WO2002098622A1 - Extrudeur pour la fabrication d'une plaque a base de liant tel que platre - Google Patents
Extrudeur pour la fabrication d'une plaque a base de liant tel que platre Download PDFInfo
- Publication number
- WO2002098622A1 WO2002098622A1 PCT/FR2002/001930 FR0201930W WO02098622A1 WO 2002098622 A1 WO2002098622 A1 WO 2002098622A1 FR 0201930 W FR0201930 W FR 0201930W WO 02098622 A1 WO02098622 A1 WO 02098622A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- binder
- grid
- extruder
- plate
- veil
- Prior art date
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 37
- 239000011507 gypsum plaster Substances 0.000 title abstract 4
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004568 cement Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 239000011505 plaster Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 235000013305 food Nutrition 0.000 claims description 2
- 230000009182 swimming Effects 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 abstract description 7
- 238000005192 partition Methods 0.000 abstract 2
- 239000011398 Portland cement Substances 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000002671 adjuvant Substances 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- 229910052602 gypsum Inorganic materials 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 229920000193 polymethacrylate Polymers 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- 229910052925 anhydrite Inorganic materials 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000008030 superplasticizer Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 239000004794 expanded polystyrene Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910001653 ettringite Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000010451 perlite Substances 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
- 229920000580 poly(melamine) Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B5/00—Producing shaped articles from the material in moulds or on moulding surfaces, carried or formed by, in or on conveyors irrespective of the manner of shaping
- B28B5/02—Producing shaped articles from the material in moulds or on moulding surfaces, carried or formed by, in or on conveyors irrespective of the manner of shaping on conveyors of the endless-belt or chain type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/12—Apparatus or processes for treating or working the shaped or preshaped articles for removing parts of the articles by cutting
- B28B11/125—Cutting-off protruding ridges, also profiled cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B19/00—Machines or methods for applying the material to surfaces to form a permanent layer thereon
- B28B19/0092—Machines or methods for applying the material to surfaces to form a permanent layer thereon to webs, sheets or the like, e.g. of paper, cardboard
-
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/04—Portland 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
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
- C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- 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
- C04B28/14—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 calcium sulfate 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
- 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
- C04B28/14—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 calcium sulfate cements
- C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/08—Producing shaped prefabricated articles from the material by vibrating or jolting
-
- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]
Definitions
- the present invention relates to binder-based plates such as plaster, cement or the like.
- plate is meant a generally flat thin product, the height of which is small, compared to the other two dimensions, whether the cross section is straight or not, for example in crenellations, sinusoidal such as a corrugated sheet, or the like.
- the object of the present invention is to propose a method for producing such plates of low cost, in particular by the fact that it is carried out continuously.
- a method of manufacturing a plate based on a binder such as plaster, cement or the like is characterized in that it comprises the steps consisting in: a) mixing a composition intended to form the body of plate with water; b) depositing the mixture on a traveling support, which is continuously driven by a belt conveyor, said mixture passing through an extruder forming a plate, said extruder being subjected to vibrations; c) cut the plate obtained at least to length.
- step c the plate is cut both in length and in width.
- the deposition according to step b) is carried out on a so-called lower facing; the deposit according to step b) is covered with a so-called upper facing.
- the facing consists of a grid and / or a veil.
- the grid is made of glass fibers.
- the veil covers the grid over its entire width; alternatively, the web is in the form of a strip and covers only the lateral edges of the grid.
- the veil is a mat, preferably made of glass fibers.
- the cut is a water jet cut.
- the lateral edges of the plates are previously formed by inverting the lower grid and then cut straight; the inverted part of the lower grid is covered with the upper grid whether or not associated with a veil; alternatively, the inverted part of the lower grid covers the upper grid whether or not associated with a veil.
- At least the lateral edges of the lower grid are associated with a veil.
- operation b) is carried out so that two of the lateral edges of the plate are thinned.
- At least one of the facings is a cardboard, replacing the grid and / or the veil.
- the present invention also relates to an extruder, for the implementation of the above method, of the kind comprising a transverse extrusion die, characterized in that said die is at least partially subjected to vibrations.
- the die is provided with an upper lip and a lower lip which carries on its lower face at least one vibrator; the distance between the upper and lower lips of the die is adjustable.
- the axis of the vibrator can be oriented horizontally and / or vertically.
- the extrusion die has the general shape of a rectangle, the ends of the lengths facing each other slightly approaching one another towards the outside.
- the present invention also relates to a binder-based plate such as plaster, cement or the like, characterized in that it is produced according to the above process.
- the present invention also relates to the use of such a plate, in which the binder is a cementitious binder, for forming or covering walls, walls, floors or roofs, inside or outside buildings, such as industrial kitchens, food laboratories, showers, bathrooms, basins or swimming pools, and / or rooms frequently washed with a water jet, such as rooms in agricultural buildings or industrial butcheries, as well as the use of such a plate, in which the binder is based on plaster, to form or cover walls, walls or other.
- the binder is a cementitious binder, for forming or covering walls, walls, floors or roofs, inside or outside buildings, such as industrial kitchens, food laboratories, showers, bathrooms, basins or swimming pools, and / or rooms frequently washed with a water jet, such as rooms in agricultural buildings or industrial butcheries, as well as the use of such a plate, in which the binder is based on plaster, to form or cover walls, walls or other.
- FIG. 1 is a representative diagram of a method according to the invention
- FIG. 2 to 4 show an extruder used in the method according to the invention, Figure 2 being an elevational view and Figures 3 and 4 views according to arrows III and IV of Figure 2 respectively;
- FIG. 5 is a view similar to Figure 3 and shows a variant
- FIG. 6 is a partial sectional view of a plate according to the invention before cutting its longitudinal edges
- FIG. 7 is a partial sectional view of a plate according to the invention after cutting its longitudinal edges along line C of Figure 6;
- Figures 8 to 17 are schematic views similar to Figure 6 each showing a variant of the plate before cutting its longitudinal edges.
- the binder of the plate body includes a mixture of Portland cement, sulfoaluminous clinker and a source of calcium sulfate (anhydrite, plaster or gypsum).
- Portland cement means a cement standardized according to European standard EN 197-1 (type I, II, III, IV and V). Examples of such cements are ordinary Portland cement as well as any other cement with additions.
- the examples of cements above have specific Blaine surfaces of between approximately 3700 cm 2 / g and approximately 5050 cm 2 / g.
- the content of Portland cement in the binder can vary between 30 and 80%. In this whole field, it is possible to obtain formulations with rapid setting. (setting start time less than 20 min). A preferential range is between 50 and 70% which allows to obtain optimal mechanical performance.
- sulfoaluminous clinker should be understood to mean any material resulting from cooking at a temperature between 900 ° C. and 1450 ° C. ("clinkering") of mixtures containing at least one source of lime (for example limestones which have a CaO content varying between 50% and 60%), at least one source of alumina (for example bauxites or other manufacturing by-product containing alumina), and at least one source of sulfate (gypsum, chemical gypsum, plaster, natural or synthetic anhydrite, sulfocalcic ash).
- the sulfoaluminous clinker used in the present invention has a content of
- the presence of free lime CaO can be tolerated up to 10% in the sulfoaluminous clinker without harming the properties of use of the binder used in the context of the present invention. This presence can occur when, for example, the clinker is obtained by cooking at relatively low temperature.
- the content of sulfoaluminous clinker can vary between 20% and 70% in the binder.
- the fineness (Blaine specific surface) of the sulfoaluminous clinker is between 2500 cm 2 / g and 7000 cm 2 / g, and particularly between 3500 and 6500 cm 2 / g, the hydration kinetics of the binder is not significantly modified , and provides rapid setting and hardening.
- the sulphate source this can be chosen indifferently from gypsum (or chemical gypsum), plaster, or anhydrite (natural or not), or even sulfocalcic ash.
- the SO 3 content from the sulphate source can be up to 10% by mass relative to the total binder (which corresponds for example to a plaster content up to 20% relative to the total binder).
- a preferred composition corresponds to a sulphate intake such that the mass ratio r defined above is close to 2. It is precisely in this case that the stoichiometric conditions for the formation of ettringite are respected:
- the preferred sulfate of the invention is plaster. If plasticity is preferred, the preferred sulfate is anhydrite.
- plasticizer entering into the composition of the adjuvant binder, it is necessary to understand any organic compound capable of improving the capacity of implementation (or workability) of the light mortar. It can also in the case of the present invention allow a significant reduction in water, with constant workability, which contributes to obtaining higher mechanical performance, for the manufacture of light plates.
- a water-reducing adjuvant makes it possible to reduce the amount of water required by at least 5% compared to a non-adjuvanted cement composition, and a high water-reducing adjuvant makes it possible to reduce the amount of water required by at least 12% compared to a non-adjuvanted cement composition.
- the water-reducing (super) plasticizers (top) used can be alkaline (Li, Na, K) or alkaline-earth (Ca, Mg) salts resulting from the condensation between ⁇ -naphthalene sulfonic acid and formaldehyde (Cimfluid 230 or 232 type (Axim, Ciments legal)), between sulfonated melamine and formaldehyde (Cimfluid ML type (Axim, Ciments für)) or lignosulfonates.
- alkaline Li, Na, K
- Ca, Mg alkaline-earth
- a preferred adjuvant in the context of the present invention is the alkaline or alkaline-earth salt resulting from the condensation between the sulfonated melamine and formaldehyde (Cimfluid ML type) which makes it possible to obtain a high fluidity and does not cause delay in setting. significant despite the high dosages used.
- the Cimfluid ML contents vary between 0.5 and 7% (% by mass relative to the weight of the binder).
- any mineral or organic compound is considered as retarder for setting, making it possible to significantly lengthen the setting time of the formulation of a mortar without penalizing its rheology.
- the advantage of such an adjuvant resides in the possibility of controlling the setting of the formulation and of possibly delaying it, to facilitate good implementation.
- Preferred retarders are citric acid, gluconates or also polyacrylates or polymethacrylates (of the Cimfluid 2000 AC type) which also bring a marked improvement in the workability of the dough.
- the water / binder weight ratio used is generally between 0.2 and 0.5. Beyond this value the mechanical performance drops vertiginously.
- the water / binder ratio used is between 0.25 and 0.40.
- composition 1 The formulation of the base is as follows (composition 1):
- the operating method consists in monitoring the rheological behavior of the composition in continuous mixing at an imposed speed of 300 rpm as a function of time.
- the usage time is then defined by the time after which the measured resistive torque is equal to 0.05 Nm
- the calculated ⁇ t 2 parameter corresponds to the time necessary for the measured resistive torque to go from 0.05 Nm to 0.1 Nm It makes it possible to give an account of the curing speed of the composition: the shorter this time, the higher the curing speed.
- the mixing of the dough is carried out for 40 sec at a speed of 250 rpm and the measurement of the spread is carried out after 1 min 20.
- the operating mode adopted consists of measuring, as a function of time, the resistance to penetration of a cylindrical needle 3 mm in diameter in the formulation to be tested using the TA XT2 texturometer (Rhéo Company) .
- the speed and the penetration distance are respectively fixed at 2 mm / s and 10 mm deep.
- the measured start and end times correspond respectively to the times necessary to obtain a force of 10N and 50N at the depth of 10 mm.
- the measurement of the setting time is carried out at rest without disturbing the sample being taken by mixing.
- the calculated parameter ⁇ ti corresponds to the time necessary for the measured force to go from 10 N to 50 N. It makes it possible to take account of the curing speed of the composition: the shorter this time, the higher the curing speed.
- This composition contains the basic formulation and the superplasticizer Cimfluid ML alone:
- a value of 60 mm corresponds to zero spreading (value of the cone diameter used for the measurement).
- compositions 2a and 2b The start times for setting measured on compositions 2a and 2b are respectively 6 min and 7 min 50 s.
- Composition 2a has a ratio r equal to 2.48.
- EXAMPLE 3 This example shows the effects on the start and end times of setting of the Portland cement content in the binder, with a plaster content kept constant and equal to 10%, the complement to 100% being clinker. sulphoaluminous. These tests are carried out in the presence of 2% of Cimfluid ML and in the absence of light aggregates, the water / binder mass ratio being 0.30.
- the following table shows that for Portland cement contents between 36 and 76%, the setting start time is equal to or less than 10 minutes.
- the formulation studied in all cases is the previous composition 2a to which polystyrene beads have been added so as to obtain a density very close to 1.
- the influence of the specific surface (Blaine) of the cement Portland and that of the sulfoaluminous clinker on mechanical performance in the very short term have been studied.
- the two adjuvants: the superplasticizer (Cimfluid ML) and the poly (meth) acrylate retarder (Cimfluid AC) are used simultaneously at the levels presented in the table below, in the basic cement composition:
- the formulations are as follows:. binder (100%) sulfoaluminous clinker 1 45% Portland cement CEM I 52.5 40%
- composition according to Example 1 the poly (meth) acrylate was replaced by an adjuvant containing a gluconate (Cimaxtard 101, Axim), in the following proportions:
- Cimaxtard 101 makes it possible to increase the time of use of the composition without penalizing the initial rheology.
- Cimfluid 2000AC alone also makes it possible to extend the duration of use of the composition up to approximately 30 min. However, if it is possible to obtain a use time of 28.6 min, it can be seen that the value of ⁇ ti is greater than that measured with the mixture [ML (2
- FIG. 1 is a diagram illustrating a manufacturing method according to the invention.
- a first metered premix 10 is produced from cement 11, a clinker 12, plaster 13 and aggregates 14, such as polystyrene beads.
- a second metered premix 20 is produced from a plasticizer 21 and a retarder 23 to which water has been added 22.
- the premixes 10 and 20 are introduced into a mixer 30; the resulting mixture is taken up by a recovery pump 31 and distributed by a distributor 32 at the inlet of an extruder 33; the distribution is made, homogeneously transversely, between two lower and upper facings made up of sheets in the form of grids, a lower grid G1 and an upper grid G2; the lower grid G1 rests on a sheet of plastic material FP, such as a sheet of polyethylene, pulled by a downstream conveyor belt 43, Figures 2 and 3, and slides on a table 46 disposed upstream of the extruder 33; at the outlet of the extruder 33, the plate thus formed is sent to a cutting station 34 where its length and its edges, therefore its width, are cut, advantageously with a water jet.
- each facing consists of a grid G1, G2 and / or a veil V, VB;
- the veil V covers the grid G1, G2 over its entire width;
- the veil is in the form of a strip VB and covers only the lateral edges of the grid G2;
- the lateral edges of the plates are previously formed by inverting the lower grid G1 then cut straight;
- the inverted part of the lower grid G1 is covered with the upper grid G2 associated or not with a web V;
- the inverted part of the lower grid G1 covers the upper grid G2 associated or not with a web V;
- the lateral edges of the lower grid G1 are associated with a web V, VB.
- the cut is made in the covering part.
- the extruder 33 is shown diagrammatically in part in FIGS. 2 to 4. It essentially consists of a table 35 carried elastically by a frame 36, by means of springs 37, here four coil springs arranged at the four corners of the table 35 generally rectangular in shape.
- the upper plate 38 of the table 35 constitutes the lower lip of a die 40, arranged transversely and of generally rectangular section, of which the upper lip is seen at 39; this upper lip 39 is here in the form of a blade and adjustable in height relative to the lower lip 38 so that one can adjust the height of the die 40, therefore the desired thickness of the plate.
- a slightly inclined deflector 41 guides the material towards it.
- the table 35 carries on its underside at least one vibrator 42, here two vibrators 42.
- a vibrator 42 is for example constituted by an electric motor whose rotor has an unbalance, adjustable, adapted to produce vibrations.
- the axes of the vibrators 42 are parallel to the arrow F; this axis can be oriented in a horizontal plane, as illustrated in FIG. 5 where we see in dashed lines another orientation of the vibrators 42; it can also be oriented in a vertical plane, the plane of Figure 2 for example; these orientations make it possible to favorably influence the homogeneity of the composition transversely at the inlet of the extruder 33.
- the die 40 has the general shape of a rectangle whose ends 44 slightly approach one another towards the outside so that the parallel lateral edges of the resulting plate are of the thinned type, such that this is defined in standard NF P72-302: this provision facilitates the installation of a coating for the jointing of two plates side by side, but of course this is not compulsory.
- the plates are removed from the mat after the mixture distribution and cutting operation; the composition according to the invention, the speed of the conveyor belt and the length of the chain are such that, at this instant, the hydration of the plates is such that each plate can be handled.
- the plates according to the present invention can have a body of very varied composition.
- This can be based on calcium sulphate hemihydrate and water, as described for example in document GB-A-2 0553 779; conventional additives can be provided, as well as 0.3 to 3% of glass fiber; it can also contain perlite, vermiculite, a formaldehyde-based resin, or the like.
- plates are obtained by mixing light components, such as expanded clays, expanded blast furnace ash, expanded shale, perlite, expanded polystyrene beads, expanded glass beads, with a hydraulic binder such as Portland cement, magnesium-based cement, aluminous cement, gypsum and / or mixture of some of these, with or without foaming agents.
- light components such as expanded clays, expanded blast furnace ash, expanded shale, perlite, expanded polystyrene beads, expanded glass beads
- a hydraulic binder such as Portland cement, magnesium-based cement, aluminous cement, gypsum and / or mixture of some of these, with or without foaming agents.
- composition is of the kind described in document WO 99/08979.
- composition is of the kind of that described in document WO 99/14449.
- composition is of the kind described in US-A-5,221,386.
- Figure 6 partially shows in section a plate according to the invention before its edges are cut; we recognize the lower grid G1, the upper grid G2, the thinned edge 44 and the aggregates 14; here, to make the edges of the plate, the lower grid G1 is laterally folded over until partially laterally covering the upper grid G2.
- a zone D of small thickness is free of aggregates 14; it is therefore a densified area, obtained thanks to the nature of the body composition of plate and extrusion under vibration; thanks to this zone, the mechanical strength of the plate is increased.
- FIG. 7 shows the plate after cutting the edge 45 along line C of FIG. 6.
- the parallel side edges are straight.
- the upper grid G2 can carry, for example by gluing, a veil V made up of a mat of glass fibers, for example; such a veil V further increases the mechanical strength of the plate; here, the veil V covers the grid G2 over its entire width.
- the grid G2, associated with a veil V covers the laterally folded part of the lower grid G1.
- FIG. 10 is similar to FIG. 8 except that the lower grid G1 is associated with a web of web VB secured for example by gluing along its longitudinal edges so that the upper grid G2, possibly associated with a web V, covers the folded part of the web strip VB which assists in making the edge of the plate.
- Figure 11 combines the arrangements described in connection with Figures 9 and 10, that is to say that it is the lower grid G1 and the web of veil VB which cover the upper grid G2 and its web V.
- the lower grid G1 could also carry a veil, such as the veil V; thus, Figures 12-15 illustrate the cases where the lower grid G1 carries a veil V, the rest being as in Figures 8, 9 with an upper grid G2 without veil, Figures 12-13, or with veil V, Figures 14- 15; the grid G1 is covered with the veil V over its entire width.
- Figures 16.17 show an arrangement similar to those of Figures 12.13, in which the web V associated with the lower grid G1 has been replaced by a strip of lateral web VB.
- the web-shaped veil VB covers only the lateral edges of the grid G1 and / or G2; thus, the upper grid G2 at least partially covers a part of the lower grid G1 which may or may not be associated with a web V, VB; alternatively, it is the upper grid G2 which is covered at least partially with a part of grid G1 associated or not with a web V, VB.
- the upper lip 39 is the lower generatrix of a cylindrical roller mounted rotating around a transverse axis.
- At least one of the facings, lower and / or upper is a cardboard, replacing the grid and / or the veil.
- a layer of latex-type polymer emulsion is deposited on the surface of the plate, on one side or on both sides; thanks to this arrangement, a protective film is obtained on the surface of the plate.
- This protective film makes it possible in particular to reduce the permeability of the plate, to improve the surface appearance, to facilitate the adhesion of any coating such as tiling and to limit, to a certain extent, the dimensional variations of the plate.
- This protective film can be deposited by surface spray, by coating with rollers, by impregnation of the grid (s) associated or not with a veil, either by passing through a bath or between rollers.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Press-Shaping Or Shaping Using Conveyers (AREA)
- Devices For Post-Treatments, Processing, Supply, Discharge, And Other Processes (AREA)
- Panels For Use In Building Construction (AREA)
- Building Environments (AREA)
- Medicinal Preparation (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Producing Shaped Articles From Materials (AREA)
- Polishing Bodies And Polishing Tools (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SK1642-2003A SK287887B6 (sk) | 2001-06-07 | 2002-06-06 | Method of fabricating a binder-based board such as plaster or cement binder based board, device for making the same and board producible by this method |
ROA200300986A RO121684B1 (ro) | 2001-06-07 | 2002-06-06 | Procedeu de obţinere a unei plăci cu liant pe bază de ciment, instalaţie de aplicare şi placăobţinută prin acest procedeu |
PL364364A PL201899B1 (pl) | 2001-06-07 | 2002-06-06 | Sposób i urządzenie do wytwarzania płyty na bazie środka wiążącego i płyta na bazie środka wiążącego |
DK02748937.6T DK1395405T3 (da) | 2001-06-07 | 2002-06-06 | Ekstruder til fremstilling af en plade på basis af et bindemiddel såsom gips |
AT02748937T ATE480379T1 (de) | 2001-06-07 | 2002-06-06 | Gleitvorrichtung zum herstellen einer platte bestehend aus bindemittel wie gips |
HU0400134A HU229533B1 (hu) | 2001-06-07 | 2002-06-06 | Extrudáló berendezés kötõanyagon - úgymint építési gipszen - alapuló tábla készítéséhez |
US10/479,964 US20040241271A1 (en) | 2001-06-07 | 2002-06-06 | Extruder for making a board based on a binder such as gypsum plaster |
NZ530077A NZ530077A (en) | 2001-06-07 | 2002-06-06 | Extruder for making a board based on a binder such as gypsum plaster |
KR1020037016013A KR100790201B1 (ko) | 2001-06-07 | 2002-06-06 | 시멘트계 바인더 보드 및 그 제조방법 |
EP02748937A EP1395405B1 (fr) | 2001-06-07 | 2002-06-06 | Extrudeur pour la fabrication d'une plaque a base de liant tel que platre |
DE60237599T DE60237599D1 (de) | 2001-06-07 | 2002-06-06 | Gleitvorrichtung zum herstellen einer platte bestehend aus bindemittel wie gips |
CA002449852A CA2449852C (fr) | 2001-06-07 | 2002-06-06 | Extrudeur pour la fabrication d'une plaque a base de liant tel que platre |
NO20035415A NO325057B1 (no) | 2001-06-07 | 2003-12-05 | Fremgangsmate for fremstilling av en plate basert pa sement som bindemiddel, samt apparatur for a utfore fremgangsmaten, og en slik plate. |
ZA2003/09595A ZA200309595B (en) | 2001-06-07 | 2003-12-10 | Extruder for making a board based on a binder such as gypsum plaster |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0107466A FR2825658B1 (fr) | 2001-06-07 | 2001-06-07 | Procede de fabrication d'une plaque a base de liant tel que platre, ciment ou autre, extrudeur pour la mise en oeuvre d'un tel procede, et plaque ainsi obtenue et son utilisation |
FR01/07466 | 2001-06-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002098622A1 true WO2002098622A1 (fr) | 2002-12-12 |
Family
ID=8864063
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/001930 WO2002098622A1 (fr) | 2001-06-07 | 2002-06-06 | Extrudeur pour la fabrication d'une plaque a base de liant tel que platre |
Country Status (18)
Country | Link |
---|---|
US (1) | US20040241271A1 (fr) |
EP (1) | EP1395405B1 (fr) |
KR (1) | KR100790201B1 (fr) |
AT (1) | ATE480379T1 (fr) |
CA (1) | CA2449852C (fr) |
CZ (1) | CZ305062B6 (fr) |
DE (1) | DE60237599D1 (fr) |
DK (1) | DK1395405T3 (fr) |
ES (1) | ES2352328T3 (fr) |
FR (1) | FR2825658B1 (fr) |
HU (1) | HU229533B1 (fr) |
NO (1) | NO325057B1 (fr) |
NZ (1) | NZ530077A (fr) |
PL (1) | PL201899B1 (fr) |
RO (1) | RO121684B1 (fr) |
SK (1) | SK287887B6 (fr) |
WO (1) | WO2002098622A1 (fr) |
ZA (1) | ZA200309595B (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014096649A1 (fr) | 2012-12-18 | 2014-06-26 | Ciments Francais | Materiau cimentaire durcissable a base de liants hydrauliques pour une mise en œuvre a basses temperatures |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MXPA05009968A (es) | 2003-03-19 | 2005-11-04 | United States Gypsum Co | Panel acustico que comprende una matriz entrelazada de yeso fraguado y metodo de fabricacion del mismo. |
US10173343B2 (en) | 2016-06-17 | 2019-01-08 | United States Gypsum Company | Slurry distribution system with vibration isolation |
CN110948643B (zh) * | 2019-12-11 | 2021-03-09 | 广州勇创混凝土有限公司 | 一种混凝土振动台 |
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US3083756A (en) * | 1959-03-30 | 1963-04-02 | United States Gypsum Co | Board-forming machine |
FR2083105A5 (fr) * | 1970-02-25 | 1971-12-10 | Knauf Westdeutsche | |
EP0482810A1 (fr) * | 1990-10-22 | 1992-04-29 | Domtar Inc. | Procédé pour le refaçonnage d'un placage en plâtre et produits ainsi obtenus |
WO1994003318A1 (fr) * | 1992-08-06 | 1994-02-17 | Georgia-Pacific Corporation | Equipement pour le traitement en continu de la fabrication de panneaux de fibres |
US20010000738A1 (en) * | 1997-09-12 | 2001-05-03 | National Gypsum Company | Cementitious panel with reinforced edges |
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US1953589A (en) * | 1932-01-13 | 1934-04-03 | United States Gypsum Co | Uniting dissimilar materials |
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US3250835A (en) * | 1963-03-06 | 1966-05-10 | Sp K Bureau Prokatdetal | Method for producing concrete and reinforced concrete slabs and substantially flat structural elements |
US3993822A (en) * | 1970-02-25 | 1976-11-23 | Gebr. Knauf Westdeutsche Gipswerke | Multi-layer plasterboard |
US4334786A (en) * | 1978-02-08 | 1982-06-15 | Saint Gobain Industries | Process and mechanism for evolutive pulp flow regulation |
AU531527B2 (en) * | 1979-05-30 | 1983-08-25 | Bpb Industries Ltd. | Cementitious building board |
GB2119703B (en) * | 1982-04-30 | 1985-10-23 | Bpb Industries Plc | Cementitious board manufacture |
IT1183353B (it) * | 1985-02-15 | 1987-10-22 | Moplefan Spa | Dispositivo per la fabbricazione in continuo di manufatti rinforzati da impasti di leganti idraulici e relativo procedimento |
US5632848A (en) * | 1989-10-12 | 1997-05-27 | Georgia-Pacific Corporation | Continuous processing equipment for making fiberboard |
JP2750919B2 (ja) * | 1989-11-02 | 1998-05-18 | 株式会社竹中工務店 | ち密なコンクリート表面の形成方法 |
US5030502A (en) * | 1990-02-02 | 1991-07-09 | Teare John W | Cementitious construction panel |
DE4127932A1 (de) * | 1991-08-23 | 1993-02-25 | Bold Joerg | Verfahren und vorrichtung zur herstellung von faserverstaerkten gipsplatten und dergleichen |
GB2316693B (en) * | 1996-08-29 | 2000-05-31 | Bpb Plc | Building board |
CA2242746C (fr) * | 1998-07-08 | 2002-06-11 | Westroc Inc. | Fabrication de placoplatre en utilisant un rouleau extenseur a corotation |
JP3315935B2 (ja) * | 1998-08-28 | 2002-08-19 | 吉野石膏株式会社 | 石膏ボードの製造方法及び装置 |
CN1416390A (zh) * | 2000-01-05 | 2003-05-07 | 美国圣戈班技术织物有限公司 | 光滑增强水泥板及其制备方法 |
US6524679B2 (en) * | 2001-06-06 | 2003-02-25 | Bpb, Plc | Glass reinforced gypsum board |
-
2001
- 2001-06-07 FR FR0107466A patent/FR2825658B1/fr not_active Expired - Fee Related
-
2002
- 2002-06-06 DE DE60237599T patent/DE60237599D1/de not_active Expired - Lifetime
- 2002-06-06 DK DK02748937.6T patent/DK1395405T3/da active
- 2002-06-06 HU HU0400134A patent/HU229533B1/hu not_active IP Right Cessation
- 2002-06-06 ES ES02748937T patent/ES2352328T3/es not_active Expired - Lifetime
- 2002-06-06 RO ROA200300986A patent/RO121684B1/ro unknown
- 2002-06-06 WO PCT/FR2002/001930 patent/WO2002098622A1/fr not_active Application Discontinuation
- 2002-06-06 CZ CZ2004-18A patent/CZ305062B6/cs not_active IP Right Cessation
- 2002-06-06 US US10/479,964 patent/US20040241271A1/en not_active Abandoned
- 2002-06-06 KR KR1020037016013A patent/KR100790201B1/ko active IP Right Grant
- 2002-06-06 EP EP02748937A patent/EP1395405B1/fr not_active Expired - Lifetime
- 2002-06-06 AT AT02748937T patent/ATE480379T1/de active
- 2002-06-06 CA CA002449852A patent/CA2449852C/fr not_active Expired - Fee Related
- 2002-06-06 NZ NZ530077A patent/NZ530077A/en not_active IP Right Cessation
- 2002-06-06 PL PL364364A patent/PL201899B1/pl unknown
- 2002-06-06 SK SK1642-2003A patent/SK287887B6/sk not_active IP Right Cessation
-
2003
- 2003-12-05 NO NO20035415A patent/NO325057B1/no not_active IP Right Cessation
- 2003-12-10 ZA ZA2003/09595A patent/ZA200309595B/en unknown
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US3083756A (en) * | 1959-03-30 | 1963-04-02 | United States Gypsum Co | Board-forming machine |
FR2083105A5 (fr) * | 1970-02-25 | 1971-12-10 | Knauf Westdeutsche | |
EP0482810A1 (fr) * | 1990-10-22 | 1992-04-29 | Domtar Inc. | Procédé pour le refaçonnage d'un placage en plâtre et produits ainsi obtenus |
WO1994003318A1 (fr) * | 1992-08-06 | 1994-02-17 | Georgia-Pacific Corporation | Equipement pour le traitement en continu de la fabrication de panneaux de fibres |
US20010000738A1 (en) * | 1997-09-12 | 2001-05-03 | National Gypsum Company | Cementitious panel with reinforced edges |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014096649A1 (fr) | 2012-12-18 | 2014-06-26 | Ciments Francais | Materiau cimentaire durcissable a base de liants hydrauliques pour une mise en œuvre a basses temperatures |
US9353002B2 (en) | 2012-12-18 | 2016-05-31 | Ciments Francais | Curable hydraulic binder-based cement material intended to be used at low temperatures |
Also Published As
Publication number | Publication date |
---|---|
KR100790201B1 (ko) | 2007-12-31 |
FR2825658A1 (fr) | 2002-12-13 |
EP1395405A1 (fr) | 2004-03-10 |
PL364364A1 (en) | 2004-12-13 |
NZ530077A (en) | 2005-11-25 |
HU229533B1 (hu) | 2014-01-28 |
CA2449852C (fr) | 2009-12-15 |
CZ200418A3 (cs) | 2004-05-12 |
EP1395405B1 (fr) | 2010-09-08 |
NO325057B1 (no) | 2008-01-21 |
CA2449852A1 (fr) | 2002-12-12 |
ATE480379T1 (de) | 2010-09-15 |
RO121684B1 (ro) | 2008-02-28 |
DE60237599D1 (de) | 2010-10-21 |
FR2825658B1 (fr) | 2007-08-31 |
NO20035415D0 (no) | 2003-12-05 |
SK287887B6 (sk) | 2012-03-02 |
HUP0400134A2 (hu) | 2005-03-29 |
US20040241271A1 (en) | 2004-12-02 |
ES2352328T3 (es) | 2011-02-17 |
KR20040016879A (ko) | 2004-02-25 |
DK1395405T3 (da) | 2011-01-10 |
SK16422003A3 (sk) | 2004-06-08 |
CZ305062B6 (cs) | 2015-04-22 |
PL201899B1 (pl) | 2009-05-29 |
ZA200309595B (en) | 2005-02-23 |
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