WO2002094523A1 - Process for carrying out panels, tiles and the like using agglomerates of different minerals - Google Patents

Process for carrying out panels, tiles and the like using agglomerates of different minerals Download PDF

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Publication number
WO2002094523A1
WO2002094523A1 PCT/IB2002/001776 IB0201776W WO02094523A1 WO 2002094523 A1 WO2002094523 A1 WO 2002094523A1 IB 0201776 W IB0201776 W IB 0201776W WO 02094523 A1 WO02094523 A1 WO 02094523A1
Authority
WO
WIPO (PCT)
Prior art keywords
panels
different
layer
tiles
carried out
Prior art date
Application number
PCT/IB2002/001776
Other languages
French (fr)
Inventor
Max Canti
Original Assignee
Canti & Figli S.R.L.
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 Canti & Figli S.R.L. filed Critical Canti & Figli S.R.L.
Priority to CA002448075A priority Critical patent/CA2448075A1/en
Priority to EP02733011A priority patent/EP1395404A1/en
Priority to JP2002591221A priority patent/JP2005506263A/en
Priority to BR0210046-0A priority patent/BR0210046A/en
Priority to US10/478,906 priority patent/US20040194421A1/en
Publication of WO2002094523A1 publication Critical patent/WO2002094523A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/242—Moulding mineral aggregates bonded with resin, e.g. resin concrete
    • B29C67/243—Moulding mineral aggregates bonded with resin, e.g. resin concrete for making articles of definite length
    • B29C67/244—Moulding mineral aggregates bonded with resin, e.g. resin concrete for making articles of definite length by vibrating the composition before or during moulding
    • 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
    • B28B23/00—Arrangements specially adapted for the production of shaped articles with elements wholly or partly embedded in the moulding material; Production of reinforced objects
    • B28B23/0081—Embedding aggregates to obtain particular properties
    • 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
    • B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B28B3/02—Producing shaped articles from the material by using presses; Presses specially adapted therefor wherein a ram exerts pressure on the material in a moulding space; Ram heads of special form
    • B28B3/025—Hot pressing, e.g. of ceramic materials

Definitions

  • the present invention refers to a process allowing to carry out fire-proof, water-proof mechanical stress-proof panels, tiles and the like with different superficial finishes, fit for floorings and coverings generally.
  • the process includes also the elements carried out by said process.
  • a method presently used for carrying out said agglomerates consists in inserting granules mixed with the resin in forms, where they are heated and subject to high vibro-compression in order to achieve the hardening of the whole mass, which becomes an enbloc. Afterward the enbloc must be cut, smoothed and worked, for carrying out the desired elements.
  • This method uses a low resin percentage, but requires presses and large dimension equipments, with consequent investments and high operational expenses. Moreover the cuts and the polishing of the raw plates produce large amount of powders and require long machining times.
  • Another method consists in forming plates having a defined thickness by positioning the powders mixed with resins into rubber trays or into belts with holding sides, and achieving the hardening of the whole mass by vacuum vibro-compression and following free baking in oven.
  • Another method currently used for carrying out the agglomerates consists in pouring the mixture of granules and resins into an open mold. In this case it is necessary to use a very large amount of resin, with consequent decrease of the mechanical strength and resistance to heat of the manufactured elements.
  • the objects of the present invention consist in carrying out fire-proof, water-proof and mechanical stress-proof panels, tiles and similar with finishes made of brickwork, melaminic, or of other types, also decorated with carvings or three-dimensional architectural elements, using means not excessively expensive and having a low resin percentage.
  • the manufactured elements can be advantageously used for floorings, staircases, coverings and furnitures generally, or also for surface of kitchens, tables, benches and similar. Adding rubber granules or recycled plastic materials, high characteristics of acoustic insulation are achieved, which allow using the panels also for floors of suspended or floating type, with suitable female-male connections.
  • the terracotta granules, or of other minerals are mixed with bi-component or thermosetting resins and distributed with a dosing device on a plan, in such a way to form a layer of desired thickness.
  • the layer is then inserted between the heated surfaces of a press, where the resin polymerizes, hardening by virtue of the simultaneous effect of pressure and heat.
  • the surfaces can be constituted by wastes of grinded bricks, to carrying out elements similar to the brick, or constituted by granules of different minerals, to carrying out marble or granite type finishes.
  • the surfaces can be also coated with melaminic sheets, or with ready laminated plastic, which are heat included into panels so manufactured already melaminic coated.
  • a stiffening frame can be added in the base portion of the layer.
  • figure 1 shows a side schematic view of a plant for carrying out panels, tiles and similar according to the process object of the present invention
  • figure 2 shows a top view of the plant of figure 1
  • figures 3 and 4 show respectively a transversal section and a top view of a panel with brick superficial finish
  • figures 5 and 6 show a transversal section and a top view of a panel with melaminic superficial finish
  • figures 7 and 8 show a transversal section and a top view of a panel with grooves creating a visible bricks effect
  • numeral 1 indicates a silo containing the granules of material to be agglomerated.
  • silos could be provided, containing different material, for instance granules or powders of brick wastes, granules of other minerals, rubber granules or recycled plastic materials.
  • the granules, positioned in the hopper 2 are transferred by a cochlea 3 into a mixer 4, where they are mixed with bi-component or thermosetting resin.
  • the two components of the resin are introduced in the mixer 4 by means of pumps 5 and 6 and the ducts 7 and 8, shown in figure 2.
  • the thermosetting resin is directly inserted into the granules.
  • the granules mixed with the resin are introduced in a dosing hopper 9, which can translate over rails 10 in order to scatter a layer of agglomerate 11 on the belt 12, provided with holding sides.
  • the scattered layer is therefore introduced in the press 13, through the belt 12.
  • the heated jaws of the press cause the polymerization of the thermosetting or bi-component resin: it is carried out a panel made of firmly bonded mineral agglomerates, with a low percentage of resin, resistant to fire, water, dirty and mechanical stresses.
  • the dosing hopper 9 can depose on the belt 12 another layer of agglomerates mixed with bi-component resin.
  • the completed panel is discharged and a new layer is loaded.
  • the static press can be substituted with a continuous press in order to eliminate the opening and closing dead time.
  • a follower cutting device must be provided at the press outlet for carrying out panels from a continuous panel.
  • the panels can be homogeneous, or with a superficial portion different from the base portion, as shown for instance in figure 3.
  • numeral 14 indicates the superficial portion
  • numeral 15 indicates the base portion.
  • the superficial portion 14 could be carried out with brick powder, to achieve a brick finishing.
  • the stamping superficial portion could be carried out also by agglomerating, with the same procedures, different mineral granules, in such a way to achieve a marble or granite type effect.
  • the base portion 15 may contain rubber granules or recycled plastic material, to confer to the panels suitable characteristics of flexibility and acoustic insulation.
  • a melaminic sheet 16 shown in figures 5 and 6, which polymerizes at the same time with the agglomerate layer or a ready plastic laminate, for which the same agglomerate acts as adhesive, in such a way to carry out a panel already coated.
  • the panel can be afterwards finished on the surface with decorations and heat and cold ceramic enamels.
  • the panels used in the building, shipbuilding fields and can be fit for floorings, also floating, or inner or external coverings of large surfaces, simulating the effects of the visible bricks with varied decorative patterns.
  • the panels can be pantograph carved, for carrying out different throated, inclined or sloped connections, or straight or rounded grooves, or ornamental patterns. Deepening the incisions through a numerical control pantograph up to consume the whole rigid layer, the panels can be stick on curved surfaces, such as columns of reinforced concrete, internal spiral staircases, arcs and vaults generally. Grids of different shape and dimension can be carried out as well.
  • panels already having cuts can be carried out, such as, for instance, the cuts indicated with numeral 17 in figures 7 and 8.
  • a stiffening frame made of fiberglass or other materials, to improve the mechanical characteristics of the panel.
  • the sandwich panel so carried out can be superficially calibrated using a sanding machine and superficially treated with wax or suitable varnishes or enamels and heat and cold ceramic decorations.
  • the panels can be cut, squared and predisposed for joints, in the same way of MDF panels.
  • agglomerating light minerals such as pumice, pearlite, aluminium silicate or hollow glass microspheres
  • inner stiffening frames shaped panels with different thickness
  • rusticated ashlars or other decorative elements usable for false ceilings, for flame trap or other.
  • the dosing device could be fixed, or positioned on a mobile belt also during casting, for instance in case of continuous press.

Abstract

The invention relates to a process for carrying out panels, tiles and similar using agglomerates of different minerals wherein the terracotta granules or other minerals are mixed with bi-components or thermosetting resins and spread by means of a dosing means onto a plan provided with side, in such a way to form a layer of desired thickness. Said layer is then inserted between the heated surface of a press, where, by virtue of the simultaneous effect of heat and pressure, it is carried out the polymerization of the resin, which hardens and transforms the agglomeration layer in a panel resistant to fire, water and mechanical stresses, usable for different applications.

Description

PROCESS FOR CARRYING OUT PANELS, TILES AND THE LIKE USING AGGLOMERATES OF DIFFERENT MINERALS
TECHNICAL FIELD
The present invention refers to a process allowing to carry out fire-proof, water-proof mechanical stress-proof panels, tiles and the like with different superficial finishes, fit for floorings and coverings generally. The process includes also the elements carried out by said process.
BACKGROUND ART
There are known synthetic marbles and granites constituted by agglomerates of different minerals, mixed with resins. A method presently used for carrying out said agglomerates consists in inserting granules mixed with the resin in forms, where they are heated and subject to high vibro-compression in order to achieve the hardening of the whole mass, which becomes an enbloc. Afterward the enbloc must be cut, smoothed and worked, for carrying out the desired elements. This method uses a low resin percentage, but requires presses and large dimension equipments, with consequent investments and high operational expenses. Moreover the cuts and the polishing of the raw plates produce large amount of powders and require long machining times.
Another method consists in forming plates having a defined thickness by positioning the powders mixed with resins into rubber trays or into belts with holding sides, and achieving the hardening of the whole mass by vacuum vibro-compression and following free baking in oven.
Another method currently used for carrying out the agglomerates consists in pouring the mixture of granules and resins into an open mold. In this case it is necessary to use a very large amount of resin, with consequent decrease of the mechanical strength and resistance to heat of the manufactured elements.
DISCLOSURE OF THE INVENTION
The objects of the present invention consist in carrying out fire-proof, water-proof and mechanical stress-proof panels, tiles and similar with finishes made of brickwork, melaminic, or of other types, also decorated with carvings or three-dimensional architectural elements, using means not excessively expensive and having a low resin percentage. The manufactured elements can be advantageously used for floorings, staircases, coverings and furnitures generally, or also for surface of kitchens, tables, benches and similar. Adding rubber granules or recycled plastic materials, high characteristics of acoustic insulation are achieved, which allow using the panels also for floors of suspended or floating type, with suitable female-male connections.
The terracotta granules, or of other minerals are mixed with bi-component or thermosetting resins and distributed with a dosing device on a plan, in such a way to form a layer of desired thickness. The layer is then inserted between the heated surfaces of a press, where the resin polymerizes, hardening by virtue of the simultaneous effect of pressure and heat. In particular, the surfaces can be constituted by wastes of grinded bricks, to carrying out elements similar to the brick, or constituted by granules of different minerals, to carrying out marble or granite type finishes. The surfaces can be also coated with melaminic sheets, or with ready laminated plastic, which are heat included into panels so manufactured already melaminic coated. A stiffening frame can be added in the base portion of the layer.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is now described in detail, with particular reference to the attached drawings, which show by way of example some possible embodiment: figure 1 shows a side schematic view of a plant for carrying out panels, tiles and similar according to the process object of the present invention; figure 2 shows a top view of the plant of figure 1; figures 3 and 4 show respectively a transversal section and a top view of a panel with brick superficial finish; figures 5 and 6 show a transversal section and a top view of a panel with melaminic superficial finish; figures 7 and 8 show a transversal section and a top view of a panel with grooves creating a visible bricks effect;
BEST MODE OF CARRYING OUT THE INVENTION With reference to figures 1 and 2, numeral 1 indicates a silo containing the granules of material to be agglomerated. Several silos could be provided, containing different material, for instance granules or powders of brick wastes, granules of other minerals, rubber granules or recycled plastic materials. The granules, positioned in the hopper 2, are transferred by a cochlea 3 into a mixer 4, where they are mixed with bi-component or thermosetting resin. The two components of the resin are introduced in the mixer 4 by means of pumps 5 and 6 and the ducts 7 and 8, shown in figure 2. The thermosetting resin is directly inserted into the granules.
The granules mixed with the resin are introduced in a dosing hopper 9, which can translate over rails 10 in order to scatter a layer of agglomerate 11 on the belt 12, provided with holding sides. The scattered layer is therefore introduced in the press 13, through the belt 12. The heated jaws of the press cause the polymerization of the thermosetting or bi-component resin: it is carried out a panel made of firmly bonded mineral agglomerates, with a low percentage of resin, resistant to fire, water, dirty and mechanical stresses.
While the heat pressing of the loaded agglomerate layer is operated, the dosing hopper 9 can depose on the belt 12 another layer of agglomerates mixed with bi-component resin. At the pressure stop, by means of the belt 12 the completed panel is discharged and a new layer is loaded.
The static press can be substituted with a continuous press in order to eliminate the opening and closing dead time. In this case a follower cutting device must be provided at the press outlet for carrying out panels from a continuous panel.
The panels can be homogeneous, or with a superficial portion different from the base portion, as shown for instance in figure 3. In such figure numeral 14 indicates the superficial portion and numeral 15 indicates the base portion. In particular, the superficial portion 14 could be carried out with brick powder, to achieve a brick finishing. The stamping superficial portion could be carried out also by agglomerating, with the same procedures, different mineral granules, in such a way to achieve a marble or granite type effect.
The base portion 15 may contain rubber granules or recycled plastic material, to confer to the panels suitable characteristics of flexibility and acoustic insulation.
On the layer 11, before the introduction into the press, it could be applied a melaminic sheet 16, shown in figures 5 and 6, which polymerizes at the same time with the agglomerate layer or a ready plastic laminate, for which the same agglomerate acts as adhesive, in such a way to carry out a panel already coated. The panel can be afterwards finished on the surface with decorations and heat and cold ceramic enamels.
The panels used in the building, shipbuilding fields and can be fit for floorings, also floating, or inner or external coverings of large surfaces, simulating the effects of the visible bricks with varied decorative patterns. The panels can be pantograph carved, for carrying out different throated, inclined or sloped connections, or straight or rounded grooves, or ornamental patterns. Deepening the incisions through a numerical control pantograph up to consume the whole rigid layer, the panels can be stick on curved surfaces, such as columns of reinforced concrete, internal spiral staircases, arcs and vaults generally. Grids of different shape and dimension can be carried out as well.
Using shaped molds, panels already having cuts can be carried out, such as, for instance, the cuts indicated with numeral 17 in figures 7 and 8.
In the layer 11 could be inserted a stiffening frame, made of fiberglass or other materials, to improve the mechanical characteristics of the panel. The sandwich panel so carried out can be superficially calibrated using a sanding machine and superficially treated with wax or suitable varnishes or enamels and heat and cold ceramic decorations. The panels can be cut, squared and predisposed for joints, in the same way of MDF panels.
By agglomerating light minerals, such as pumice, pearlite, aluminium silicate or hollow glass microspheres, with inner stiffening frames, shaped panels with different thickness can be carried out, with rusticated ashlars or other decorative elements, usable for false ceilings, for flame trap or other.
With the described process panels can be carried out with different types of finish, resistant to fire, water, dirty, mechanical stress and acoustically insulated: the specified objects have been therefore achieved.
The dosing device could be fixed, or positioned on a mobile belt also during casting, for instance in case of continuous press.

Claims

1) Process for carrying out panels, tiles and similar using agglomerates of different minerals characterized in that the terracotta granules or other minerals are mixed with bi- components or thermosetting resins and spread by means of a dosing means onto a plan provided with side, in such a way to form a layer of desired thickness, which is then inserted between the heated surface of a press, where, by virtue of the simultaneous effect of heat and pressure, it is carried out the polymerization of the resin, which hardens and transforms the agglomeration layer in a panel resistant to fire, water and mechanical stresses, usable for different applications.
2) Process according to claim 1 characterized in that the deposed layer can be homogeneous, or can have a superficial portion different from the base portion; that in particular the superficial portion can be made of wastes of grinded bricks, to carried out elements similar to the brick, or made of a mixture of different mineral, for achieving marble or granite type effects.
3) Process according to any of the preceding claims characterized in that before the introduction into press, the agglomerate and resin layer is covered with a sheet of melaminic material, or similar, which polymerizes at the same time with the agglomerate layer, or is covered with a ready plastic laminate, to which said agglomerate acts as adhesive, in such a way to carried out a panel already coated or afterwards decorated with decorations and heat and cold ceramic enamels.
4) Process according to any of the preceding claims characterized in that shaped molds are used in the press, in order to carried out panels with cuts, with rusticated ashlars, or generally other decorations.
5) Process according to any of the preceding claims characterized in that in the base portion it is inserted a stiffening frame, and/or rubber or recycled plastic materials granules, fit for giving suitable flexibility and acoustic insulation to the elements.
6) Panels, tiles and similar carried out through the process according to any of the preceding claims characterized in that they are constituted by one or more layers of mineral agglomerates, mixed with a low percentage of thermosetting or bi-component resin and heat pressed; that said layers can be homogeneous, or with a superficial portion (14) different from the base portion (15), carried out for instance with brick powder, to achieve a brick finish, or with different mineral, for having marble or granulated type finishes.
7) Panels, tiles and similar according to claim 6 characterized in that the base portion (15) contains rubber or recycled plastic material granules, fit for giving suitable flexibility and acoustic insulation to the panels, which are engraved up to consume the whole rigid layer in order to cover curved surfaces.
8) Panels, tiles and similar according to claims 6 and 7 characterized in that they can be press shaped or pantograph carved, in order to carry out different throated, inclined or sloped connections, or straight or rounded grooves, or ornamental patterns, or grids with different shapes.
9) Panels, tiles and similar according to claims 6, 7 and 8, characterized in that they are made of agglomerates of light mineral, such as pumice, pearlite, aluminium silicate or hollow glass microspheres, with stiffening frames and are used for false-ceilings, furnitures, trap- fire doors or other uses.
PCT/IB2002/001776 2001-05-24 2002-05-23 Process for carrying out panels, tiles and the like using agglomerates of different minerals WO2002094523A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002448075A CA2448075A1 (en) 2001-05-24 2002-05-23 Process for carrying out panels, tiles and the like using agglomerates of different minerals
EP02733011A EP1395404A1 (en) 2001-05-24 2002-05-23 Process for carrying out panels, tiles and the like using agglomerates of different minerals
JP2002591221A JP2005506263A (en) 2001-05-24 2002-05-23 Process to realize panels, tiles, etc. using different mineral agglomerates
BR0210046-0A BR0210046A (en) 2001-05-24 2002-05-23 Process of making panels, tiles and similar products by using agglomerates of different minerals
US10/478,906 US20040194421A1 (en) 2001-05-24 2002-05-23 Process for carrying out panels, tiles and the like using agglomerates of different minerals

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITPS2001A000017 2001-05-24
IT2001PS000017A ITPS20010017A1 (en) 2001-05-24 2001-05-24 PROCEDURE FOR OBTAINING TILES AND SIMILAR PANELS WITH VARIOUS MINERAL AGGLOMERATES AND POSSIBLE ADDITION OF RUBBER OR PLASTIC MATERIALS

Publications (1)

Publication Number Publication Date
WO2002094523A1 true WO2002094523A1 (en) 2002-11-28

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PCT/IB2002/001776 WO2002094523A1 (en) 2001-05-24 2002-05-23 Process for carrying out panels, tiles and the like using agglomerates of different minerals

Country Status (7)

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US (1) US20040194421A1 (en)
EP (1) EP1395404A1 (en)
JP (1) JP2005506263A (en)
BR (1) BR0210046A (en)
CA (1) CA2448075A1 (en)
IT (1) ITPS20010017A1 (en)
WO (1) WO2002094523A1 (en)

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WO2009005384A2 (en) * 2007-07-05 2009-01-08 Labicer - Laboratório Industrial Cerâmico, S.A. A process for the production of panels for cladding formed by a conglomerate of minerals and special aggregates mixed with two-component adhesive and/or thermosetting resins
EP2942208A1 (en) * 2014-05-09 2015-11-11 Akzenta Paneele + Profile GmbH Method for producing a decorated wall or floor panel
US10350938B2 (en) 2014-02-25 2019-07-16 Akzenta Paneele + Profile Gmbh Method for producing decorative panels
US10618346B2 (en) 2015-08-19 2020-04-14 Akzenta Paneele + Profile Gmbh Method for producing a decorated wall or floor panel

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US8591677B2 (en) 2008-11-04 2013-11-26 Ashtech Industries, Llc Utility materials incorporating a microparticle matrix formed with a setting agent
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US20160237704A1 (en) 2015-02-14 2016-08-18 Prime Forming & Construction Supplies, Inc., dba Fitzgerald Formliners Formliners and methods of use
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009005384A2 (en) * 2007-07-05 2009-01-08 Labicer - Laboratório Industrial Cerâmico, S.A. A process for the production of panels for cladding formed by a conglomerate of minerals and special aggregates mixed with two-component adhesive and/or thermosetting resins
WO2009005384A3 (en) * 2007-07-05 2009-05-14 Labicer Lab Ind Ceramico S A A process for the production of panels for cladding formed by a conglomerate of minerals and special aggregates mixed with two-component adhesive and/or thermosetting resins
US10350938B2 (en) 2014-02-25 2019-07-16 Akzenta Paneele + Profile Gmbh Method for producing decorative panels
US11117417B2 (en) 2014-02-25 2021-09-14 Akzenta Pancele + Profile GMBH Method for producing decorative panels
EP2942208A1 (en) * 2014-05-09 2015-11-11 Akzenta Paneele + Profile GmbH Method for producing a decorated wall or floor panel
WO2015169647A1 (en) * 2014-05-09 2015-11-12 Akzenta Paneele + Profile Gmbh Method for producing a decorated wall or floor panel
RU2647233C1 (en) * 2014-05-09 2018-03-14 Акцента Панееле + Профиле Гмбх Method for manufacturing decorated wall or floor panel
EP3403846A1 (en) * 2014-05-09 2018-11-21 Akzenta Paneele + Profile GmbH Method for producing a decorated wall or floor panel
US10479134B2 (en) 2014-05-09 2019-11-19 Akzenta Paneele + Profile Gmbh Method for producing a decorated wall or floor panel
US10618346B2 (en) 2015-08-19 2020-04-14 Akzenta Paneele + Profile Gmbh Method for producing a decorated wall or floor panel

Also Published As

Publication number Publication date
JP2005506263A (en) 2005-03-03
EP1395404A1 (en) 2004-03-10
ITPS20010017A1 (en) 2002-11-24
US20040194421A1 (en) 2004-10-07
CA2448075A1 (en) 2002-11-28
BR0210046A (en) 2004-08-17

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