NO171780B - PROCEDURE FOR MANUFACTURING BUILDING MATERIALS - Google Patents
PROCEDURE FOR MANUFACTURING BUILDING MATERIALS Download PDFInfo
- Publication number
- NO171780B NO171780B NO872459A NO872459A NO171780B NO 171780 B NO171780 B NO 171780B NO 872459 A NO872459 A NO 872459A NO 872459 A NO872459 A NO 872459A NO 171780 B NO171780 B NO 171780B
- Authority
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- Norway
- Prior art keywords
- concrete
- slag
- weight
- combination
- silicon
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000004566 building material Substances 0.000 title claims description 3
- 239000004567 concrete Substances 0.000 claims description 44
- 239000002893 slag Substances 0.000 claims description 33
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910001868 water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000395 magnesium oxide Substances 0.000 claims description 18
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 15
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 15
- 239000004571 lime Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 235000021317 phosphate Nutrition 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 230000002787 reinforcement Effects 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- -1 NaHSOA Chemical compound 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- DYRBFMPPJATHRF-UHFFFAOYSA-N chromium silicon Chemical compound [Si].[Cr] DYRBFMPPJATHRF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910021487 silica fume Inorganic materials 0.000 claims 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims 1
- 239000011398 Portland cement Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 7
- 239000012190 activator Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011214 refractory ceramic Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 206010042674 Swelling Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Vending Machines For Individual Products (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte ved fremstilling av et byggemateriale gjennom aktivering av latent hydraulisk, finmalt, granulert, amorft, basisk masovnslagg til et direkte-virkende hydraulisk bindemiddel. The present invention relates to a method for the production of a building material through the activation of latent hydraulic, finely ground, granulated, amorphous, basic blast furnace slag into a direct-acting hydraulic binder.
Portlandsement anses generelt som det beste hydrauliske bindemiddel, som bare ved tilsetning av vann herder til et stenlignende materiale (betong) i løpet av noen få timer til det får den endelige styrke i løpet av omtrent en måned. Virkningen beror hovedsakelig på kjemiske reaksjoner mellom basisk kalk og kiselsyre. Portlandsementens analyse viser ca. 64 % CaO, 20 % Si02, 2,5 % MgO, 6 % A1203, 3,5 % Fe203 + FeO, 2 % K20 + Na20, 1,5 % S03. En ulempe med sement er at ikke all kalk bindes i betongen, og at et stadig forekommende overskudd på ubestandig kalkhydrat, som danner seg mot slutten av herdingsprosessen, relativt lett utleskes ved innvirkning av vann og luftens karbondioksyd med fare for skadelig karbonatisering. Dessuten er den kjemiske bestandigheten mot sure og basiske angrep meget begrenset. Portland cement is generally considered the best hydraulic binder, which just by adding water hardens to a stone-like material (concrete) within a few hours until it reaches its final strength in about a month. The effect is mainly due to chemical reactions between basic lime and silicic acid. Portland cement's analysis shows approx. 64% CaO, 20% SiO2, 2.5% MgO, 6% Al2O3, 3.5% Fe2O3 + FeO, 2% K2O + Na2O, 1.5% SO3. A disadvantage of cement is that not all lime is bound in the concrete, and that a constantly occurring excess of unstable lime hydrate, which forms towards the end of the hardening process, is relatively easily leached out by the influence of water and the carbon dioxide in the air, with the risk of harmful carbonation. In addition, the chemical resistance to acid and alkaline attacks is very limited.
Eksempel: Ødeleggelse av betongbelegg på veier med veisalt eller av betongbroer med havvann. Risiko for rustangrep på stålarmering og store vanskeligheter med glassfiberarmering. Example: Destruction of concrete pavements on roads with road salt or of concrete bridges with seawater. Risk of rust attack on steel reinforcement and major difficulties with fiberglass reinforcement.
For å unngå Portlandsementens iblant forstyrrende svak-heter, har man i lang tid søkt etter materialer med lignende sammensetning, men med en forsterkning av de komponenter som øker både den kjemiske og mekaniske bestandigheten. Det lå derfor nær at man gjorde forsøk med finmalt, granulert, basisk masovnslagg, ettersom det nettopp inneholder en større prosent-del av meget resistente forbindelser. Analysen er følgende avhengig av kilden: ca. 30-40 % CaO, 35-40 % Si02, 7-10 % MgO, 10-2 0 % A1203, 0, 5-2 % Fe203 + FeO, 1-2 % K20 + Na20, 0,5-3 % S03. I forhold til Portlandsement er kalkinnholdet bare ca. halv-parten, men Si02- og Al203-innholdene omtrent dobbelt så store, og MgO nesten 4 ganger så stort. Nettopp disse forbindelsene gir imidlertid silikater den høyeste mekaniske og kjemiske bestandighet, det vil si øket trykk- og strekkfastighet og bestandighet mot kjemisk påvirkning. In order to avoid Portland cement's sometimes disturbing weaknesses, for a long time people have searched for materials with a similar composition, but with a reinforcement of the components that increase both the chemical and mechanical resistance. It was therefore close to experimenting with finely ground, granulated, basic blast furnace slag, as it precisely contains a larger percentage of highly resistant compounds. The analysis is as follows depending on the source: approx. 30-40% CaO, 35-40% SiO2, 7-10% MgO, 10-2 0% A12O3, 0.5-2% Fe2O3 + FeO, 1-2% K20 + Na20, 0.5-3% S03 . Compared to Portland cement, the lime content is only approx. half, but the SiO2 and Al203 contents about twice as large, and MgO almost 4 times as large. Precisely these compounds, however, give silicates the highest mechanical and chemical resistance, that is, increased compressive and tensile strength and resistance to chemical influences.
Masovnslagg dannes for en stor del som uanvendelig restprodukt ved jern- og ståltilvirkning og foreligger inter-nasjonalt i 100-talls millioner tonn. "Granulert" betyr i allminnelighet "finfordelt", men i forbindelse med slagg menes normalt at slagget i ennå glødende tilstand har vært utsatt for en rask avkjøling med vann eller en kombinasjon av kaldt vann og kald luft, hvorigjennom slagget blir glassaktig og amorft. Til tross for den gunstige kjemiske sammensetningen er det finmalte, granulerte masovnslagget bare "latent" hydraulisk, dvs. binder ikke direkte etter blanding med vann. Grunnen er at det danner seg en kiselsyrerik, tett gel som omslutter slaggkornene og hindrer hydratiseringen. Forutsetningen for at en aktivering kan komme i gang, er at denne gelen brytes opp. Aktivatoren har således en dobbel oppgave, den må først bryte opp gelen og siden reagere med selve slagget. Geldannelsen har imidlertid også en positiv virkning, ettersom gelporene er jevnt fordelt, hvorigjennom man får bedre frostbestandighet enn med kapillarporer i betong av Portlandsement. Blast furnace slag is formed to a large extent as an unusable residual product from iron and steel production and is available internationally in the hundreds of millions of tonnes. "Granulated" generally means "finely divided", but in connection with slag it is normally understood that the slag, while still glowing, has been subjected to rapid cooling with water or a combination of cold water and cold air, through which the slag becomes glassy and amorphous. Despite its favorable chemical composition, the finely ground, granulated blast furnace slag is only "latently" hydraulic, i.e. does not bind directly after mixing with water. The reason is that a silicic acid-rich, dense gel forms which surrounds the slag grains and prevents hydration. The prerequisite for an activation to start is that this gel is broken up. The activator thus has a double task, it must first break up the gel and then react with the slag itself. However, the gel formation also has a positive effect, as the gel pores are evenly distributed, which results in better frost resistance than with capillary pores in Portland cement concrete.
Allerede på slutten av 1800-tallet forsøkte man å aktivere masovnslagg. Det eldste patentet stammer fra 1892 (Passow), hvori en blanding av slagg med Portlandsement anbefales, og hvorved kalken som var dannet på sluttrinnet av hydratiseringen i form av Ca(OH)2 fungerer som aktivator. Derved skjer reaksjonen med slagget sent, og gir anledning til en langsom holdfasthetsutvikling. Dessuten er faren for krymping ved avkjølingen ganske stor. Det er bakgrunnen for at den såkalte slaggsement knapt lenger anvendes. Already at the end of the 19th century, attempts were made to activate blast furnace slag. The oldest patent dates from 1892 (Passow), in which a mixture of slag with Portland cement is recommended, whereby the lime formed at the final stage of the hydration in the form of Ca(OH)2 acts as an activator. As a result, the reaction with the slag takes place late, giving rise to a slow development of holding strength. In addition, the risk of shrinkage during cooling is quite high. This is the reason why the so-called slag cement is hardly used anymore.
Foruten kalk er de allerede lenge kjente aktivatorene (Se H. Kuhl, Zement-Chemie, Berlin 1951) alkali og sulfater. Hittil anså man at alkaliaktivering gir de høyeste holdfasthetene, men den medfører en hel del ulemper. Langtidsholdfasthetene er ikke tilfredsstillende, dessuten foreligger stor risiko for krymping, saltutfelling og karbonatisering. Binding skjer altfor fort, mellom 10 og 3 0 minutter, og støping på byggeplassen er derfor ikke mulig. Anvendelsen begrenser seg til tilvirkning av prefabrikerte betongelementer. Alkali-aktivering har også ulempen med dannelse av sterkt etsende NaOH. Kalk- og sulfat-aktivering har ulempen med mindre god korttidsholdfasthet og risiko for svelling. For alle disse kjente metoder er det også vanskelig å regulere bindingshastigheten, som enten er for rask eller for langsom. Besides lime, the already long-known activators (See H. Kuhl, Zement-Chemie, Berlin 1951) are alkali and sulphates. Until now, it was considered that alkali activation gives the highest holding strengths, but it entails a lot of disadvantages. The long-term holding strengths are not satisfactory, and there is also a high risk of shrinkage, salt precipitation and carbonation. Bonding takes place far too quickly, between 10 and 30 minutes, and casting on the building site is therefore not possible. The application is limited to the production of prefabricated concrete elements. Alkali activation also has the disadvantage of forming highly corrosive NaOH. Lime and sulphate activation has the disadvantage of less good short-term retention and the risk of swelling. For all these known methods, it is also difficult to regulate the binding speed, which is either too fast or too slow.
Hos de allerede kjente aktivator-pulvere har det vist seg at deres blanding med slaggpulver under lengre lagring, men også under transport, ofte fører til en viss bindingsvirkning. Det er viktig å unngå denne svakhet i et nytt aktiveringssystem. With the already known activator powders, it has been shown that their mixture with slag powder during longer storage, but also during transport, often leads to a certain binding effect. It is important to avoid this weakness in a new activation system.
En meget sikrere form for aktivering får man ifølge opp-finnelsen ved at slagget blandes foruten med vann, sand og ballastmateriale, med en kombinasjon av sure og basiske bestanddeler, hvorved de sure bestanddelene utgjøres av fosfater, eventuelt i kombinasjon med kraftigvirkende sulfater, og de basiske bestanddelene er magnesiumoksyd, eventuelt i kombinasjon med oksyder av jordartsmetaller og/eller eventuelt i kombinasjon med sink, hvorved det selv uten oppvarming, dannes en betong med lavt kalkinnhold og med stor mekanisk styrke og med høy kjemisk bestandighet. According to the invention, a much safer form of activation is obtained by mixing the slag with water, sand and ballast material, with a combination of acidic and basic components, whereby the acidic components are made up of phosphates, possibly in combination with powerful sulphates, and the the basic ingredients are magnesium oxide, optionally in combination with oxides of earth metals and/or optionally in combination with zinc, whereby even without heating, a concrete with a low lime content and with great mechanical strength and with high chemical resistance is formed.
Jordartsmetaller er foruten magnesium - kalsium, strontium, barium, aluminium, beryllium, gallium, indium, tallium, titan og zirkonium, samt de såkalte sjeldne jordmetallene. Mest virksomt er magnesiumoksyd som har den beste forbedringsvirkning på silikater, ettersom den øker trykk- og strekkfastheten samt elastisiteten, reduserer krympingen og gir et ikke-hygroskopisk produkt. Normalt kan MgO innbygges i silikater bare ved inn-smelting ved høy temperatur. Sammen med fosfater, eventuelt i kombinasjon med sulfater, får man en hydraulisk-virkende reaksjon av finmalt, granulert, basisk masovnslagg. Den beste virkning har man med kalsinert magnesiumoksyd (dødbrent ved 1750°C) , hvorved alt vann og karbondioksyd er drevet ut. Mindre egnet er MgO-holdige materialer, f.eks. dolomit, som virker mer som fyllmiddel. Jordmetallforbindelsene anvendes hensiktsmessig i en mengde på 0,3-3 vekt% beregnet på den tørre betongen (dvs. slagg + sand + ballastmateriale) eller 2-20 vekt% beregnet på slagget. Earth metals are besides magnesium - calcium, strontium, barium, aluminium, beryllium, gallium, indium, thallium, titanium and zirconium, as well as the so-called rare earth metals. Most effective is magnesium oxide, which has the best improving effect on silicates, as it increases compressive and tensile strength as well as elasticity, reduces shrinkage and gives a non-hygroscopic product. Normally, MgO can be incorporated into silicates only by fusion at high temperature. Together with phosphates, possibly in combination with sulphates, you get a hydraulic-acting reaction of finely ground, granulated, basic blast furnace slag. The best effect is achieved with calcined magnesium oxide (burnt to death at 1750°C), whereby all water and carbon dioxide have been expelled. Less suitable are MgO-containing materials, e.g. dolomite, which acts more as a filler. The earth metal compounds are suitably used in an amount of 0.3-3% by weight calculated on the dry concrete (ie slag + sand + ballast material) or 2-20% by weight calculated on the slag.
De sure komponentene inngår hensiktsmessig i en mengde på 0,3-6 vekt% beregnet på den tørre betongen, eller 2-40 vekt% beregnet på slagget. The acidic components are suitably included in an amount of 0.3-6% by weight calculated on the dry concrete, or 2-40% by weight calculated on the slag.
Videre har det vist seg at reaksjonen ble meget mer aktiv hvis man også tilsetter et tensid eller nitrat som reduserer overflatespenningen, dispergerer og forhindrer klumpdannelse. Samme virkning får man hvis man tar et fosfat med tensid-virkning, f.eks. Na-tripolyfosfat. MgO og fosfat for seg reagerer ikke med slagg og vann, men bare i kombinasjon. Furthermore, it has been shown that the reaction becomes much more active if you also add a surfactant or nitrate that reduces the surface tension, disperses and prevents lump formation. You get the same effect if you take a phosphate with a surfactant effect, e.g. Sodium tripolyphosphate. MgO and phosphate alone do not react with slag and water, but only in combination.
Iblant er det fordelaktig med et samvirke av MgO med andre jordmetallforbindelser. A1203 har lignende positive virkninger som MgO, øker slaggets reaksjonsevne og bestandigheten mot klorider. Titanoksyd gir bestandighet mot sure påvirkninger, f.eks. i forurenset luft (svovelnedfall) og danner resistente krystaller med silikagel. Zr02 gir pålitelig sikkerhet mot alkaliangrep. Sometimes it is advantageous to have MgO interact with other earth metal compounds. A1203 has similar positive effects as MgO, increasing the slag's reactivity and resistance to chlorides. Titanium oxide provides resistance to acidic influences, e.g. in polluted air (sulphur precipitation) and forms resistant crystals with silica gel. Zr02 provides reliable safety against alkali attack.
Som eksempel på et kraftig virkende sulfat kan nevnes natriumbisulfat NaHS04, som på grunn av sin sterkt sure reaksjon ofte anvendes teknisk i stedet for svovelsyre. As an example of a strong-acting sulphate, sodium bisulphate NaHS04 can be mentioned, which, due to its strongly acidic reaction, is often used technically instead of sulfuric acid.
De hittil kjente aktivatorene binder for det meste raskt (i tilfellet Portlandsement for langsomt) uten at en passende regulering kunne bevirkes. Det er likevel mulig med den nye metoden, delvis gjennom tilsetning av overflatespennings-reduserende midler eller med flyte-(plastifiserings-)midler, f.eks. lignosulfonat, melamin naftalen-formaldehyd, natrium-glykonat o.l. eller ved gips henholdsvis anhydrit (ca. 3 %), eller ved blanding av forskjellige fosfattyper som har for-skjellig reaksjonstid. Således kan man få et bindemiddel som herder i løpet av en halvtime for fabrikerte betongelementer, hvorigjennom flere støpinger muliggjøres per døgn, - eller man kan forlenge bindingstiden til ca. 2,5 timer, som trengs for støping på byggeplasser. The previously known activators mostly bind quickly (in the case of Portland cement too slowly) without a suitable regulation being able to be effected. It is nevertheless possible with the new method, partly through the addition of surface tension-reducing agents or with flow (plasticizing) agents, e.g. lignosulfonate, melamine naphthalene-formaldehyde, sodium gluconate etc. or in the case of gypsum or anhydrite (approx. 3%), or in the case of a mixture of different phosphate types that have different reaction times. Thus, you can get a binder that hardens within half an hour for fabricated concrete elements, which enables several castings per day, - or you can extend the bonding time to approx. 2.5 hours, which are needed for casting on construction sites.
Ved tilsetning av amorf kiselsyre, f.eks. i form av den filtrerte restproduksjon fra elektrometallurgiske prosesser (så som silisium-, ferrosilisium- eller kromsilisiumtilvirkning) med Si02-innhold mellom 75 og nær 100 %, og spesifikk overflate på vanligvis minst 20 m<2>/g, såkalt silisiumtuft eller silika, kan trykkfastigheten og tettheten økes ytterligere. Her gjerne i kombinasjon med plastifiseringsmiddel. By adding amorphous silicic acid, e.g. in the form of the filtered residual production from electrometallurgical processes (such as silicon, ferrosilicon or chromium silicon production) with a SiO2 content between 75 and close to 100%, and a specific surface area of usually at least 20 m<2>/g, so-called silicon tuft or silica, the compressive strength and density can be further increased. Here preferably in combination with a plasticizer.
Den amorfe kiselsyren anvendes hensiktsmessig i en mengde på 0,6-2 vekt% beregnet på den tørre betongen, eller 4-15 vekt% beregnet på slagget. The amorphous silicic acid is suitably used in an amount of 0.6-2% by weight calculated on the dry concrete, or 4-15% by weight calculated on the slag.
Det nye materialet er tettere enn betong og Portlandsement, lysere i fargen og lettere i vekt. Den nye betongen kan også anvendes som puss eller lettbetong henholdsvis lettvektsbetong hvis man tilsetter noe poredannende middel eller lettvekts-aggregat: av typen perlit eller vermikulit. Eventuelt kan man innblande betongballast, stål-, glass-, mineral- eller plastfibre eller flygeaske. Kombinasjon med bitumen (asfalt) er mulig. The new material is denser than concrete and Portland cement, lighter in color and lighter in weight. The new concrete can also be used as plaster or lightweight concrete or lightweight concrete if you add some pore-forming agent or lightweight aggregate: of the type perlite or vermiculite. Optionally, concrete ballast, steel, glass, mineral or plastic fibers or fly ash can be mixed in. Combination with bitumen (asphalt) is possible.
Fordelen med den forbedrede slaggbetongen ifølge foreliggende oppfinnelse i forhold til vanlig betong av Portlandsement, er fremfor alt høyere trykk- og strekkfasthet, slik det fremgår av nedenstående tabell. Det gjelder både høyere korttidsholdfasthet som muliggjør formrivning på bygget for veggformer etter ca. 10 timer, og for hvelvformer etter ca. 16 timer, hvilket fører til store besparelser - og dessuten stigende holdfasthet også gjennom flere måneder, mens vanlig betong oppnår maksimalverdier etter ca. 28 døgn. The advantage of the improved slag concrete according to the present invention compared to ordinary Portland cement concrete is, above all, higher compressive and tensile strength, as can be seen from the table below. This applies to both higher short-term holding strength, which enables form demolition on the building for wall forms after approx. 10 hours, and for vaulted forms after approx. 16 hours, which leads to great savings - and also increasing holding strength even over several months, while normal concrete achieves maximum values after approx. 28 days.
Saltbestandigheten ble prøvet på Chalmers Tekniska Hogskola i Goteborg i 4 måneder i en 30 % kalsiumkloridløsning. Ingen nedbrytning eller sprekker kunne iakttas, hvilket inntreffer i vanlig betong etter noen få uker i sterkt konsentrert kalsium-kloridløsning. The salt resistance was tested at Chalmers Tekniska Hogskola in Gothenburg for 4 months in a 30% calcium chloride solution. No degradation or cracking could be observed, which occurs in ordinary concrete after a few weeks in a highly concentrated calcium chloride solution.
Beskyttelse mot rustangrep skyldes i vanlig betong derimot at den på slutten av hydratiseringen dannede frie kalk i form av Ca(0H)2 legger seg på stålflatene, og gjenom høy pH beskytter stålet mot oksydering gjennom inntrengning av vann, oksygen henholdsvis C02 fra luften. Kalsiumhydroksyd er imidlertid en ubestandig forbindelse som oppløses av vann og forvandles av C02 (karbonatisering). I den nye betongen danner MgO med høyere pH enn kalk rustbeskyttelsen. Dødbrent MgO er bestandig mot vann, syre og C02, og således mye sikrere enn kalk. Dertil kommer at den nye betongen er meget tettere (mindre porøs) og gir derfor mer motstand mot inntrengende vann, oksygen og C02, hvilket også fører til bedre hefte av stålarmeringen. Bestandigheten av den høye pH-verdien i den nye betongen ble også kontrollert på Chalmers Tekniska Hogskola ved et bad i fenolftalein som er indikator for pH. Vedvarende høy pH vises av uforandret rødfarging, hvilket ikke er tilfellet ved Portlandsementbetong. Protection against rust attack in ordinary concrete, on the other hand, is due to the fact that the free lime formed at the end of hydration in the form of Ca(0H)2 settles on the steel surfaces, and thanks to the high pH, the steel protects against oxidation through the penetration of water, oxygen or C02 from the air. However, calcium hydroxide is an unstable compound that is dissolved by water and transformed by C02 (carbonation). In the new concrete, MgO with a higher pH than lime forms the rust protection. Burnt MgO is resistant to water, acid and C02, and thus much safer than lime. In addition, the new concrete is much denser (less porous) and therefore provides more resistance to penetrating water, oxygen and C02, which also leads to better adhesion of the steel reinforcement. The stability of the high pH value in the new concrete was also checked at Chalmers Tekniska Hogskola by a bath in phenolphthalein, which is an indicator of pH. Persistently high pH is indicated by unchanged red colouring, which is not the case with Portland cement concrete.
Kombinasjonen MgO:fosfat er hittil mest kjent fra tilvirkning av ildfast keramikk, men gir også øket brannsikkerhet for det aktiverte masovnslagget. Vanlig betong tåler derimot ikke høyere"temperatur enn ca. 500°C. The combination MgO:phosphate is so far best known from the production of refractory ceramics, but also provides increased fire safety for the activated blast furnace slag. Ordinary concrete, on the other hand, cannot withstand temperatures higher than approx. 500°C.
Årsaken til Portlandsementens ømfintlighet mot høy varme er hovedsakelig det kjemisk bundne vann. Det fysikalsk bundne vannet (kapillarvann) går vekk ved ca. 105°C uten noen skade-virkninger. Det kjemisk bundne vannet løsgjøres først senere, men under sprekkdannelse, som senere leder til oppløsning. Den ubestandige, frie kalken Ca(OH)2 går over til CaO og H20. Samtidig angriper det frigjorte vannet også det under hydratiseringen dannede tri- og dikalsiumsilikat, ■ som blir ubestandig kalsiumsilikathydrat. Dertil kommer at den i betongen forekommende a-fasen av kvarts (Si02) omvandles til en annen krystallform under volumøkning, hvilket også bidrar til sprekkdannelse (se R. K. Iler "Chemistry of Silicates"). I The reason for Portland cement's sensitivity to high heat is mainly the chemically bound water. The physically bound water (capillary water) goes away at approx. 105°C without any damaging effects. The chemically bound water is only released later, but during cracking, which later leads to dissolution. The unstable, free lime Ca(OH)2 changes to CaO and H20. At the same time, the released water also attacks the tri- and dicalcium silicate formed during hydration, ■ which becomes unstable calcium silicate hydrate. In addition, the a-phase of quartz (SiO2) present in the concrete is converted into another crystal form during volume increase, which also contributes to cracking (see R. K. Iler "Chemistry of Silicates"). IN
kombinasjonen masovnslagg - fosfat/MgO finnes ingen fri kalk og Si02 i granulert slagg er amorf, og disse risikoer finnes derfor ikke. Ved anvendelser hvor temperaturer over 1000°C kan oppstå, er det eventuelt sikrest å erstatte stenmaterialet i ballaster som kan utvides i altfor høy varme med ildfast, keramisk materiale, hvilket imidlertid bare kreves i unntakstilfeller. the combination blast furnace slag - phosphate/MgO contains no free lime and SiO2 in granulated slag is amorphous, and these risks therefore do not exist. In applications where temperatures above 1000°C can occur, it is possibly safest to replace the stone material in ballasts, which can expand in excessively high heat, with refractory ceramic material, which is, however, only required in exceptional cases.
Den nye betongen kan også kombineres med bitumen (asfalt) ved veibelegning. The new concrete can also be combined with bitumen (asphalt) when paving roads.
Som eksempel på virkning av de nye kombinasjoner av aktivatorer med hensyn til trykk- og strekkfastheten kan nevnes følgende prøvningsresultat med en blanding av 100 enheter slagg, 10 enheter Na-tripolyfosfat, 7,5 enheter MgO, 353 enheter sand og 4 0 enheter vann. As an example of the effect of the new combinations of activators with regard to the compressive and tensile strength, the following test result can be mentioned with a mixture of 100 units of slag, 10 units of Na-tripolyphosphate, 7.5 units of MgO, 353 units of sand and 40 units of water.
Allerede disse verdier er betydelig fordelaktigere enn tilsvarende hos Portlandsement (etter 28 døgn 49,0 henholdsvis 7,3 MPa). Ved tilsetningene som er nevnt i teksten ovenfor, kan Already these values are significantly more advantageous than the equivalent for Portland cement (after 28 days 49.0 and 7.3 MPa respectively). With the additions mentioned in the text above, can
tabellens verdier forbedres ytterligere. the table's values are further improved.
I forhold til betong av Portlandsement gir den nye betongen bl.a. følgende fordeler: 1. Større mekanisk bestandighet, dvs. høyere trykk- og strekkfasthet. Compared to concrete made from Portland cement, the new concrete provides, among other things, the following advantages: 1. Greater mechanical resistance, i.e. higher compressive and tensile strength.
2. Større kjemisk bestandighet. 2. Greater chemical resistance.
3. Ingen karbonatisering, dvs. utfelling av ubundet kalk, som kan føre til at betongen faller fra hverandre. 4. Ingen saltangrep. Veibelegget blir ikke skadet ved veisalt. Lengre levetid for betongbroer. Mulighet for 3. No carbonation, i.e. precipitation of unbound lime, which can cause the concrete to fall apart. 4. No salt attack. The road surface is not damaged by road salt. Longer service life for concrete bridges. Possibility of
resistente betongbåter. resistant concrete boats.
5. Ikke alkalisk tross pH 12. Ingen ubundet kalk. Derfor glassfiberarmering mulig. (Eventuelt kan en spesialtype 5. Not alkaline despite pH 12. No unbound lime. Therefore fiberglass reinforcement possible. (Possibly a special type
med Zr02 tilvirkes.) with Zr02 is produced.)
6. Lettere en Portlandsement-betong, konstruksjonen kan gjøres tynnere. 7. Mulighet for tynnere skikt henholdsvis tykkelse gjør konstruksjonen billigere, bortsett fra at slagg er 6. Lighter than Portland cement concrete, the construction can be made thinner. 7. The possibility of thinner layers or thickness makes the construction cheaper, except that slag is
billigere enn Portlandsement. cheaper than Portland cement.
8. Meget tettere. 8. Much closer.
9. Derved bedre hefte av stålarmering og beskyttelse mot rustangrep på stålarmeringen. 9. As a result, better adhesion of the steel reinforcement and protection against rust attack on the steel reinforcement.
10. Høyere ildfasthet, (brannsikkerhet). 10. Higher fire resistance, (fire safety).
11. Frostbestandighet. 11. Frost resistance.
12. Lettere støping ved kalde værforhold. 12. Easier casting in cold weather conditions.
13. Egenskapene muliggjør også anvendelse som flytesparkel. 13. The properties also enable use as a floating trowel.
14. Bedre materiale enn sementbruk ved pussing. 14. Better material than using cement when plastering.
15. Lavere krav til fuktighetsherding av nystøpt betong. 15. Lower requirements for moisture curing of newly cast concrete.
16. I likhet med vanlig betong kan også det nye materialet gjøres porøst for å få en lettbetong som har store fordeler sammenlignet med tradisjonell lettbetong henholdsvis lettvektsbetong ettersom cellestrukturen blir mekanisk sterkere 16. Like normal concrete, the new material can also be made porous to obtain a lightweight concrete that has major advantages compared to traditional lightweight concrete or lightweight concrete as the cell structure becomes mechanically stronger
og at det nye materialet ikke er hygroskopisk. and that the new material is not hygroscopic.
17. Lysere farge. 17. Lighter color.
Claims (7)
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SE8504754A SE8504754D0 (en) | 1985-10-14 | 1985-10-14 | PROCEDURE FOR MANUFACTURING BUILDING MATERIAL |
PCT/SE1986/000473 WO1987002354A1 (en) | 1985-10-14 | 1986-10-14 | Method of preparing building materials |
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NO872459L NO872459L (en) | 1987-08-12 |
NO171780B true NO171780B (en) | 1993-01-25 |
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NO (1) | NO171780C (en) |
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1986
- 1986-10-14 DE DE8686906023T patent/DE3677519D1/en not_active Expired - Lifetime
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NO872459L (en) | 1987-08-12 |
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