EP0507895A1 - Verfahren zur herstellung von einem spherosilikatzement und daraus hergestellter zement - Google Patents

Verfahren zur herstellung von einem spherosilikatzement und daraus hergestellter zement

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Publication number
EP0507895A1
EP0507895A1 EP91914369A EP91914369A EP0507895A1 EP 0507895 A1 EP0507895 A1 EP 0507895A1 EP 91914369 A EP91914369 A EP 91914369A EP 91914369 A EP91914369 A EP 91914369A EP 0507895 A1 EP0507895 A1 EP 0507895A1
Authority
EP
European Patent Office
Prior art keywords
sio
parts
spherosilicate
silicate
equal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91914369A
Other languages
English (en)
French (fr)
Inventor
André LERAT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Holcim Ltd
Original Assignee
Holderbank Financiere Glarus AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Holderbank Financiere Glarus AG filed Critical Holderbank Financiere Glarus AG
Publication of EP0507895A1 publication Critical patent/EP0507895A1/de
Withdrawn legal-status Critical Current

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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
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • 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
    • 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

  • the present invention relates to a process for preparing a cement of the spherosilicate type which hardens quickly at room temperature, as well as the cement obtained by this process. More specifically, the mineral compositions described in the invention make it possible to obtain a cement of the spherosilicate type having a setting time equal to or greater than 30 minutes at the temperature of 20 ° C. and a curing speed making it possible to obtain resistances at compression (Rc) equal to or greater than 15 MPa, after only U hours at 20 C, when tested according to the standard standard applied to hydraulic binder mortars with a binder / sand ratio equal to 0.38 and a ratio water / binder between 0.22 and 0.27.
  • Rc resistances at compression
  • the mineral compositions of the spherosilicate type according to the present invention making it possible to obtain a cement of the spherosilicate type with rapid hardening, (Rc)> 15 MPa at 4 h - 20 C, essentially comprise three reactive elements.
  • the first reagent is an aluminum silicate oxide (2SiO_, ALO_) having the cation Al in coordination (IV-V) as determined by the analysis spectrum of Nuclear Magnetic Resonance MASS-NMR
  • this alumino-silicate oxide (2Si0 2 , ALO-) is obtained by heat treatment, in an oxidizing medium, of natural hydrated alumino-silicates, in which the cation Al is in coordination (VI) as determined by the spectrum Resonance analysis
  • the second reagent is a sodium and / or potassium disilicate, soluble in water, (Na 2 , K_) (H_SiO ⁇ ) 2 ; potassium disilicate K 2 (H 3 SiO 2 ) 2 will preferably be used although the sodium disilicate Na- (H, SiO 2 ) 2 also makes it possible to produce mineral compositions of the spherosilicate type according to the invention. It is also possible to use a mixture of the two alkaline disilicates.
  • the third reagent is a basic calcium silicate, that is to say with a Ca / Si atomic ratio equal to or greater than 1. It will be essentially characterized by its ability to generate, under the action of an alkaline attack, the formation of weakly basic calcium silicate, that is to say having a Ca / Si atomic ratio of less than 1, preferably close to 0 , 5. This characterization will be established using X-ray Photoelectron Spectrometry (X.p. s.) And by analysis of the Ca_ / Si- relationships as indicated by M. Regourd, Phil. Trans. Royal Society London, A.310, pages 85-92 (1983).
  • the mineral compositions of the invention are also called mineral compositions of the spherosilicate type, since the cement of the spherosilicate type obtained results from a mineral polycondensation reaction as opposed to traditional hydraulic binders in which hardening is the result of hydration of calcium aluminates and calcium silicates.
  • the means of investigation used is the Magnetic Resonance spectrum
  • the fast-curing mineral binder, (Rc) 15 MPa at 4h - 20 ° C corresponds to a material of the spherosilicate type of the type (Ca, K) -poIy (sialate-siIoxo) of formula varying between
  • Binders and cements having rapid hardening and based on reactions of the mineral polycondensation type involving the three reagents used in the present invention have been proposed in the past.
  • This composition comprises 840 g of a so-called "standard" reaction mixture to which has been added, in addition to inert fillers, 220 g of ground blast furnace slag.
  • the reaction components of the spherosilicate type are characterized by the molar ratios of the oxides:
  • composition of the spherosilicate type comprising 1 mole of the oxide alumino-silicate (2SiO 2 , ALO 3 ), i.e. 222 g, 1.12 moles of potassium disilicate K 2 (H 3 SiO _, or 300 g, 0.21 moles K 2 0 corresponding to 28 g of anhydrous KOH at 90 I, and 290 g of water and 220 g of slag.
  • the mineral compositions of the spherosilicate type are characterized by the molar ratios between the three reactive elements which are equal or between
  • the amount of alkaline disilicate is reduced from 200% to 300% compared to the prior state of the art. It was not enough, for this, to simply lower the amount of this alkaline disilicate. Indeed, it was surprising to note that it was essentially necessary to change the physical state of the constituents.
  • the aforementioned known compositions are in the liquid phase.
  • the slag is added to an aqueous reaction mixture containing the aluminum silicate oxide (2SiO 2 , ALO 2 ), the alkalis, the water and the potassium polysilicate in solution.
  • the mineral compositions of the spherosilicate type are in the solid phase, in particular the second reagent, the sodium and / or potassium disilicate (Na 2 , K 2 ) (f-SiO. is a finely divided powder, water being added only in the final phase of mixing the mortar or binder.
  • mineral powder compositions for example mineral compositions comprising:
  • amorphous silica In this latter composition, the role of amorphous silica is essentially to replace part of the potassium silicate necessary for mineral polycondensation, that is to say that the amorphous silica reacts with potassium hydroxide to produce, in the mortar, the quantity of potassium silicate desired.
  • potassium silicate means industrial potassium silicate, in powder form, corresponding to the formula K 2 O, 3SiO 2 , 3H 2 O, soluble in water and making it possible to produce binders and adhesives having the same properties as "soluble glasses” or alkali silicate in solution.
  • the compressive strength Rc at 4 h - 23 C is only around 6.9 MPa, which is much lower than (Rc)> 15 MPa at 4 h - 20 ° C, as claimed in the present invention.
  • Rc at 4 h - 23 C is only about 4.6 MPa, while in still other examples, only Rc at around 65 C are given, Rc at 4 - 23 C being too weak to be mentioned.
  • the powdered alkaline disilicate makes it possible to obtain a cement of the spherosilicate type having a rapid hardening, at 20 ° C., in a few hours, i.e. (Rc)> 15 MPa at 4h - 20 ° C.
  • the mineral composition of the spherosilicate type comprises for 52 parts of metakaolin, 24 to 28 parts of potassium hydroxide, 73 to 120 parts of silica smoke, 18 to 29 parts of slag.
  • Silica smoke reacts with potassium hydroxide to produce potassium silicate in the mixture, which is a way of lowering the cost price of this very expensive reagent.
  • K 2 (H 3 SiO) 2 from 0.215 to 0.25 moles which gives a ratio K j on (2SiO 2 , ALO_) between 0.93 and 1.08, again practically the ratios discussed above.
  • mixture A oxide (2Si0 2 , AL0 3 ) 400 g micronized mica 100 g
  • mixture B oxide (2Si0 2 A! 2 0 3 ) 400 g silica smoke 100 g
  • liquid 1 40% potassium silicate solution 520 g
  • liquid 2 40% sodium silicate solution 1040 g
  • the mixture between the powder and the liquid is carried out according to the pro ⁇ portions indicated in the table, and the mineral polycondensation is followed by Differential Thermal Analysis.
  • the values of the J / g ratio are compared, that is to say the amount of energy measured in Joules on the weight of the sample in grams.
  • the mineral polycondensation temperature is 60 C.
  • test No. 2 (with silica smoke) is divided by 5 compared to that of test No. 1 (without silica smoke), and that of test No. 3 is divided by 2.
  • amorphous silica such as silica fume or other silicas which it is known that they can easily transform into potassium or sodium silicate, at moderate or even ambient temperature, will be added in such a quantity that it will not disturb the natural exothermicity of the mixture of the spherosilicate type.
  • Amorphous silica such as, for example, silica smoke, rice ash, diatomaceous earth, silicic smectites, certain strongly silicic pozzolans (with a high percentage of allophane and glass of volcanic origin) are considered as finely divided, reactive loads.
  • the third reagent of the invention is weakly basic calcium silicate with the Ca / Si atomic ratio of less than 1.
  • This third reagent is linked to the preceding ones by the molar ratios between the three reactive elements equal to or comprised between
  • the sum of the number of moles of calcium disilicate, Ca (H, SiO y ) _, and the number of moles of potassium disilicate, K_ (H, SiO y ) _, is equal to the number of moles of the aluminum silicate oxide (2SiO_, ALO_).
  • This alumino-silicate oxide (2Si0 2 , AL0 3 ) determines all the reaction conditions of the mineral compositions of the spherosilicate type. It will react with an alkaline or alkaline earth disilicate to form, after mineral polycondensation, a compound (Si 2 O_, ALO 2 , Si 2 O 5 , (K 2 O, CaO)), i.e. (K, Ca) -poly (sialate-siloxo) of formula between
  • the oxide (2Si0 2 , AL0 3 ) reacts first with the most soluble disilicate which is always the alkaline disilicate (Na 2 , K 2 ) (H 3 SiO.) 2 .
  • the amount of calcium dislicate involved in the mineral polycondensation reaction is essentially determined by the amount of alkaline disilicate. If the sum of the moles of these disilicates is greater than 1, the non-reacting part will be that which is the least soluble, that is to say the calcium disilicate.
  • Calcium disilicate Ca (H_SiO i .) 2 can be produced separately, for example by hydrothermal reaction between lime and silica.
  • the starting material is a basic calcium silicate, that is to say with the Ca / Si atomic ratio greater than or equal to 1.
  • This will be for example wollastonite Ca (Si0 3 ), gehlenite (2CaO .AI 2 0 3. Si0 2 ), bicalcium silicate C 2 S (2CaO.Si0 2 ), tricalcium silicate CS (3CaO .Si0 2 ), Akermanite (2CaO.SiO 2 ).
  • Blast furnace slag essentially contains the basic silicates gehlenite, akermanite, wollastonite and is therefore very suitable.
  • This process is very regular and can be completed in 30 minutes, at room temperature.
  • C 2 S there occurs in a few seconds a high concentration of weakly basic silicate Ca / Si less than 1; then the attack is stopped, and then continues more regularly. This is called the "flash-set" or formation of a gel creating a false catch.
  • setting retarders like those commonly used in cement mixtures portiand.
  • the mineral polycondensation reaction used in the present invention should not be confused with the simple alkaline activation of hydraulic binders, or with the action of alkali setting accelerator on portland cements and other hydraulic binders. Indeed, the simple action of alkalis, NaOH or KOH, on portland cements or blast furnace slag, results in the production of hydrated calcium silicates, as mentioned above. In contrast to what happens in the present invention, these hydrated silicates crystallize to form CSH, the main constituent of hydraulic calcium cements.
  • the CSH is a monosilicate and / or a bisilicate, that is to say that the SiO 2 tetrahedra which constitute it belong to the category (QO), (Ql) and possibly (Q2).
  • the mineral polycondensation leads to the formation of SiO tetraera of type (Q4, as determined by the analysis spectrum in Nuclear Magnetic Resonance MASS-NMR for 29 Si.
  • alkalis, NaOH and KOH are setting accelerators, they do not constitute hardening accelerators capable of achieving the object of the invention, that is to say (Rc) 15 MPa at 4 h - 20 ° C .
  • the hardening accelerator is usually temperature or the addition of portiand cement. It is for example known to use a cement based on slag, portian cement or lime, and an alkaline accelerator such as NaOH and sodium and or potassium carbonates.
  • a mixture comprising alumino-silicate oxide (2Si0 2 , AL0 3 ), slag (or cement) and alkalies KOH, NaOH, does not constitute a mineral binder of mineral polycondensation according to the present invention. It is known that a mortar made with this mixture and water does not harden at 20 C for 24 hours. Thus it is known that if the oxide (2Si0 2 , ALO_) is not masked by a polysilicate solution against the attack of strong bases KOH, NaOH, a simple poly (sialate) of the type is formed. hydroxysodalite and which precipitates without binding function. It is known that hydroxysodalite constitutes a binder only in ceramic pastes, with very little water and when the material is compressed.
  • the third reagent of the mineral polycondensation composition is calcium silicate. It can be accompanied by complex calcium aluminates and silicates.
  • blast furnace slag is partly formed of a glass composed inter alia of gehlenite 2CaO.AL0 3 .Si0 2 , of akermanite 2Ca0.Mg0.2Si0 2 , of wollastonite.
  • AI (V1) equal to or greater than 1.
  • SiO j (Q) is 4 to 6 times greater than the sum of the concentrations of SiO tetrahedrons ask(QO) + (Q1) + (Q2), and depending on the nature of the charges we will have
  • Blast furnace slag is a cheap source of wollastonite, gehlenite and ackermanite.
  • the mineral polycondensation compositions of the invention containing blast furnace slag make it possible to produce a mineral polycondensation binder, in powder form, containing: a) 100 parts by weight of aluminum silicate oxide (2SiO-, ALO,) having the cation Al in coordination
  • the mortar obtained by adding a quantity of water such that the water / binder ratio is between 0.20 and 0.27 and a quantity of standardized sand such that the binder / sand ratio 0.38 hardens cold and develops after 4 hours at 20 ° C a compressive strength greater than or equal to 15 MPa.
  • setting is considered to be slow, since it takes place after a time of more than 30 minutes without the addition of retarder, which allows use in industry, with traditional mixers .
  • retarder which allows use in industry, with traditional mixers .
  • the table groups the setting times for different milk / water weight ratios, compositions involving alkali silicate solutions and inorganic polycondensation compositions containing powdered alkaline disilicates, according to the present invention.
  • start of setting (at 20 ° C.) for the present invention 30 min 60 min 90 min 3 hours
  • potassium disilicate K 2 H., SiO 2
  • sodium disilicate Na 2 H, SiO tt _
  • sources of impure alkalis containing both potassium and sodium This is often the case for industrial waste very rich in alkalis such as filter dust from portain cement calcining furnaces or alkaline detergents from the mining industry or chemical.
  • the advantage of the present invention also lies in the fact that the use of alkaline disilicate (Na 2 , K 2 ) (H 3 SiO 2 ) 2 in powder makes it possible to use inexpensive raw materials coming from industrial waste.
  • An interesting source of amorphous silica is the silica smoke recovered in the filters above the melting furnaces of ferro-silicone steels. These silica fumes contain 90-95% Si0 2 , carbon, and 0.5-1% finely dispersed metallic silicon. These silica fumes make it possible to manufacture the alkaline disilicate at very low temperatures, even at ordinary temperature.
  • silica sands it is generally necessary to work in an autoclave when reacting alkali hydroxides, or in fusion when using alkali carbonates. It is also possible to use amorphous silica of natural origin such as diatomaceous earth, very siliceous smectics and gaizes, very siliceous volcanic glasses and pozzolans. Ash rich in silica, obtained by calcining plants (rice for example), can also be used for this purpose.
  • the manufacture of aluminum silicate oxide (2SiO 2 , ALO,) is carried out by treating between 650 ° C and 800 ° C kaolinitic clays.
  • Kaolinitic sands can be used as raw material, as well as certain clays containing at the same time kaolinite, montmorillonite and illite; likewise lateritic soils and laterites containing both kaolinite. Tests carried out on pyrophillites show that these materials are suitable for mineral polycondensation.
  • the heat treatment temperatures of the raw materials must be adjusted so that they allow optimum production of aluminum silicate oxide (2SiO 2 , AO 3 ) having the highest concentration of Al coordinating Al (IV-V) as
  • the alkalis are generally the sodium and / or potassium hydroxides produced industrially by electrolysis. They are also the result of the chemical reaction between an alkaline salt and calcium hydroxide or a material producing it in situ.
  • the alkaline salts are selected from sodium and potassium carbonates, potassium sulfates, potassium sulfites. It is thus possible to use the dust collected on the filters of portiand cement kilns which are very rich in sulfites and sulfates. potassium, convert them to carbonates using the Leblanc process, or react them with clinker to produce potassium hydroxide in situ.
  • the powdered alkaline disilicates obtained in this case during the reaction between the amorphous silicas and the alkalis as in Example 1 below are rather double potassium and calcium disilicates. They also allow the present invention to be carried out.
  • the molar ratio K 2 (H 3 SiO.) 2 / (2Si0 2 , AL0 3 ) is equal to 0.43.
  • the dairy / alkaline disilicate weight ratio is equal to
  • a mortar is made as in example 2.
  • the molar ratio K 2 (H 3 SiO 2 / (2Si0 2 , ALO,) is equal to 0.56.
  • the milk / alkaline disilicate weight ratio is equal to
  • Example 2 22 parts of (2Si0 2 , AL0 3 ), 15 parts of slag, 20 parts of silica smoke and 11 parts of KOH are mixed dry, then the sand is added and then 25 parts of water. A mortar is thus obtained as in Example 2. There is no setting, even at 24 hours at 20 ° C.
  • a mixture containing 27 parts of (2SiO 2 , ALO_), 21 parts of slag, 15 parts of fumed silica and 19 parts of potassium disilicate K 2 (H 3 SiO 2 prepared according to Example 1) is prepared dry. 215 parts of standardized sand and then 21.5 parts of water.
  • the starts after 35 minutes, and the resistance Rc after 4 hours at 20 ° C is 16 MPa, with a water / binder ratio 0.26.
  • the molar ratio K 2 (H 3 SiO 2 is equal to 0.58.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
EP91914369A 1990-09-03 1991-08-24 Verfahren zur herstellung von einem spherosilikatzement und daraus hergestellter zement Withdrawn EP0507895A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH285090 1990-09-03
CH2850/90 1990-09-03

Publications (1)

Publication Number Publication Date
EP0507895A1 true EP0507895A1 (de) 1992-10-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP91914369A Withdrawn EP0507895A1 (de) 1990-09-03 1991-08-24 Verfahren zur herstellung von einem spherosilikatzement und daraus hergestellter zement

Country Status (8)

Country Link
EP (1) EP0507895A1 (de)
AU (1) AU8422591A (de)
CS (1) CS270091A3 (de)
EC (1) ECSP910776A (de)
ES (1) ES2033584B1 (de)
GB (1) GB2247453A (de)
MX (1) MX9100897A (de)
WO (2) WO1992004295A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH682561A5 (de) * 1990-09-03 1993-10-15 Holderbank Financ Glarus Tectoalumosilicat-Zement, daraus erhaltene Bindemittelmatrix, und Beton mit dieser Bindemittelmatrix.
BR0114402A (pt) * 2000-10-05 2003-07-29 Suz-Chung Ko Cimento de escórias
FR2882276A1 (fr) * 2005-02-21 2006-08-25 Philippe Pichat Fabrication d'un materiau solide a partir d'un hydroxyde alcalin
WO2007109862A1 (en) 2006-03-29 2007-10-04 Zeobond Research Pty Ltd Dry mix cement composition, methods and systems involving same
FR2904972B1 (fr) * 2006-08-21 2009-12-18 Philippe Pichat Composition a prise hydraulique.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3071695D1 (en) * 1979-09-04 1986-09-18 Joseph Davidovits Synthetic inorganic polymer of the silicoaluminate family and process for the preparation thereof; moulded articles containing this polymer, and process for their preparation
US4509985A (en) * 1984-02-22 1985-04-09 Pyrament Inc. Early high-strength mineral polymer
US4642137A (en) * 1985-03-06 1987-02-10 Lone Star Industries, Inc. Mineral binder and compositions employing the same
US4640715A (en) * 1985-03-06 1987-02-03 Lone Star Industries, Inc. Mineral binder and compositions employing the same
WO1988002741A1 (fr) * 1986-10-14 1988-04-21 Nicolas Davidovits Materiau composite ceramique-ceramique et procede d'obtention
FR2657867B1 (fr) * 1990-02-05 1994-01-14 Joseph Davidovits Ciment rapide geopolymerique a base de ciment portland et procede d'obtention.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9204295A1 *

Also Published As

Publication number Publication date
MX9100897A (es) 1992-05-04
CS270091A3 (en) 1992-03-18
ES2033584B1 (es) 1994-04-01
ECSP910776A (es) 1992-05-25
ES2033584A1 (es) 1993-03-16
GB2247453A (en) 1992-03-04
AU8422591A (en) 1992-03-30
GB9118639D0 (en) 1991-10-16
WO1992004295A1 (fr) 1992-03-19
WO1992004294A1 (fr) 1992-03-19

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