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WO2003035573A1 - Precurseur composite fibreux hybride - Google Patents

Precurseur composite fibreux hybride Download PDF

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Publication number
WO2003035573A1
WO2003035573A1 PCT/GB2002/004825 GB0204825W WO03035573A1 WO 2003035573 A1 WO2003035573 A1 WO 2003035573A1 GB 0204825 W GB0204825 W GB 0204825W WO 03035573 A1 WO03035573 A1 WO 03035573A1
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WO
WIPO (PCT)
Prior art keywords
acid
fibrous material
organic
treated
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2002/004825
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English (en)
Inventor
Dutiro Cuthbert
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Individual
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to EP20020779644 priority Critical patent/EP1497242A1/fr
Publication of WO2003035573A1 publication Critical patent/WO2003035573A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/12—Multiple coating or impregnating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/18—Waste materials; Refuse organic
    • C04B18/24—Vegetable refuse, e.g. rice husks, maize-ear refuse; Cellulosic materials, e.g. paper, cork
    • C04B18/28—Mineralising; Compositions therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to a building material, which is based on modified natural fibres precursor mass treated to make them more suitable for use in manufacturing mass products for construction and building.
  • a method of mass treating pumped organic fibrous material which method comprises (i) contacting the organic fibrous material dispersion with a mixture of the polymer precursor (adduct, semi-cured, oxidizing or reducing) and sodium silicate and (ii) contacting the treated material with an acid to deposit polymer precursor-silicate hybrid, an polymer precursor-silicic acid or polymer precursor- polysilic acid on the fibrous material and then (iii) contacting the treated fibrous material with an aluminium oxide containing compound.
  • the sodium silicate is preferably a neutral or alkaline solution e.g. of the type commonly known as water glass.
  • the stoichiometric composition for a neutral composition of sodium silicate is a SiO 2 :Na 2 O ratio of 3.3:1 and for an alkaline sodium silicate a SiO 2 :Na 2 O ratio of ⁇ 3.3: 1.
  • a typical alkaline grade sodium silicate has a SiO 2 : Na 2 O ratio of 2: 1.
  • the organic polymer precursor can take the form of any liquid two part or one part 'self- curing polymeric species, e.g. acetic acid/acetic anhydride or epoxy based adducts, polyvinyl or acetate, acrylic acrylate, polyurethane based or alkyd resin based preferred.
  • the quantity of polymer precursor to silicate solution is 1 : 10.
  • a solution of sodium silicate is used in which the viscosity of the solution is low enough to enable the sodium silicate solution to flow over the fibrous material and to penetrate the fibres.
  • a typical commercially available solid concentration is 40% solids content, which is about 142 g/1 for a neutral grade sodium silicate solution and 99g/l for an alkaline grade sodium silicate, but these concentrations are not critical.
  • the fibrous material is mass treated in a water dispersion preferably in a pipe/confined volume as shown in the diagram (Fig 5) as it is pumped through the system to allow enough mixing time and make use of the turbulence in the pipe during transport to allow the organic polymer precursor/silicate solution to interact with all the fibrous material.
  • the acid used to contact the treated fibrous material is a preferably a mineral acid e.g. sulphuric acid.
  • the pH of the acid should be between 2 and 4 and, for sulphuric acid; an acid solution of about 10 to 30% weight acid is suitable.
  • the acid solution should be mixed with a salt of the acid to saturate the acid solution and, in the case of sulphuric acid, any salt can be used e.g. sodium sulphate, but the less soluble salts e.g. calcium sulphate are preferred.
  • the preferred concentration of the salt is 10% to 20% weight in the solution.
  • the treatment of the material with the acid/salt solution preferably takes place at 20°C to 100°C, more preferably at 20 °C to 60 °C.
  • the fibrous material dispersion is continuously pumped and hence mixed with the organic polymer/sodium silicate solution, earlier in the process (Fig 2) and the acid /salt solution introduced at a later stage (Fig 3) at a rate automatically matched by an ordinary/electronically operated dispenser (Fig.4) with the organo-silicate hybrid, this is then dewatered (Fig 5) to obtain the treated fibrous material which is subsequently treated with an aluminium compound during the building product making phase.
  • the aluminium compound is preferably a solution or cementitious paste containing alumina or an aluminium salt and any aluminium oxide paste.
  • the treatment with the aluminium compound is believed to result in the formation of aluminium silicate sites on the fibrous and organic polymer precursor-fibre material.
  • the presence of the alumina silicate sites results in improved fireproofing of the treated organic material and in better matrix bonding properties.
  • the inclusion of the organic polymer precursor believed to be adsorbed as well as ionically and covalently bonded to the organic fibre (as shown in Figure 20) in the treatment process results in the adsorbed polymer being dispersed in the paste to fill out the air voids during mixing, and the ionically and covalently bonded sections.
  • the dispersion of the treated material in alkalis such as cements and concrete is increased by treatment by the method of the invention.
  • the treated product can be wetted and dried normally with no loss of fire resistance.
  • the coating imparts improved toughness, work of fracture, acoustic absorption, flexural strength and further resistance to insect attack, e.g. from termites, and to fungal or microbial attack to the cementitious composites formed with it.
  • the dispersed organic polymer precursor is also believed to further react with itself and form a layer on top of the product due to its density and act as a hydrophobic barrier for water penetration.
  • the organic polymer precursor is attached to the fibre and does not freely flow and disperse away with the water to clog various equipment components.
  • the polymer precursor forms a network of poly-organo-inorganic compounds as an additional binder with the cementitious phases to form stronger composites handleable to service strength within 5 days.
  • the silicic or polysilicic acids are precipitated in such a manner that they trap parts of the polymer precursor forming particles, which regularly deposit on the natural fibre surface, form into larger conglomerations with a diameter in the nanometer range.
  • the cellulosic chains on the fibre also partially react with the organic polymer precursor on the surface, which might also be containing the silica or silicic acid.
  • a network of organic/inorganic compounds is formed ( Figure 19).
  • the majority of the groups are believed to be hydrophobic (e.g. Figure 21), some of the free reactive groups will be hydrophilic and ionic allowing further reaction with cementitious compounds within the pastes used to form the products.
  • the surface of the fibrous material is charged and this charge is neutralised by cations such as Al 3+ , Mg 2+ , Na + , Fe 2+ , Ca + ions present in cement.
  • cations such as Al 3+ , Mg 2+ , Na + , Fe 2+ , Ca + ions present in cement.
  • the handling properties of the treated fibrous materials are similar to the untreated material ready to be used for the manufacturing process but have improved resistance to wetting and improved resistance to alkali attack and to insectoidal, fungal or microbial attack.
  • a solid polymer precursor-silicate- cellulose product is formed when the multi-component solution (polymer precursor blended silicate alkaline solution and the fibrous substance) is treated with an acid solution containing preferably about 10 to 20 percent by weight of H 2 S0 , about 10 to 20 percent by weight of Na 2 S0 4 or preferably CaS0 4 at a temperature of 20°C to 100°C, preferably about 20°C to 60°C, for a sufficient time.
  • An aluminium containing solution is added at the processing stage.
  • the aluminium will react strongly with the surface of the organic polymer precursor/poly-silicic acid hybrid sites if there is enough of it in the solution.
  • the treatment can be carried out with for example, at a temperature of 0°C to 100°C, preferably about 20°C to 60°C, for a sufficient time.
  • the polymer precursor silicate hybrid has been precipitated in such a manner that its primary particles, regularly distributed on the cellulose fibre backbone, form into larger agglomerations with a diameter measurable in nanometers which can be seen on SEM micrographs or other optical-microscopic methods ( Figure 22).
  • the natural fibrous materials which can be treated by the method of the invention include softwood/hardwood fibres after pulping, as fresh or waste pulp from paper mills, with compositions of 40-45% cellulose, 15-35% hemicellulose, 17-35% lignin as neutral, acid, sulphite, kraft, or mechanical pulps.
  • Cotton or fibrous cotton lint waste with more than 2% impurity of any kind and all naturally occurring organic fibrous materials whose aspect ratio is greater than 500 can also be used.
  • the basic cellulosic backbone and reactive groups as shown in Figures 21.
  • the surface groups on for example waste pulp fibres are mainly carboxylic (- COOH) and sulphonic (-SO 3 H) acid groups and their anionic nature gives them an affinity for cationic additives and can also be reacted with reactive groups of the organic polymer precursor.
  • - COOH carboxylic
  • -SO 3 H sulphonic
  • the untreated fibres are attacked if they are exposed to any form of fungal attack although it is a well proven concept that wood fibres can be mixed in a cement matrix without the risk of microbial attack due to the inaccessibility of such fibres to the microbes, as they are normally fully embedded in the reinforced matrix at fibre volume fractions of less than 9% by volume.
  • the treated fibres are resistant to fungal attack.
  • the treated fibrous material of the invention can be used as a reinforcing fibre for any suitable binder or construction material matrix such as concrete or cement, mud etc.
  • suitable binder or construction material matrix such as concrete or cement, mud etc.
  • the materials formed by the method of the invention when mixed with cement gains enough strength to be handled as if in service within 48 hours can also be used as a construction material due to their increased water penetration resistance and biological attack.
  • a total of 1000kg of waste pulp was mass treated by pumping it through a pipe ( Figure 5) and contacting it at valve inlet 1 ( Figure 2) with an alkaline solution containing 142g/l neutral grade sodium silicate (contained in Figure 10) dispensed with an alkaline/acid resistant electronic injector (Figure 3) at a rate of 5g/s at 25°C.
  • the second acid solution (contained in Figure 9) was injected at the second injection valve ( Figure 4) matched with the first injection at lg/s of an acid mixture of 30g/l sulphuric acid/50g/l sodium sulphate solution and 14.2 g/1 of acetic anhydride at 30 °C for 1 hour.
  • the treated fibres were then dried using mechanical squeezer (Figure 7), and bagged ( Figure 8) ready for mass production of building products. Sample treated fibres were taken, washed and boiled with water and dried to be used in Examples 2-6.
  • examples 1 and 2 were tested for fire resistance by heating in air at a temperature of 20°C to 1000°C at a rate of 10 degrees a minute for 90 minutes and the results compared with untreated pulp.
  • Example 1 lost 30 to 44% of its weight below 520°C to 752°C as shown on a TGA curve shown in Figure 11 compared with the untreated material which lost 93% of its weight below 337 °C as shown on a TGA curve shown in Figure 12.
  • the product of Example 2 lost 20-40% of its weight below 478 °C as shown on a TGA curve shown in Figure 13 compared with 93% below 326 °C for untreated material as shown on a TGA curve shown in Figure 14.
  • the samples reinforced with the treated fibre show less than 5% weight gain and no dampness on the lower side B.
  • Samples reinforced with untreated fibre show a 13- 22% weight gain and some dampness on lower side B.
  • SEM pictures taken on the surface of the specimen shown in Figure 17 a flatter surface on the treated fibre reinforced composites and fibroids of cross-linking network of polymer.
  • Example 4 The same samples made as for Example 4 were tested for standard 3 point bending flexure on a Testometric machine after 5 days and the graphs shown in Figure 18 were obtained.
  • the samples with treated fibre have a load carrying capacity greater than four times that of silicate treated and untreated fibre and hence exceed service strength during this period.
  • Example 6 Commercial Scale treatment of Pulp crumble at Art Corporation, Mutare /Pulp Mill, Moscow Samples of STD pulp crumble and pulp crumble treated according to example 1 effluent were taken from effluent facility every two hours and handsheets made in the laboratory.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne un procédé de traitement permettant d'obtenir, à partir de fibres organiques naturelles, un matériau de construction hybride possédant une perméabilité de surface à l'eau améliorée, une résistance au feu améliorée, une résistance à la flexion initiale améliorée, pouvant être utilisé comme matériau de renfort pour du ciment ou du béton. Ce procédé consiste à mélanger les fibres organiques naturelles avec une solution renfermant du silicate de sodium et un précurseur autopolymérisable organique polymère, à les traiter avec une solution renfermant un sel et un acide minéral et à les mettre en contact avec une solution ou une pâte contenant de l'aluminium.
PCT/GB2002/004825 2001-10-23 2002-10-23 Precurseur composite fibreux hybride Ceased WO2003035573A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20020779644 EP1497242A1 (fr) 2001-10-23 2002-10-23 Precurseur composite fibreux hybride

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0125368A GB0125368D0 (en) 2001-10-23 2001-10-23 Hybrid 01
GB0125368.1 2001-10-23

Publications (1)

Publication Number Publication Date
WO2003035573A1 true WO2003035573A1 (fr) 2003-05-01

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ID=9924325

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Application Number Title Priority Date Filing Date
PCT/GB2002/004825 Ceased WO2003035573A1 (fr) 2001-10-23 2002-10-23 Precurseur composite fibreux hybride

Country Status (3)

Country Link
EP (1) EP1497242A1 (fr)
GB (1) GB0125368D0 (fr)
WO (1) WO2003035573A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2466295A (en) * 2008-12-20 2010-06-23 Sentinel Corp A method of mass treating organic fibrous material

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE903672C (de) * 1951-08-17 1954-02-08 Reinhold Pohlenz Verfahren zur Herstellung einer Faserplatte
US3297616A (en) * 1963-12-02 1967-01-10 Koppers Co Inc Self-curing silicate and acrylate coatings
US3567645A (en) * 1964-11-25 1971-03-02 Kali Chemie Ag Silica desiccants and method of manufacture
GB1483270A (en) * 1973-11-30 1977-08-17 Bayer Ag Inorganic-organic plastics
US4360440A (en) * 1981-05-13 1982-11-23 Fulbright & Jaworski Insulating fiber mixture, adhesive, and process
US4366136A (en) * 1977-09-06 1982-12-28 Ciba-Geigy Corporation Moldable prepolymers based on alkali metal silicates and alkaline earth metal silicates
EP0185003A1 (fr) * 1984-12-12 1986-06-18 Boliden Aktiebolag Procédé de fabrication de panneaux de fibres, et panneaux résultant de l'application de ce procédé
CA1269804A (fr) * 1985-05-07 1990-06-05 Staffan Lundstrom Production d'une masse a mouler a teneur de silicate de sodium
US5194087A (en) * 1990-05-18 1993-03-16 Norsk Proco A/S Fireproof, waterproof and acidproof binder
DE4413964A1 (de) * 1994-04-13 1995-10-19 Heinz B Mader Holzziegel aus Reststoffen
US5500402A (en) * 1991-11-08 1996-03-19 Ab Carl Munters Method for the manufacture of a contact body for the exchange of moisture or heat
WO2002024597A2 (fr) * 2000-09-20 2002-03-28 Goodrich Corporation Compositions et composites pour matrice minerale et leur procede de fabrication

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE903672C (de) * 1951-08-17 1954-02-08 Reinhold Pohlenz Verfahren zur Herstellung einer Faserplatte
US3297616A (en) * 1963-12-02 1967-01-10 Koppers Co Inc Self-curing silicate and acrylate coatings
US3567645A (en) * 1964-11-25 1971-03-02 Kali Chemie Ag Silica desiccants and method of manufacture
GB1483270A (en) * 1973-11-30 1977-08-17 Bayer Ag Inorganic-organic plastics
US4366136A (en) * 1977-09-06 1982-12-28 Ciba-Geigy Corporation Moldable prepolymers based on alkali metal silicates and alkaline earth metal silicates
US4360440A (en) * 1981-05-13 1982-11-23 Fulbright & Jaworski Insulating fiber mixture, adhesive, and process
EP0185003A1 (fr) * 1984-12-12 1986-06-18 Boliden Aktiebolag Procédé de fabrication de panneaux de fibres, et panneaux résultant de l'application de ce procédé
CA1269804A (fr) * 1985-05-07 1990-06-05 Staffan Lundstrom Production d'une masse a mouler a teneur de silicate de sodium
US5194087A (en) * 1990-05-18 1993-03-16 Norsk Proco A/S Fireproof, waterproof and acidproof binder
US5500402A (en) * 1991-11-08 1996-03-19 Ab Carl Munters Method for the manufacture of a contact body for the exchange of moisture or heat
DE4413964A1 (de) * 1994-04-13 1995-10-19 Heinz B Mader Holzziegel aus Reststoffen
WO2002024597A2 (fr) * 2000-09-20 2002-03-28 Goodrich Corporation Compositions et composites pour matrice minerale et leur procede de fabrication

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2466295A (en) * 2008-12-20 2010-06-23 Sentinel Corp A method of mass treating organic fibrous material

Also Published As

Publication number Publication date
EP1497242A1 (fr) 2005-01-19
GB0125368D0 (en) 2001-12-12

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