller than that of natural fine aggregate.
- an active filler produced by the process of the in ⁇ vention, it is possible to compensate the lacking grain size area by an inactive and/or weakly active basic material, the surface of which is activated by means of a pozzolanic substance.
- a product of this kind has substantially cheaper production costs than a product with cement properties having the same ef- feet on the strength development of concrete.
- Very fine materials increase the need for water in connection with the prepara ⁇ tion of concrete, when they are dosed in traditional manners.
- the main part of the fine material in the product prepared according to the invention has ad- hered during grinding to the surface of the basic ma ⁇ terial, and consequently, it does not increase the need for water in concrete.
- a plasticizer as e.g. lig- nosulphate, is preferably added into the mill at the preparation of the product, which plasticizer adhered to the surface of the fine particles ensures a dis ⁇ persion of the fine material in the concrete mix.
- a typical composition (% by weight) of the raw material mixture and thus of the final product dis- cussed in the process is, depending on the use, as follows:
- inactive materials ' as limestone ⁇ 15 % 0 > grinding additive, as lignosulphate ⁇ 5 % the rest weakly active materials, as lump slag.
- grinding additive contributing to the grinding as well as to a dispersion of the finest grains into the concrete mix.
- the grain size curve of the product is adjusted in such a way that it compensates the lacking grain sizes of the concrete in the best possible manner.
- the grain size distribution is adjusted by dosing into the mill materials to be ground in different ways in a ratio desired. In the product created in this way, the main part of the material belongs to the grain size area of 0...300 ⁇ m.
Abstract
The invention relates to a process for producing an active fine aggregate, i.e. an active filler, for the preparation of concrete. In the process are ground pozzolanic substances, practically silica, together with inactive and/or weakly active components, as lump slag, which makes it possible to have the silica in the filler in very small particles activating the surfaces of the other components to react easily with the calcium hydroxide.
Description
Process for producing an active fine aggregate for the preparation of concrete
In addition to cement and cement binders, also various fine aggregates, as for example so-called pozzolanic substances, are used as binders in con¬ crete. These substances are characterized therein that they contain glass-like silicon oxide, which re¬ acts with the calcium hydroxide generated at a hydra- tation of cement and forms compounds giving strength to the concrete. To the most used pozzolanas belong fly ash produced from the combustion of coal and peat and silica produced from the preparation of silicon. The reactivity of a pozzolana in concrete is influ- enced except by the chemical composition, also by the grain size thereof. The grain size of silica is con¬ siderably smaller than that of fly ash. As the grain size of a pozzolana decreases, the need for water in concrete increases. Therefore, the Finnish concrete standard always presupposes a use of a plasticizer when silica is used.
The bulk density of the silica produced in the industry is very low. To transport and dose it as such into concrete is difficult and even impossible. Attempts have been made to eliminate the problem by pelletizing the silica into very big pellets with respect to its grain size. The problems with trans¬ port and dosage are thus eliminated, but the silica does not decompose properly in a concrete mixer, which prevents the silica from acting in the concrete in the best possible manner. Studies have shown that undecomposable silica pellets have been found in a concrete prepared according to the instructions, which pellets do not provide the concrete with the properties searched for by means of the use of sili-
ca. This problem has been decreased by sludging the silica in water before use. Moreover, admixtures have been used at the sludging. The typical content of dry substance in silica sludge is 50 %. Also this process has its drawbacks, as e.g. storing, transport and dosage.
The object of the present invention is to eli¬ minate the drawbacks described above and to provide a process by means of which it is possible to produce in an entirely new manner an active fine aggregate considerably more efficient than the previous ones, the use of which aggregate makes it always possible to achieve the final result desired. This object is achieved by means of the process of the invention characterized in that a raw material mixture is made containing substantially dry inactive and/or weakly active components selected from a group consisting of e.g. limestone, quartz, lump slag, granulated and pelletized blast-furnace slag; and silica or another substance containing an abundance of fine amorphous silicon oxide; and that this substantially dry raw material mixture is ground in a mill or the like, as a result of which joint grinding the silica or the other substance containing an abundance of fine amor- phous silicon oxide activates the surfaces of the inactive and/or weakly active components to react easily with the calcium hydroxide.
In the process of the invention, the silica or the other substance containing an abundance of fine amorphous silicon oxide is thus ground in a mill to¬ gether with the inactive and/or only weakly active materials. The silica, preferably pelletized, then decomposes into very small particles, and according to research, a large part of these particles adheres to the surface of the rest ■of the material ground and
changes the surface of the inactive and/or weakly active material to react very easily with the calcium hydroxide. Another advantage of the process is that the need for water in concrete does not increase at all even though silica is used. The silica added to the grinding can also be unpelletized. This kind of silica changes during grinding in such a way that it can be used for the preparation of concrete. In practice, the share of the pozzolanic substances is some percentages by weight, as practical upper limit can be considered 50 % by weight.
When using the process of the invention, atten¬ tion is paid to the grain size distribution of the product created. The grain size distribution is se- lected in such a way that it fills as well as pos¬ sible the area remaining between the smallest grains of natural stone aggregate and the largest cement grains, which area by nature lacks grains. Conse¬ quently, the average grain size of this product, which can, for instance, be called an active filler, is larger than the average grain size of cement and smaller than that of natural fine aggregate. By using the active filler produced by the process of the in¬ vention, it is possible to compensate the lacking grain size area by an inactive and/or weakly active basic material, the surface of which is activated by means of a pozzolanic substance. A product of this kind has substantially cheaper production costs than a product with cement properties having the same ef- feet on the strength development of concrete.
Very fine materials, as e.g. silica, increase the need for water in connection with the prepara¬ tion of concrete, when they are dosed in traditional manners. The main part of the fine material in the product prepared according to the invention has ad-
hered during grinding to the surface of the basic ma¬ terial, and consequently, it does not increase the need for water in concrete. Because, however, a part of the fine material consists of very small loose particles in the product, a plasticizer, as e.g. lig- nosulphate, is preferably added into the mill at the preparation of the product, which plasticizer adhered to the surface of the fine particles ensures a dis¬ persion of the fine material in the concrete mix. Results of research
In tests was used a fine aggregate containing 3 % of silica ground together with lump slag. The dos¬ age of this aggregate into the concrete was 50 kg/m3. 200 kg/m3 of cement was used in the concrete. It was possible to prove by means of calculations that the effect of the silica on the compression strength of the concrete at the age of 28 days was 4...5 MPa. To achieve a corresponding additional strength it would have been necessary to add approximately 20 kg/m3 of cement instead of the 1,5 kg of silica now added. Consequently, the activity of silica obtained was over 10 compared with cement. According to the test results of the literature and to the applicant' s own test results, the activity of silica compared with cement is about 3. In accordance with these tests, the activity of silica increased more than threefold. Example
A typical composition (% by weight) of the raw material mixture and thus of the final product dis- cussed in the process is, depending on the use, as follows:
0 > silica < 10 %
0 > inactive materials, ' as limestone < 15 % 0 > grinding additive, as lignosulphate < 5 % the rest weakly active materials, as lump slag.
In connection with grinding, to the mill is preferably added grinding additive contributing to the grinding as well as to a dispersion of the finest grains into the concrete mix. The grain size curve of the product is adjusted in such a way that it compensates the lacking grain sizes of the concrete in the best possible manner. The grain size distribution is adjusted by dosing into the mill materials to be ground in different ways in a ratio desired. In the product created in this way, the main part of the material belongs to the grain size area of 0...300 μm.
By changing the grading, the activity of the basic material and the quality and dosage of the poz- zolana, it is possible to produce different fine agg¬ regates for different concretes.
Claims
1. A process for producing an active fine agg¬ regate for the preparation of concrete, c h a r - a c t e r i z e d in that a raw material mixture is made containing substantially dry inactive and/or weakly active components selected from a group con¬ sisting of e.g. limestone, quartz, lump slag, granu¬ lated and pelletized blast-furnace slag; and silica or another substance containing an abundance of fine amorphous silicon oxide; and that this substantially dry raw material mixture is ground in a mill or the like, as a result of which joint grinding the silica or the other substance containing an abundance of fine amorphous silicon oxide activates the surfaces of the inactive and/or weakly active components to react easily with the calcium hydroxide.
2. A process according to claim 1, c h a r ¬ a c t e r i z e d in that the share of silica or another substance containing an abundance of fine silicon oxide is 50 % by weight at the most, prefer¬ ably less than 10 % by weight.
3. A process according to claim 1 or 2, c h a r a c t e r i z e d in that the composition of the fine aggregate is as follows:
- 10 % by weight of silica at the most;
15 % by weight of inactive components, as limestone, at the most;
- 5 % by weight of a grinding additive, as lignosulphonate, at the most; and
- the rest inactive components, as lump slag.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT90915482T ATE102591T1 (en) | 1989-10-26 | 1990-10-24 | PROCESS FOR PRODUCTION OF AN ACTIVE FINE AGGREGATE FOR CONCRETE MANUFACTURING. |
DE90915482T DE69007294D1 (en) | 1989-10-26 | 1990-10-24 | METHOD FOR PRODUCING AN ACTIVE FINE INGREDIENT FOR CONCRETE PRODUCTION. |
NO921603A NO307750B1 (en) | 1989-10-26 | 1992-04-24 | Process for the preparation of an active, finely divided aggregate for use in concrete |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI895090A FI88284C (en) | 1989-10-26 | 1989-10-26 | Process for producing an active fine material intended for making concrete |
FI895090 | 1989-10-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991006513A1 true WO1991006513A1 (en) | 1991-05-16 |
Family
ID=8529223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI1990/000250 WO1991006513A1 (en) | 1989-10-26 | 1990-10-24 | Process for producing an active fine aggregate for the preparation of concrete |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0498815B1 (en) |
DE (1) | DE69007294D1 (en) |
FI (1) | FI88284C (en) |
NO (1) | NO307750B1 (en) |
WO (1) | WO1991006513A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0696262B2 (en) † | 1993-04-30 | 2003-10-01 | RONIN, Vladimir P. | Method for producing cement |
WO2009015771A1 (en) * | 2007-07-27 | 2009-02-05 | Forschungszentrum Karlsruhe Gmbh | Single-phase hydraulic binder, methods for the production thereof and structural material produced therewith |
WO2009015770A1 (en) * | 2007-07-27 | 2009-02-05 | Forschungszentrum Karlsruhe Gmbh | Single-phase hydraulic binder, methods for the production thereof and structural material produced therewith |
US7537653B2 (en) | 2005-01-31 | 2009-05-26 | Gcc Technology And Processes S.A. | Microsilica materials with improved pozzolanic activity |
US11279658B2 (en) | 2018-03-09 | 2022-03-22 | Specification Products, Inc. | Compositions for improved concrete performance |
US11866366B2 (en) | 2019-09-03 | 2024-01-09 | Specification Products, Inc. | Wear-resistant concrete formulations and methods for their preparation |
US11884600B2 (en) | 2018-03-22 | 2024-01-30 | Specification Products, Inc. | Method for preparing an improved finished concrete product |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8908159B2 (en) | 2011-05-11 | 2014-12-09 | Leddartech Inc. | Multiple-field-of-view scannerless optical rangefinder in high ambient background light |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2259898A1 (en) * | 1972-12-07 | 1974-06-12 | Steag Handel Gmbh | Concrete with increased fine grain character - by addn of fly ash to the cement |
DE2458304A1 (en) * | 1974-12-10 | 1976-06-16 | Kropfhammer Georg Dr Ing | Slag granulate obtd. from coal burning plant - where slag is milled with cement or lime to form hydraulic binder |
BE839899A (en) * | 1976-03-22 | 1976-07-16 | PROCESS FOR RECOVERING METALLURGIC SLAGS | |
US4306912A (en) * | 1979-05-31 | 1981-12-22 | Flowcon Oy | Process for producing a binder for slurry, mortar, and concrete |
-
1989
- 1989-10-26 FI FI895090A patent/FI88284C/en active IP Right Grant
-
1990
- 1990-10-24 WO PCT/FI1990/000250 patent/WO1991006513A1/en active IP Right Grant
- 1990-10-24 DE DE90915482T patent/DE69007294D1/en not_active Expired - Lifetime
- 1990-10-24 EP EP19900915482 patent/EP0498815B1/en not_active Expired - Lifetime
-
1992
- 1992-04-24 NO NO921603A patent/NO307750B1/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2259898A1 (en) * | 1972-12-07 | 1974-06-12 | Steag Handel Gmbh | Concrete with increased fine grain character - by addn of fly ash to the cement |
DE2458304A1 (en) * | 1974-12-10 | 1976-06-16 | Kropfhammer Georg Dr Ing | Slag granulate obtd. from coal burning plant - where slag is milled with cement or lime to form hydraulic binder |
BE839899A (en) * | 1976-03-22 | 1976-07-16 | PROCESS FOR RECOVERING METALLURGIC SLAGS | |
US4306912A (en) * | 1979-05-31 | 1981-12-22 | Flowcon Oy | Process for producing a binder for slurry, mortar, and concrete |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0696262B2 (en) † | 1993-04-30 | 2003-10-01 | RONIN, Vladimir P. | Method for producing cement |
US7537653B2 (en) | 2005-01-31 | 2009-05-26 | Gcc Technology And Processes S.A. | Microsilica materials with improved pozzolanic activity |
US8226763B2 (en) | 2007-07-27 | 2012-07-24 | Karlsruher Institut Fuer Technologie | Single-phase hydraulic binder, methods for the production thereof and structural material produced therewith |
WO2009015770A1 (en) * | 2007-07-27 | 2009-02-05 | Forschungszentrum Karlsruhe Gmbh | Single-phase hydraulic binder, methods for the production thereof and structural material produced therewith |
CN101855184A (en) * | 2007-07-27 | 2010-10-06 | 卡尔斯鲁厄技术研究院 | Single-phase hydraulic binder, it production method and use the material of construction that it makes |
US8226764B2 (en) | 2007-07-27 | 2012-07-24 | Karlsruher Institut Fuer Technologie | Single-phase hydraulic binder, methods for the production thereof and structural material produced therewith |
WO2009015771A1 (en) * | 2007-07-27 | 2009-02-05 | Forschungszentrum Karlsruhe Gmbh | Single-phase hydraulic binder, methods for the production thereof and structural material produced therewith |
TWI455903B (en) * | 2007-07-27 | 2014-10-11 | Karlsruher Inst Technologie | Monophase hydraulic binder, manufacturing method thereof and building material made using the same |
TWI455904B (en) * | 2007-07-27 | 2014-10-11 | Karlsruher Inst Technologie | Monophase hydraulic binder, manufacturing method thereof and building material made using the same |
EA023619B1 (en) * | 2007-07-27 | 2016-06-30 | Карлсруер Институт Фюр Технологи | Single-phase hydraulic binder, method for the production thereof and structural material produced therewith |
EA023750B1 (en) * | 2007-07-27 | 2016-07-29 | Карлсруер Институт Фюр Технологи | Single-phase hydraulic binder, method for the production thereof and structural material produced therewith |
US11279658B2 (en) | 2018-03-09 | 2022-03-22 | Specification Products, Inc. | Compositions for improved concrete performance |
US11884600B2 (en) | 2018-03-22 | 2024-01-30 | Specification Products, Inc. | Method for preparing an improved finished concrete product |
US11919823B2 (en) | 2018-03-22 | 2024-03-05 | Specification Products, Inc. | Compositions for improved concrete performance |
US11866366B2 (en) | 2019-09-03 | 2024-01-09 | Specification Products, Inc. | Wear-resistant concrete formulations and methods for their preparation |
Also Published As
Publication number | Publication date |
---|---|
DE69007294D1 (en) | 1994-04-14 |
NO921603D0 (en) | 1992-04-24 |
EP0498815B1 (en) | 1994-03-09 |
NO921603L (en) | 1992-06-26 |
NO307750B1 (en) | 2000-05-22 |
FI88284B (en) | 1993-01-15 |
EP0498815A1 (en) | 1992-08-19 |
FI88284C (en) | 1993-04-26 |
FI895090A0 (en) | 1989-10-26 |
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