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
  • 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
  • C04B28/34—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 cold phosphate binders
• • 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
  • C04B12/02—Phosphate cements
• • 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
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

• the invention relates to a new hydraulic phosphomagnesium binder and a mortar obtained from this new binder.
• Phosphomagnesium cements are hydraulic binders, that is to say binders which, in the presence of water, solidify. They are characterized by a binder based on phosphorus and magnesium compounds.
• cements are particularly interesting for their rapid setting and their high mechanical properties. This very rapid setting is particularly advantageous in applications such as the repair of structures for which rapid return to service is desired.
• Phosphomagnesium binders like most hydraulic binders, however, exhibit a degradation of their mechanical properties after exposure to high temperatures. This degradation does not allow them to be used in applications such as sealing for chimney flues or fire panels.
• the object of the present invention is to provide a new phosphomagnesium binder which makes it possible to obtain a material which retains its mechanical properties after exposure to high temperatures.
• This object is achieved by the present invention which relates to a phosphomagnesium binder which comprises at least one magnesium compound and a mixture of phosphorus compounds, the mixture of phosphorus compounds comprising at least two compounds chosen from an aluminum phosphate, a phosphate potassium and an ammonium phosphate.
• the invention also relates to a cement matrix which comprises the phosphomagnesium binder of the invention and granular elements.
• the invention also relates to a method for preparing a mortar which comprises adding water to the cementitious matrix and, mixing the matrix added with water to obtain a homogeneous and fluid mortar, the quantity of water added being such that the ratio E / L is between 0.20 and 0.50, E representing the amount of water and L the amount of magnesium compound and phosphorus compound, the mortar thus obtained, and the articles capable of 'be obtained from phosphomagnesium mortar.
• a phosphomagnesium binder comprising a particular mixture of phosphorus compounds makes it possible to obtain articles which have good mechanical properties at room temperature and whose mechanical properties are preserved after exposure to high temperatures.
• the term "mortar” indifferently denotes mortars or grouts based on phosphomagnesium binder.
• phosphorus compound all of the phosphorus-based compounds can be used insofar as they comprise phosphorus pentoxide, available directly or in the form of a precursor.
• ammonium, aluminum and potassium salts of the following phosphorus compounds may be mentioned without intending to be limited, as ammonium phosphate, potassium phosphate and aluminum phosphate: phosphorus pentoxide, phosphoric acid or derivatives such as orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid.
• the phosphomagnesium hydraulic binder can contain these phosphorus compounds alone or as a mixture provided that a mixture as defined above is obtained.
• the mixture of phosphates is a mixture which comprises an ammonium phosphate and at least one phosphorus compound chosen from a potassium phosphate and an aluminum phosphate.
• the phosphate mixture comprises an aluminum phosphate and a potassium phosphate.
• the mixture comprises an aluminum phosphate, an ammonium phosphate and a potassium phosphate.
• the ammonium salt is a phosphate or an ammonium hydrogenphosphates, alone or as a mixture. Even more preferably, the ammonium salt is ammonium dihydrogenophosphate, optionally mixed with ammonium tripolyphosphate.
• the potassium salt is a potassium phosphate.
• the aluminum salt is an aluminum phosphate or metaphosphate, alone or as a mixture. Even more preferably, the aluminum salt is aluminum metaphosphate.
• the amount of each of the phosphorus compounds in the mixture varies depending on the intended application.
• the quantity of ammonium phosphate (s) is predominant compared to the total quantity of phosphorus compounds entering into the composition of the phosphomagnesium binder.
• the phosphorus compounds can be in liquid or solid form, preferably solid.
• the phosphorus compounds are in the form of particles whose particle size is more particularly at most 300 ⁇ m. It should be noted that this value is not critical and that, if it is possible to use constituents whose particle size is greater than 300 ⁇ m, grinding before incorporation into the composition according to the invention may be desirable . This grinding can improve the kinetics of dissolution of phosphorus compounds.
• the phosphorus compounds are used in a form adsorbed on a porous support.
• a porous support mention may be made, for example, of diatomaceous earth, clay, bentonite, silica, alumina.
• the adsorption is carried out in a manner known per se.
• the phosphorus compounds, in solution or in suspension are brought into contact with the support, with stirring, then the resulting suspension is heated so as to evaporate the excess liquid.
• This operation can likewise be carried out by impregnating the support in a drum or on a rotating disc.
• the phosphomagnesium binder also comprises at least one magnesium compound.
• Any magnesium-based compound is suitable for the present invention as long as it reacts with the phosphorus compound in the presence of water.
• the following magnesium compounds magnesium oxide, magnesium hydroxide, magnesium carbonate.
• a compound based on magnesium oxide is used.
• Particularly suitable for so-called “dead bumed” magnesia usually obtained after calcination of magnesium carbonate at temperatures above 1200 ° C.
• the magnesium oxide can be used in a pure form or can optionally comprise at least one element of the calcium, silicon, aluminum or even iron type, these elements being generally in the form of oxide or hydroxide.
• this type of compound mention may be made of dolomite, a mixture comprising in particular magnesium oxide and calcium oxide.
• magnesium oxide is used in pure form, the purity of the oxide is at least 80%.
• Magnesium compounds are preferably used whose specific surface is less than 10 m 2 / g. More specifically, the specific surface is less than 2 m 2 / g.
• the particle size of the magnesium compound is usually between 10 and 500 ⁇ m. It would be possible to use compounds whose particle size is outside the aforementioned range, but without this bringing any particular advantages. Thus, if the particle size is greater than 500 ⁇ m, a grinding step prior to incorporation into the composition may be necessary. Furthermore, if the particle size of said constituents was less than 10 ⁇ m, one could observe a modification of the properties of the composition brought into contact with water. One can in particular note an increase in the setting speed of the cement, except to increase the content of agent delaying the setting, which will be discussed in the following description. As a result, the mortar according to the invention could be less advantageous from the point of view of implementation or from an economic point of view. In the phosphomagnesium binder, the proportion of the magnesium compound
• the phosphomagnesium binder of the present invention can be used for the preparation of mortar.
• a mortar is obtained from a cementitious matrix which comprises, in addition to the phosphomagnesium binder as defined above, granular elements whose average size varies according to the envisaged application, and optionally additives known in the field of hydraulic binders.
• the size of the granular elements can conventionally vary between 1 and 500 ⁇ m.
• the mortar is prepared by kneading the cement matrix with water, the W / L ratio being between 0.20 and 0.5, preferably 0.22 and 0.38, E representing the amount of water, L the amount of phosphorus compounds and magnesium compounds constituting the binder.
• sand SiO 2 , TiO 2 , AI 2 O 3 , ZrO 2 , Cr 2 O 3 , talc, mica, kaolin, bentonite, metakaolin, crude dolomite , chromium ore, clinker, vermiculite, periite, mica, cellulose, slag.
• They can be synthetic products. They can be crystallized or amorphous compounds obtained, for example, by grinding and sieving to the desired size. It is also possible to use the smoke of condensed silica, ground silica, fumed silica, fly ash.
• a mixture of mineral fillers preferred according to the invention is a mixture which contains little or no sand-lime sands.
• stable mineral elements will be used in the temperature range considered.
• the fly ash that can be used are generally silicoaluminous ashes from combustion in thermal power plants in particular.
• the particle size of these ashes is usually between 0.5 and 200 ⁇ m.
• the condensed silica smoke, optionally constituting the composition according to the invention generally has a specific surface of between 20 and 30 m 2 / g.
• the amount of granular elements is between 0 and 1000 parts by weight per 100 parts by weight of binder.
• the amount of sand, silica or the other granular elements mentioned in this list is generally between 0 and 900 parts by weight relative to the same reference as above.
• the amount of condensed silica smoke or fly ash is between 0 and 100 parts by weight.
• the binder can comprise any conventional additive in the field of hydraulic binders, such as water repellents; plasticizers, in particular alkoxysilanes; anti-foaming agents, in particular anti-foaming agents based on polydimethyl-siloxanes.
• defoaming agents mention may in particular be made of silicones in the form of a solution, of a solid, and preferably in the form of a resin, of an oil or of an emulsion, preferably , in water.
• Particularly suitable are silicones essentially comprising M units ) and D (R2SiO).
• the radicals R which are identical or different, are more particularly chosen from hydrogen and alkyl radicals comprising 1 to 8 carbon atoms, the methyl radical being preferred.
• the number of patterns is preferably between 30 and 120.
• the amount of silicone used in the cement according to the invention is less than or equal to 10 parts by weight per 100 parts by weight of binder, and preferably less than or equal to 5 parts by weight.
• the binder may include texturing and viscosity agents, for example cellulose fibers, guar, starch, cellulose ether, starch ethers, polyvinyl alcohol.
• the cement comprises an agent delaying setting. More particularly, this agent is chosen from compounds capable of complexing magnesium.
• the latter may in particular be carboxylic acids, such as citric, oxalic, tartaric acids, acids, esters or salts containing boron, acids, esters or salts containing phosphorus, such as sodium tripolyphosphate, ferrous sulfate, sodium sulfate and lignosulfonate, zinc chloride, copper acetate, sodium gluconate, sulfate sodium acetate cellulose, the product of the reaction of formaldehyde with aminolignosulfate, dialdehyde starch, N, N- dimethyloldihydroxyethylene urea, silicofluorides, tall oil and sucrose, these compounds being taken alone or as a mixture.
• carboxylic acids such as citric, oxalic, tartaric acids, acids, esters or salts containing boron
• acids, esters or salts containing phosphorus such as sodium tripolyphosphate, ferrous sulfate, sodium sulfate and lignosulf
• the carboxylic acids are used, alone or as a mixture, and preferably the acids, esters or salts containing boron.
• the acids, esters or salts containing boron there may be mentioned, without intending to be limited, boric acid and its salts, such as the alkali metal salts, such as sodium (borax), the amine or ammonium.
• Esters of acid boric are also suitable for the implementation of the invention, such as trialkyloxyborates, triaryloxyborates.
• the amount of agent delaying setting is at most 10% by weight relative to the weight of binder. Preferably, this amount is at most 5%. Generally, such additives do not represent more than 10 parts by weight per 100 parts by weight of binder phase. Preferably, the amount of additives is between 0 and 5 parts by weight. According to a particular mode, the additive (s) are used in the form of a powder whose average diameter is from 10 to 200 ⁇ m.
• the amount of water to be introduced for the preparation of the mortar according to the invention is such that a homogeneous and malleable plastic paste is obtained. It depends on the subsequent application of the mortar. Indeed, if one wishes to make internal coatings of piping, the paste is in general more cohesive than a mortar intended to constitute a floor covering, or the preparation of slabs or panels.
• the mixing of the phosphomagnesium binder, the granular elements, any additives and water can be carried out by any suitable method.
• a composition is generally prepared comprising the phosphomagnesium binder, the granular elements, if necessary the retarding agent and all or part of the optional additives previously mentioned in general in solid form.
• This composition is then mixed with water, the latter comprising, if this is the case, the elements not introduced in the previous stage of preparation of the composition, such as liquid additives.
• a cement matrix all of the elements of which are in the form of a powder, in order to have to add only water during mixing.
• the essential point of the process is that it is implemented so as to obtain a distribution of all the constituent elements as homogeneous as possible in the mass of the mortar.
• the components are mixed by any known means and preferably under shearing conditions, for example using a mixer.
• the mixing operation is advantageously carried out at a temperature close to room temperature.
• the mortar thus obtained can be used as repair and sealing mortars, for example in the rapid repair of structures. It can be used to seal cracks, holes or cover degraded areas as well as for the repair of reinforced structures.
• mortars or grouts in addition to resistance to exposure to high temperatures, have good adhesion to so-called Portland cements and significant mechanical properties of resistance to bending and compression, making them particularly suitable for this type. applications. They can also be used as floor coverings, pipes, even in contact with aggressive media.
• the mortar can also be used for the production of panels, in particular interior or exterior facing panels which can be exposed to high temperatures.
• the mortar is poured into a suitable mold, to give slabs or panels.
• Mortar can also be sprayed.
• the molded or sprayed products are then allowed to dry, advantageously at a temperature close to room temperature.
• the mortar of the present invention previously described may contain fibers.
• Composite materials are thus obtained.
• polypropylene polyester
• polyaramide fibers such as, for example, KEVLAR®
• carbon fibers polyamide
• polyvinyl alcohol polyvinyl alcohol
• amorphous cast ribbons glass fibers.
• glass fibers usually used in cements are suitable. It is therefore possible to use alkali-resistant fibers, such as special glass fibers obtained in particular by treatment with zirconium, as well as soda-lime glass fibers. Standard fibers are also suitable for obtaining composite materials according to the invention. Thus, conventional glasses like borosilicate glasses usually destroyed in an alkaline medium.
• the fibers have lengths varying from 1 mm to several tens of millimeters.
• the amount of fibers in the composite material according to the invention is between 0.1 and 10% relative to the weight of binder, preferably between 0.1 and 4%.
• the composite materials according to the invention are obtained by mixing the cement as described above, with the fibers.
• the samples tested are produced using a Perrier type mixer by mixing the constituents described below for 4 minutes to dryness, then adding water. Then knead two minutes at slow speed and then two minutes at fast speed. The mixture is poured into prismatic molds (10mmX10mmX10 cm).
• test pieces are removed from the mold 1 hour after setting time and stabilized in an air-conditioned atmosphere at 20 ° C. and constant humidity for 1 to 2 days. The test pieces are then placed in an oven at the desired temperature for 1/2 day. The flexural rupture stresses are measured after cooling.
• the tests are carried out in three-point bending (NFP 18407) with a spacing of 70 mm and a speed of 0.5 mm per minute on six test pieces using a hydraulic testing machine (200 kN).
• the following phosphomagnesium binder is produced (% by weight) 50% by weight of MgO (magnesia)
• the following phosphomagnesium binder is produced (% by weight)
• the Water / Binder ratio is equal to 0.26.
• the following phosphomagnesium binder is produced (% by weight) 50% MgO
• ammonium phosphate binder (NH 4 ) 2 HPO 4 marketed by Rhodia 5% aluminum phosphate (analytical purity, marketed by Aldrich), 17.5% potassium phosphate (analytical purity, marketed by Aldrich), 10% aluminum metaphosphate, (analytical purity, marketed by Aldrich).
• the water / binder ratio is equal to 0.16.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Structural Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)

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• 2000
  • 2000-06-05 FR FR0007146A patent/FR2809724B1/fr not_active Expired - Fee Related
• 2001
  • 2001-06-01 WO PCT/FR2001/001707 patent/WO2001094270A1/fr not_active Application Discontinuation
  • 2001-06-01 US US10/297,073 patent/US20030127025A1/en not_active Abandoned
  • 2001-06-01 EP EP01940667A patent/EP1289907A1/fr not_active Withdrawn
  • 2001-06-01 AU AU2001274179A patent/AU2001274179A1/en not_active Abandoned
  • 2001-06-01 CA CA002408504A patent/CA2408504A1/fr not_active Abandoned
  • 2001-06-01 MX MXPA02011902A patent/MXPA02011902A/es unknown

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