LT3519B - Method for reducing allergic effect induced by water-soluble cr(vi) available in cements and /or cement- containing half-finished products - Google Patents
Method for reducing allergic effect induced by water-soluble cr(vi) available in cements and /or cement- containing half-finished products Download PDFInfo
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- LT3519B LT3519B LTIP1952A LTIP1952A LT3519B LT 3519 B LT3519 B LT 3519B LT IP1952 A LTIP1952 A LT IP1952A LT IP1952 A LTIP1952 A LT IP1952A LT 3519 B LT3519 B LT 3519B
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- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/26—Carbonates
- C04B14/28—Carbonates of calcium
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- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/146—Silica fume
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- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
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- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1075—Chromium-free or very low chromium-content materials
- C04B2111/1081—Chromium VI, e.g. for avoiding chromium eczema
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- 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
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- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Dental Preparations (AREA)
- Processing Of Solid Wastes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Removal Of Specific Substances (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Catalysts (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
Išradimas susietas su alerginio poveikio, kurį sukelia tirpus vandenyje CrVI, esantis cementuose ir/arba cemento turinčiuose ruošiniuose, slopinimo būdu, kelio užkirtimu alerginėms reakcijoms asmenims, kurie kontaktuoja su cementais ir/arba šiniais (chromatinė egzema).The invention relates to the inhibition of allergenic effects caused by water soluble Cr VI in cements and / or cementitious preparations, the prevention of allergic reactions in persons in contact with cements and / or sidings (chromatic eczema).
Žinoma, kad tirpus vandenyje alergines reakcijas. Be to, Fe (II) sulfato. H2O, gali būti kiekiai.Water-soluble allergic reactions are known. In addition, Fe (II) sulfate. H 2 O, quantities may be present.
cemento turinčiais ruochromatas gali sukelti žinoma, kad, pridedant efektyviai sumažinti CrVI cement-containing rochromate can cause the known to add effective reduction of Cr VI
Geležies sulfatas (Fe(II)-sulfatas) vandeniniuose cemento mišiniuose redukuoja šešiavalentį tirpų vandenyje chromą (CrVI) iki trivalenčio chromo (Cr111), tuo būdu gali būti užslopintos alerginės reakcijos 6-valenčio chromo atžvilgiu (EP Nr. 0125267 Al, EP Nr. 0160747 Al, EP Nr. 0160746 Al, EP Nr. 0133434 Al, EP Nr. 0054314 Al).Iron sulfate (Fe (II) sulfate) in aqueous cement mixtures reduces hexavalent water-soluble chromium (Cr VI ) to trivalent chromium (Cr 111 ), thereby inhibiting allergic reactions to 6-valent chromium (EP 0125267 Al, EP No. 0160747 A1, EP 0160746 A1, EP 0133434 A1, EP 0054314 A1).
Sandėliuojant cementus ir/arba sausus cemento turinčius ruošinius prekybinius standartus atitinkančioje taroje, ilgėjant sandėliavimo laikui geležies sulfatas praranda savo kaip reduktoriaus savybes (persandėliavimo efektas) . Be to, į plaučius patenkantys geležies sulfatai sukelia fibrogeninius plaučių audinio pakitimus, tuo būdu smulkiai sumalto geležies sulfato panaudojimas, žiūrint iš darbo higienos pozicijų, atrodo rizikingai.During storage of cements and / or dry cementitious preforms in commercially acceptable containers, ferrous sulphate loses its reducing properties (storage effect) over time. In addition, iron sulphates that enter the lungs cause fibrogenic changes in the lung tissue, so that the use of finely ground iron sulphate from the standpoint of occupational hygiene appears to be risky.
EP Nr. 0524999 Al tirpaus vandenyje CrVI redukavimui cemento klijuose, skiediniuose ir betonuose siūlomas naudoti mangano sulfatas. Tačiau ar būtent panaudojant mangano sulfatą galima užkirsti kelią galimam sveikatai kenkiančiam geležies sulfato poveikiui, ir ar tuo būdu gali būti išspręsta persandėliavimo problema, mažų mažiausiai kelia abejonę.EP no. 0524999 Manganese sulphate is proposed for use in the reduction of Cr VI in water soluble Cr VI in cement adhesives, mortars and concrete. However, whether or not manganese sulfate is used to prevent the potentially harmful health effects of ferrous sulfate, and whether it can solve the problem of overpopulation, is at least questionable.
TT
Išradimo uždavinys yra rasti būdą, kuriuo vandens/cemento mišinyje būtų sumažintas alergijas sukeliantis tirpaus vandenyje CrVI poveikis, panaudojant priemonę, kuri sausuose cemento mišiniuose beveik neribotą laiką išsaugotų savo poveikio savybes, būtų nepavojinga iš darbo higienos pozicijų ir jos gavimas būtų nebrangus.The object of the invention is to find a way to reduce the allergenic effect of water-soluble Cr VI in a water / cement mixture by using an agent that preserves its effect properties in dry cement mixtures for almost indefinitely, is safe from work hygiene and is inexpensive to obtain.
Šis uždavinys sprendžiamas pasinaudojant 1 punkto požymiais. Kitus pirmenybę turinčius išradimo patobulinimus apibūdina žemiau einantys išradimo apibrėžties punktai.This problem is solved by using the features of point 1. Other preferred improvements of the invention are described in the following claims.
Pagal išradimą naudojami ligninsulfonatai. Neracionalu, kai ligninsulfonatas, dedamas į cementą ir/arba cemento turinčius ruošinius. Jį galima pridėti, pavyzdžiui, į klinkerį betarpiškai prieš arba malimo metu, į sumaltą cementą prieš arba sauso cemento mišinio gaminimo metu, arba prieš arba vandens pridėjimo į šviežią cemento mišinį metu; ligninsulfonatas gali būti pridedamas prekybinius standartus atitinkančių miltelių pavidale arba kaip tirpalas.The present invention uses lignin sulfonates. It is impractical for lignin sulphonate to be added to cement and / or cementitious preparations. It can be added, for example, to the clinker immediately before or during milling, to the ground cement before or during the dry cement mixture, or before or during the addition of water to the fresh cement mixture; lignin sulphonate may be added as a commercially available powder or as a solution.
Kokiu būdu ligninsulfonatai veikia tirpų vandenyje CrVI, iki šiol dar nėra išsiaiškinta. Nustatyta, kad tikslingiausia būtų naudoti 300 mg ligninsulfonato 1 mg CrVI su sąlyga, kad cemente yra nuo apie 0,0005 iki 0,0015 mg, esant reikalui, net iki apie 0,004 masės %, tirpaus vandenyje CrVI; jei yra daugiau arba mažiau tirpaus vandenyje CrVI, gali būti pridedami atitinkamai suderinti ligninsulfonato kiekiai.How lignin sulfonates act on water soluble Cr VI has not yet been elucidated. It has been found to be most convenient to use 300 mg of lignin sulfonate 1 mg Cr VI , provided that the cement contains from about 0.0005 to 0.0015 mg, if necessary up to about 0.004% by weight, of water soluble Cr VI ; in the case of more or less water soluble Cr VI , appropriate quantities of lignin sulphonate may be added.
Ligninsulfonatai yra žinomi kaip lignino rūgšties druskos, medyje augančio natūralaus lignino dariniai; jie turi bazinę fenolio struktūrą, kur eterinant fenolinę OH-grupę stiprios fenolinės savybės yra neutralizuojamos. Kaip stambiamolekulinė gamtinė medžiaga ligLT 3519 B ninsulfonatai yra- polimeriškai nevienalyčiai; jie susideda iš Įvairiais kondensacijos laipsnio molekulių mišinio, kur, pvz., nevalytų ir netaurintų pušų ligninsulfonatų molekuliniai svoriai gali būti nuo 500 iki 50000 intervale. Priešingai, techninių ligninsulfonatų iš buko medžio molekuliniai svoriai neviršija 10000. Molekulinis svoris Įtakoja taurinimo procesai ir, priklausomai nuo panaudojimo, gali būti nustatyti, pvz., aukštesni ar žemesni kondensacijos laipsniai.Lignin sulphonates are known as salts of ligninic acid, a naturally occurring lignin derivative of wood; they have a basic phenolic structure where the strong phenolic properties are neutralized by etherification of the phenolic OH group. As a high molecular weight natural material ligLT 3519 B ninsulphonates are polymeric heterogeneous; they consist of a mixture of molecules of varying degrees of condensation, where, for example, the molecular weights of the crude lignin sulfonates of unpurified and pine can range from 500 to 50,000. In contrast, technical lignin sulphonates from beech wood have molecular weights not exceeding 10,000.
Jau daug metų ligninsulfonatai naudojami dispergavimo priemonėmis cemento mišiniams. Šiandien jie daug kur pakeisti labiau tinkamomis, geriau veikiančiomis priemonėmis. Giluminių gręžinių cemento mišiniuose naudojami, pvz., geležies ligninsulfonatai, kurie aukštesnėse temperatūrose turi reguliuoti surišimo laiką.For many years, lignin sulphonates have been used as dispersants in cement mixtures. Today, they have been replaced in many ways by more appropriate, better-functioning measures. Deep-well cementitious mixtures use, for example, iron lignin sulphonates, which at higher temperatures must control the setting time.
Yra žinoma, kad ligninsulfonatai natrio arba kalcio ligninsulfonatų pavidale cemento mišiniuose iš esmės veikia suskystinančiai ir sudaro oro poras, o taip pat gali Įtakoti surišimo laiką, pagrindinai šie ligninsulfonatai naudojami dėl suskystinimo efekto. Tokie pardavime esantys skaitlingi ligninsulfonato tipai, kaip natrio, kalcio, geležies, chromo-geležies ir t.t. ligninsulfonatai iš esmės nėra pritaikyti tirpaus vandenyje CrVI alerginio poveikio slopinimui. Kadangi iki šiol reakcijos mechanizmas dar nėra žinomas, tai pagal išradimą išankstinių bandymų pagalba empiriškai turi būti išsiaiškinta, koks ligninsulfonato tipas efektyviai Įtakoja tirpaus vandenyje CrVI redukciją. Tačiau išradimo rėmuose iš esmės buvo nustatyta, kad geležies ligninsulfonatai redukuoja CrVI efektyviau, negu kiti ligninsulfonato tipai, tuo būdu, esant tam pačiam veikimui, reikia mažesnių kiekių geležies ligninsulfonato, lyginant su kitais ligninsulfonato kiekiais.It is known that lignin sulphonates, in the form of sodium or calcium lignin sulphonates in cement mixtures, act essentially as liquefiers and form pores in the air, and can also influence the binding time, mainly due to the liquefaction effect. The numerous types of commercially available lignin sulphonates such as sodium, calcium, iron, chromium-iron, etc. are essentially not suitable for suppressing the water soluble Cr VI allergenicity. Since the mechanism of the reaction is not yet known, the present invention requires empirical investigation of the type of lignin sulfonate that effectively affects the water-soluble Cr VI reduction. However, it has been found within the scope of the invention that ferric lignin sulphonates reduce Cr VI more efficiently than other types of lignin sulphonate, thus requiring, in the same manner, lower amounts of ferric lignin sulphonate than other amounts of lignin sulphonate.
Pasinaudojant sekančiais pavyzdžiais, išradimas yra detaliau paaiškinamas žemiau.Using the following examples, the invention is explained in more detail below.
pavyzdysexample
Į po 1 kg trijų cemento rūšių 1, 2 ir 3 sauso portlandcemento pridedami skirtingi kiekiai geležies ligninsulfonato ir po to sumaišoma su vandeniu. Paskui CrVI kiekis nustatomas analitiškai. Rezultatai pateikti žemiau esančioje I lentelėje.To 1 kg of dry Portland cement of the three cement grades 1, 2 and 3 different amounts of ferric lignin sulphonate are added and then mixed with water. The Cr VI content is then determined analytically. The results are shown in Table I below.
I lentelėTable I
LS=ligninsulfonatasLS = lignin sulphonate
Išeinant iš to, kad pagal literatūrą siekiama, jog tirpaus vandenyje CrVI kiekis būtų mažesnis nei 0,1 10 3 masės %, tai galima konstatuoti, kad 300 mg bandomojo ligninsulfonato priedo 1 mg CrVI jau užtenka šios ribinės reikšmės peržengimui.Assuming that the water-soluble Cr VI content is less than 0.1 10 3 wt%, it can be stated that 300 mg of the test lignin sulfonate additive 1 mg Cr VI is already sufficient to exceed this limit.
pavyzdysexample
Kaip ir 1 pavyzdyje, į 1 kg to paties 2 cemento rūšies portlandcemento pridėti įvairūs kiekiai kalcio ligninsulfonato. Rezultatai pateikti II lentelėje.As in Example 1, various amounts of calcium lignin sulphonate were added to 1 kg of Portland cement of the same cement type 2. The results are shown in Table II.
II lentelėTable II
LS=ligninsulfonatasLS = lignin sulphonate
Nustatyta, kad, norint pasiekti pakankamą tirpaus vandenyje CrVI alerginio poveikio slopinimą, 1 mg CrVI reikia pridėti jaugiau nei 400 mg Ca-ligninsulfonato.It has been found that more than 400 mg Ca-lignin sulphonate should be added to 1 mg Cr VI to achieve sufficient inhibition of the water soluble Cr VI allergy.
3 pavyzdys kg kito portlandcemento, turinčio 1,32.10 3 masės % tirpaus vandenyje Crn, buvo sumaišytas su įvairių tipų ligninsulfonatais ir vandeniu, o po to buvo anali15 zuojamas CrVI kiekis. Rezultatai pateikti III lentelėje.Example 3 kg of other portland 1,32.10 containing 3% by weight of water-soluble Cr n, was then mixed with various types of lignin sulfonate and water, and then was anali15 Cr VI content is subject. The results are shown in Table III.
III lentelėTable III
LS=ligninsulfonatasLS = lignin sulphonate
LSI: kalcio ligninsulfonatas LS2: natrio ligninsulfonatas LS3: natrio ligninsulfonatas LS4: geležies-chromo ligninsulfonatasLSI: Calcium lignin sulphonate LS2: Sodium lignin sulphonate LS3: Sodium lignin sulphonate LS4: Iron-chromium lignin sulphonate
LS5: geležies ligninsulfonatasLS5: Iron lignin sulphonate
LS6: kalcio ligninsulfonatasLS6: Calcium lignin sulfonate
LS7: natrio ligninsulfonatasLS7: Sodium lignin sulphonate
Iš III lentelės seka, jog 5, 6 ir 7 ligninsulfonato 300 mg LS/mg CrVI kiekiai yra efektyvūs, ir Crvr koncentracijos reikšmė cemente yra sumažinama žemiau 0,1.10 3 masės % tirpaus vandenyje CrVI ribos.Table III shows that 5, 6, and 7 ligninsulfonate 300 mg LS / mg Cr VI is effective and the Cr vr concentration in the cement is reduced below 0.1.10 to 3 wt.% Of water soluble Cr VI .
Jei cementai arba cemento turintys ruošiniai jau turi ligninsulfonatų kitiems tikslams, reikia patikrinti, ar ir kokiu mastu šie ligninsulfonatai gali įtakoti tirpaus vandenyje CrVI žalingą poveikį. Pagal išradimą, esant reikalui, alerginio poveikio slopinimui reikia pridėti papildomus kiekius atitinkamai veikiančio ligninsulfonato .If the cements or cementitious preparations already contain lignin sulphonates for other purposes, it must be checked whether and to what extent these lignin sulphonates can contribute to the deleterious effects of water-soluble Cr VI . According to the invention, additional amounts of lignin sulfonate, respectively, are required for the suppression of allergic activity, if necessary.
Pagal išradimą naudojant ligninsulfonatą, tam tikromis aplinkybėmis atsirandančius pašalinius efektus, kaip suskystinimas ir/arba oro porų susidarymas ir/arba surišimo laiką įtakojantis veikimas, galima reguliuoti atitinkamomis priemonėmis. Tokios rūšies priemonės yra žinomos. Pvz., suskystinantį ligninsulfonato poveiki galima eliminuoti pridedant smulkiadispersines medžiagas. Tačiau reikia atkreipti dėmesį į tai, kad ne kiekvienas ligninsulfonatas veikia suskystinančiai. Todėl kiekvienu atskiru atveju reikia patikrinti, ar atsiranda suskystinantis poveikis ir kokiais kiekiais smulkiadispersinės medžiagos šį efektą galima reguliuoti. Pavyzdžiui, naudojant ligninsulfonatą LSI pagal III lentelę, 10 masės % mikrosilikato priedas, skaičiuojant cemento svoriui, kompensuoja suskystinantį poveikį. Naudojant LS3 pagal III lentelę, norint kompensuoti suskystinantį ligninsulfonato poveikį, užtenka 5 masės % mikrosilikato. Geležies ligninsulfonato LS5 pagal III lentelę atveju suskystinančio poveikio nėra,By the use of lignin sulphonate according to the invention, side effects such as liquefaction and / or formation of air pores and / or effect on the binding time can be controlled by appropriate means. These types of tools are known. For example, the liquefying action of lignin sulfonate can be eliminated by the addition of finely dispersed substances. However, it should be noted that not every lignin sulphonate acts as a liquefier. It is therefore necessary to check on a case-by-case basis whether a liquefying effect occurs and with what quantities of fine dispersible material this effect can be controlled. For example, when using lignin sulfonate LSI according to Table III, a 10 wt% microsilicate additive, based on the weight of the cement, compensates for the liquefaction effect. When using LS3 according to Table III, 5% by weight of microsilicate is sufficient to compensate for the liquefying effect of lignin sulfonate. In the case of iron lignin sulphonate LS5 according to Table III, there is no liquefaction,
I tuo būdu reologinis kompensavimas šiuo atveju nebūtinas .Thus, rheological compensation is not necessary in this case.
pavyzdysexample
Iš žemiau pateikto pavyzdžio seka, kad ligninsulfonato poveikis yra ir tuo atveju, kai į pardavime esančius produktus, pridedant vandenį, kartu yra pridedamas ir ligninsulfonatas. Į dviejų rūšių statybines medžiagas, klijus plytelėms ir skiedinį plyšių užtaisymui pridėjus LS, buvo nustatomas tirpus vandenyje CrVI prieš ir po geležies ligninsulfonato pagal III lentelę pridėjimo. Gauti rezultatai pateikti žemiau esančioje IV lentelėje .It follows from the example below that the effect of lignin sulphonate is also the case when commercially available products are combined with lignin sulphonate when added to water. For two types of building materials, the adhesive for tiles and mortar for the filling of cracks with LS was determined by the water soluble Cr VI before and after the addition of iron lignin sulphonate according to Table III. The results obtained are shown in Table IV below.
IV lentelėTable IV
LS=ligninsulfonatasLS = lignin sulphonate
Pagal išradimą cemento turintys ruošiniai yra, pvz., skiedinys, klijai plytelėms, skiedinys plyšių užtaisymui, tinkas arba panašūs.Cement-containing preforms according to the invention are, for example, mortar, tile adhesive, cracking mortar, plaster or the like.
II
IŠRADIMO APIBRĖŽTISDEFINITION OF INVENTION
Claims (7)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE19934321077 DE4321077A1 (en) | 1993-06-24 | 1993-06-24 | Process for the depression of the allergy-causing effect of water-soluble Cr · V ·· I · in cements and / or preparations containing cement |
Publications (2)
Publication Number | Publication Date |
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LTIP1952A LTIP1952A (en) | 1995-01-31 |
LT3519B true LT3519B (en) | 1995-11-27 |
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LTIP1952A LT3519B (en) | 1993-06-24 | 1994-06-14 | Method for reducing allergic effect induced by water-soluble cr(vi) available in cements and /or cement- containing half-finished products |
Country Status (14)
Country | Link |
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EP (1) | EP0630869B1 (en) |
AT (1) | ATE148434T1 (en) |
CZ (1) | CZ284621B6 (en) |
DE (2) | DE4321077A1 (en) |
DK (1) | DK0630869T3 (en) |
EE (1) | EE9400026A (en) |
ES (1) | ES2102100T3 (en) |
GR (1) | GR3022781T3 (en) |
HU (1) | HU215460B (en) |
LT (1) | LT3519B (en) |
LV (1) | LV11316B (en) |
PL (1) | PL303961A1 (en) |
RU (1) | RU2129868C1 (en) |
SK (1) | SK76194A3 (en) |
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ES2208976T3 (en) * | 1998-01-27 | 2004-06-16 | Chemische Werke Zell-Wildshausen Gmbh | CHROME ION REDUCTION AGENT (VI) IN CEMENT. |
EP0960865A1 (en) * | 1998-05-25 | 1999-12-01 | Chemische Werke Zell-Wildshausen GMBH | Agent for the reduction of chromium (VI) ions in cement |
AU2718699A (en) * | 1998-01-27 | 1999-08-09 | Chemische Werke Zell-Wildshausen Gmbh | Medium for reducing chromium (vi) ions in a water-curing mass |
ATE256087T1 (en) * | 1998-07-29 | 2003-12-15 | Holderbank Financ Glarus | METHOD FOR PRODUCING CHROMATE-FREE INORGANIC BINDERS |
SK282086B6 (en) | 1999-10-12 | 2001-10-08 | Pova�Sk� Cement�Re�, A. S. | Manufacturing method for cement with lowered contents of chrome |
BRPI0416622A (en) | 2003-11-21 | 2007-01-16 | Grace W R & Co | sulfate dispersion chromate reducer |
JP2007520416A (en) * | 2004-02-04 | 2007-07-26 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Liquid additives for mutual ground cement |
GB0507566D0 (en) * | 2005-04-14 | 2005-05-18 | Brine Shield Uk Ltd | Skin protection |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0054314A1 (en) | 1980-12-17 | 1982-06-23 | Aktieselskabet Aalborg Portland-Cement-Fabrik | A method and a plant for producing a dry cement composition |
EP0125267A1 (en) | 1982-11-17 | 1984-11-21 | Aktieselskabet Aalborg Portland-Cement-Fabrik | Methods of producing a dry cement mixture and a free flowing ferrous sulphate hydrate product and products prepared by the methods |
EP0133434A1 (en) | 1983-01-20 | 1985-02-27 | Cementa Ab | A method of reducing eczema-inducing chromium in cement by adding ferrous sulfate, an additive comprising ferrous sulfate and the use of the additive |
EP0524999A1 (en) | 1990-04-11 | 1993-02-03 | Aalborg Portland As | A cement composition and methods for producing same. |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE248055C (en) * | ||||
GB466639A (en) * | 1935-07-24 | 1937-06-01 | Dewey & Almy Ltd | Improvements in or relating to concrete and hydraulic cement |
DD262852A1 (en) * | 1987-08-03 | 1988-12-14 | Zementind Rationalisierung | METHOD FOR REDUCING THE CHROMATE CONTENT IN THE CEMENT LINKER |
-
1993
- 1993-06-24 DE DE19934321077 patent/DE4321077A1/en not_active Withdrawn
-
1994
- 1994-06-08 EP EP19940108800 patent/EP0630869B1/en not_active Expired - Lifetime
- 1994-06-08 DK DK94108800T patent/DK0630869T3/en active
- 1994-06-08 ES ES94108800T patent/ES2102100T3/en not_active Expired - Lifetime
- 1994-06-08 DE DE59401688T patent/DE59401688D1/en not_active Expired - Fee Related
- 1994-06-08 AT AT94108800T patent/ATE148434T1/en not_active IP Right Cessation
- 1994-06-14 LT LTIP1952A patent/LT3519B/en not_active IP Right Cessation
- 1994-06-21 LV LVP-94-129A patent/LV11316B/en unknown
- 1994-06-22 RU RU94021646A patent/RU2129868C1/en active
- 1994-06-22 HU HU9401886A patent/HU215460B/en not_active IP Right Cessation
- 1994-06-22 CZ CZ941543A patent/CZ284621B6/en unknown
- 1994-06-23 SK SK761-94A patent/SK76194A3/en unknown
- 1994-06-23 PL PL30396194A patent/PL303961A1/en unknown
- 1994-07-18 EE EE9400026A patent/EE9400026A/en unknown
-
1997
- 1997-03-11 GR GR970400465T patent/GR3022781T3/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0054314A1 (en) | 1980-12-17 | 1982-06-23 | Aktieselskabet Aalborg Portland-Cement-Fabrik | A method and a plant for producing a dry cement composition |
EP0160746A1 (en) | 1980-12-17 | 1985-11-13 | Aktieselskabet Aalborg Portland-Cement-Fabrik | A dry cement composition |
EP0160747A1 (en) | 1980-12-17 | 1985-11-13 | Aktieselskabet Aalborg Portland-Cement-Fabrik | A dry cement composition and a method for producing the same |
EP0125267A1 (en) | 1982-11-17 | 1984-11-21 | Aktieselskabet Aalborg Portland-Cement-Fabrik | Methods of producing a dry cement mixture and a free flowing ferrous sulphate hydrate product and products prepared by the methods |
EP0133434A1 (en) | 1983-01-20 | 1985-02-27 | Cementa Ab | A method of reducing eczema-inducing chromium in cement by adding ferrous sulfate, an additive comprising ferrous sulfate and the use of the additive |
EP0524999A1 (en) | 1990-04-11 | 1993-02-03 | Aalborg Portland As | A cement composition and methods for producing same. |
Also Published As
Publication number | Publication date |
---|---|
SK76194A3 (en) | 1995-02-08 |
LTIP1952A (en) | 1995-01-31 |
DK0630869T3 (en) | 1997-02-17 |
RU2129868C1 (en) | 1999-05-10 |
DE59401688D1 (en) | 1997-03-13 |
ES2102100T3 (en) | 1997-07-16 |
DE4321077A1 (en) | 1995-01-05 |
HU9401886D0 (en) | 1994-09-28 |
HUT67949A (en) | 1995-05-29 |
LV11316B (en) | 1996-12-20 |
EE9400026A (en) | 1995-12-15 |
EP0630869A1 (en) | 1994-12-28 |
CZ284621B6 (en) | 1999-01-13 |
HU215460B (en) | 1999-01-28 |
CZ154394A3 (en) | 1995-01-18 |
RU94021646A (en) | 1996-05-27 |
GR3022781T3 (en) | 1997-06-30 |
EP0630869B1 (en) | 1997-01-29 |
ATE148434T1 (en) | 1997-02-15 |
LV11316A (en) | 1996-06-20 |
PL303961A1 (en) | 1995-01-09 |
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Legal Events
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MM9A | Lapsed patents |
Effective date: 19990614 |