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WO2009001263A1 - Procédé de fabrication de produits à base de ciment et de fibres, comprenant l'utilisation d'un matériau pouzzolanique, et suspension aqueuse de matériau pouzzolanique utilisée dans ledit procédé - Google Patents

Procédé de fabrication de produits à base de ciment et de fibres, comprenant l'utilisation d'un matériau pouzzolanique, et suspension aqueuse de matériau pouzzolanique utilisée dans ledit procédé Download PDF

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Publication number
WO2009001263A1
WO2009001263A1 PCT/IB2008/052443 IB2008052443W WO2009001263A1 WO 2009001263 A1 WO2009001263 A1 WO 2009001263A1 IB 2008052443 W IB2008052443 W IB 2008052443W WO 2009001263 A1 WO2009001263 A1 WO 2009001263A1
Authority
WO
WIPO (PCT)
Prior art keywords
fibre
fraction
cement
pozzolanic
particles
Prior art date
Application number
PCT/IB2008/052443
Other languages
English (en)
Inventor
Alessandro Quadrio Curzio
Original Assignee
Petracem 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 Petracem S.R.L. filed Critical Petracem S.R.L.
Priority to EP08763400A priority Critical patent/EP2173682A1/fr
Publication of WO2009001263A1 publication Critical patent/WO2009001263A1/fr

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
    • C04B20/0076—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 characterised by the grain distribution
    • C04B20/008—Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder
    • C04B20/0084—Conditioning, e.g. preparing suspensions thereof
    • 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

Definitions

  • the present invention concerns a process for the manufacturing of cementitious products made of cement and fibres wherein a material having pozzolanic properties is employed.
  • the invention also comprises an aqueous suspension of the material exhibiting pozzolanic properties used in said process.
  • asbestos-cement employing asbestos fibres sunk in a cement-based matrix was largely widespread in Italy.
  • the properties of the asbestos fibres, as construction material to be used for the manufacture of cement manufactured products were really outstanding, and they were paired with a very low cost, both factors having determined the above-said wide diffusion.
  • fibre-cement having to use less effective and less cement-compatible strengthening fibres than asbestos, both from the point of view of the mechanical and elastic properties, and due to its potential for causing the various layers of which fibre-cement consists to adhere to one another
  • silica fume is a by-product of the electric-arc manufacture of silica, silica-iron and other silica-based metallic alloys.
  • the main features of silica fume are the extremely high fineness and the high pozzolanic properties thereof: it consists almost exclusively of amorphous silica highly reactive with cement.
  • Silica fume has proved of fundamental importance also in the manufacture of fibre-cement, where it is used mixed with cement, in amounts which generally vary between 3% and 12% of cement weight, especially because it allows to obtain good mutual adhesion of the various layers which make up the fibre- cement manufactured items (flat sheets, corrugated sheets, pipes and other special pieces) without which it is not possible to obtain good-quality fibre-cement. Thereby the limits are compensated which currently-used fibres have over asbestos, with which, instead, no particular mineral admixture was necessary, such as silica fume, to obtain the necessary adhesion between the layers .
  • the fineness of the individual silica fume particles is, in theory, generally comprised between 0.05 ⁇ m and 0.5 ⁇ m.
  • the silica fume particles tend to aggregate, probably due to electrostatic reasons, forming particle aggregates (sort of clusters) which, for practical purposes, tend to behave as an individual particle.
  • mechanical actions are generally performed also on silica fume to disperse the particles of such aggregates.
  • the dispersion of these aggregates does not require high amounts of work and energy such as in the case of proper milling, but work is nevertheless necessary.
  • silica fume has a particularly high amount of very fine particles (or smaller aggregates) below 1 ⁇ m.
  • Silica fume is a product having definitely unique features both in terms of fineness and of pozzolanic reactivity and, for this reason, the fields of application thereof keep growing ever more in various sectors: manufacture of special concretes, refractory concretes, prefabrication, etc. Over the last few years this has determined a reduced availability of this material - which, as said, is a by-product of other manufacturing processes and hence, as such, is not manufactured per se - and, consequently, a dramatic increase of the price thereof. Moreover, various other types of materials exhibiting pozzolanic properties exist, of both natural and artificial origin. The name pozzolana comes from Pozzuoli, i.e.
  • Pozzolana is a mainly siliceous or siliceous-aluminous material which, in its powder form, is capable of hardening, mixed with water and lime, producing hydrated calcium silicates and aluminates, very similar to those obtained in the hydration of Portland cement.
  • the pozzolanic properties depend on various factors, among which the chemical characteristics, the temperature reached during the natural or thermal process and the cooling speed, the reactive surface, the fineness, etc.
  • the main object of the present invention is hence to identify a material which is apt to replace silica fume in the manufacture of fibre-cement, such as to allow the manufacture of a fibre-cement having a suitable performance, but characterised by greater market availability, and hence of a decidedly lower price than silica fume.
  • Another object of the invention is that of devising a manufacturing method having a limited cost and of easy execution for the manufacture of such new mineral admixture .
  • a further object of the invention is finally that of providing a new method for the manufacture of fibre-cement, characterised by a lower cost and by a greater consistency of the characteristics of the manufactured items obtained using, as partial replacement of the cement component, the same replacement material identified above, treated in the same plant with a different process.
  • a fibre-cement manufacturing method comprising the mixing of cement with strengthening fibres, additives, mineral admixtures and any other known components, characterised in that one of said mineral admixtures is a micronised material with pozzolanic properties, wherein the percentage of particles having a size below 1 ⁇ m is greater than 12%, preferably greater than 16% and even more preferably greater than 20%.
  • the itiicronised material having pozzolanic properties is used in the form of an aqueous suspension.
  • a further opportunity, according to the present invention, is to use the above material with pozzolanic properties, suitably milled, for partially replacing (between 15% and 50%) the cement component.
  • This fineness range is the one which characterises also the cements normally available on the market and among these also pozzolanic cements, as well as fly ash which are residues of coal combustion: nothing new in such respect.
  • the invention identifies the opportunity for optimising costs and efficiency of the fibre-cement manufacturing process through the co-manufacture of a non-micronised material having pozzolanic properties, but more coarsely milled, according to specific granulometric features, with the advantage of a content of pozzolanic substances having more controlled and more stable chemical-physical features and of accomplishing scale economies using all or part of the same plant used for micronisation, mentioned before, also for manufacturing such material.
  • a further, advantageous feature of the invention is that of being able to use treatment waters coming from the same fibre- cement manufacturing process for the preparation of the aqueous suspension of micronised pozzolanic material, following the possible addition to said waters of suitable additives and fluidisers .
  • figs. 1 to 6 are diagrams showing granulometric curves of various silica fume samples with different granulometric features which have been successfully used industrially for fibre-cement manufacture: they display important granulometric differences, since some fibre-cement manufacturers require higher granulometric fineness measures and others less so; Figs.
  • alternative pozzolanic materials are available on the market, with various degrees of reactivity, and with different physical, chemical, mineralogical features and colours. For the choice of the most suitable type, it is useful to proceed to a verification phase taking into account the above factors as well as local ones, such as material availability, transportation costs, consistency of characteristics etc. In this respect, it must be underlined that the more pronounced the pozzolanic properties, the greater the benefit, especially in terms of the mechanical resistances of fibre- cement. In terms of characteristics, alternative pozzolanic materials will be preferably such as to be able to be considered suitable, according to the UNI EN and/or American ASTM standards, for the use thereof in cement or in concrete.
  • figures 1 to 6 have differentiated granulometric curves of wet-milled silica fume (in these granulometric curves, performed with a wet laser granulometer, particle aggregates are identified a single, larger-sized particle) and used for manufacturing fibre-cement from various manufacturers: in all the drawings it can be detected how silica fume has, even though with differentiated granulometric features, a characteristic minimum point at about 1 ⁇ m and a relatively large proportion of particles of a size below l ⁇ m.
  • Figures 7 to 20 show granulometric curves of wet pozzolanas micronised in different ways and times. Natural pozzolanas have all been milled in two steps: the first step with ball mills to reduce size, generally below 100-300 ⁇ m, the second step to perform the more extreme milling with microsphere mills wherein it is unsuitable to introduce particles having a size larger than 100-300 urn.
  • Aqueous suspensions have generally been prepared with concentrations ranging between 40% and 60% of dry substance.
  • fluidisers and/or dispersant which are easily found on the market and are compatible with the manufacturing of fibre-cement have sometimes been used.
  • Figures 1 to 4 show the granulometric curves of silica fume which, despite not being particularly fine, i.e. having a remarkable amount of particles sized above 2 ⁇ m, were suitable for the manufacturing of good-quality fibre-cement.
  • Figures 5 to 6 show instead the granulometric curves of finer silica fume destined to a more demanding fibre-cement manufacturer, and suitable for this second fibre-cement manufacturer.
  • micronised pozzolanas it is suitable for micronised pozzolanas to have an amount of particles sized below 1 ⁇ m equal to at least 12%. More preferably equal to at least 16%. Even more preferably equal to at least 20%. As highlighted by the experiments carried out, better results are obtained the narrower the distribution curve of particle size. It is hence preferable for alternative pozzolanic materials to have an amount of particles of a size below 2 ⁇ m equal to at least 30%. More preferably equal to at least 36%. Even more preferably equal to at least 42%. As a consequence of the fact that the desired fineness IS obtained through extreme milling, also the fraction of larger-sized particles is nevertheless generally smaller-sized than that typical of the granulometric curves of silica fume. Preferably hence 90% of the particles will have a size below 14 ⁇ m, preferably below 9 ⁇ m and more preferably below 5 ⁇ m.
  • Such finely-milled pozzolanic materials allow to manufacture fibre-cement manufactured items having sufficiently high mechanical properties to be able to meet the standards provided by reference standards.
  • the solution identified as the most suitable one is that of wet milling in an aqueous suspension.
  • this milling procedure has proved by far more efficient than dry milling: through wet milling, a much higher degree of fineness at a relatively low cost and in a short time may be obtained. On the contrary, through dry milling enormously longer times are required.
  • aqueous phase the same process water of fibre-cement manufacturing may be used, at least in part, previously treated with suitable fluidisers and additives.
  • microsphere mills by "microsphere” bodies having a size generally varying between 0.5 and 3 mm are understood.
  • pozzolanas to be milled are coarse (understanding by "coarse" size values generally above 100-500 ⁇ m)
  • a preliminary granulometric-reduction process will be necessary, so that the particles be reduced to a size preferably below 100-300 ⁇ m before being sent to the wet milling phase by microsphere mill.
  • the preliminary granulometric reduction phase may be performed regardlessly through various known dry or wet milling technologies.
  • the cost of the pozzolanic materials obtained from wet micronisation may generally vary, between 1/6 and 1/2.5 with respect to the cost of silica fume and this depends mainly on the local availability of good-quality alternative pozzolanic materials and on the costs of silica fume, in addition to other factors such as the quantities dealt with, the cost of electric energy, the labour cost, etc.
  • micronised alternative pozzolanic material necessary to fully or partly replace silica fume will have to take into account a volume replacement of dry material and the difference will hence have to be considered between the absolute specific weight of the pozzolana which one intends to use (generally, materials having pozzolanic properties with specific weights ranging between 2.2 and 2.85 g/1 exist) with respect to the silica fume (2.2 - 2.3 g/1) .
  • the optimal amount will have to be established, generally empirically, with a possible oscillation which may generally be of about ⁇ 25% by weight.
  • a detail which may prove useful in choosing the silica-fume alternative pozzolanic material and which may positively affect fibre-cement properties is the fact that this material, the micronisation degree being equal, be chosen among those having a larger specific surface, i.e., due to its own mineralogical characteristics, a more rugged surface. This characteristic does not emerge from the measurements performed with a laser granulometer, which performs readings detecting the outermost profile of the individual particles as if they were all small spheres, and it must hence be identified by other methods or instruments .
  • fibre-cement is manufactured by using a mixture of various components among which cement, fibres, mineral admixtures, etc. Compared to the other cement-based products, fibre-cement is a very difficult product to obtain, therefore it is fundamental for the raw materials to have certain characteristics and for said characteristics to be consistent .
  • this second portion also of less-fine pozzolanic materials to be prepared and used in the form of aqueous suspension.

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

Abstract

L'invention concerne un procédé de fabrication d'articles en ciment, comprenant au moins une phase de mélange de ciment avec des fibres de renforcement, de l'eau, des additives et des mélanges minéraux, dans lequel lesdits mélanges minéraux comprennent entre autre une première fraction de matériau pouzzolanique micronisé, dans laquelle le pourcentage de particules ayant une taille inférieure à 1 µm en poids sec est supérieure à 12 %, de préférence de 16 %, et mieux encore de 20 %. 90 % des particules de ladite fraction sont inférieures à 14 µm, de préférence inférieures à 9 µm, et mieux encore inférieures à 5 µm. Lesdits mélanges minéraux comprennent en outre une deuxième fraction de matériau pouzzolanique ayant une taille de particules solides moyenne comprise dans la plage allant de 12 µm à 40 µm. L'invention concerne en outre une suspension aqueuse contenant lesdites première et deuxième fractions de matériau pouzzolanique.
PCT/IB2008/052443 2007-06-22 2008-06-20 Procédé de fabrication de produits à base de ciment et de fibres, comprenant l'utilisation d'un matériau pouzzolanique, et suspension aqueuse de matériau pouzzolanique utilisée dans ledit procédé WO2009001263A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08763400A EP2173682A1 (fr) 2007-06-22 2008-06-20 Procédé de fabrication de produits à base de ciment et de fibres, comprenant l'utilisation d'un matériau pouzzolanique, et suspension aqueuse de matériau pouzzolanique utilisée dans ledit procédé

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI20071269 ITMI20071269A1 (it) 2007-06-22 2007-06-22 Procedimento di fabbricazione di manufatti cementizi a base di cemento e fibre, comprendente l'utilizzo di un materiale pozzolanico, e sospensione acquosa di materiale pozzolanico utilizzata in detto procedimento.
ITMI2007A001269 2007-06-22

Publications (1)

Publication Number Publication Date
WO2009001263A1 true WO2009001263A1 (fr) 2008-12-31

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PCT/IB2008/052443 WO2009001263A1 (fr) 2007-06-22 2008-06-20 Procédé de fabrication de produits à base de ciment et de fibres, comprenant l'utilisation d'un matériau pouzzolanique, et suspension aqueuse de matériau pouzzolanique utilisée dans ledit procédé

Country Status (3)

Country Link
EP (1) EP2173682A1 (fr)
IT (1) ITMI20071269A1 (fr)
WO (1) WO2009001263A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010007534A3 (fr) * 2008-07-18 2010-04-29 Lafarge Formulations aqueuses
WO2014066736A1 (fr) * 2012-10-25 2014-05-01 Hanson Pipe & Precast Llc Béton renforcé de fibres et compositions de formation associées

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0263723A2 (fr) * 1986-11-28 1988-04-13 Dansk Eternit-Fabrik A/S Procédé de fabrication de produits renforcés par des fibres
US5167710A (en) 1989-06-09 1992-12-01 Saint-Gobain Recherche Process for manufacturing a cement mixture containing reinforcing fibers and products obtained therefrom
WO1997021640A1 (fr) 1995-12-15 1997-06-19 New Jersey Institute Of Technology Procede de preparation de cendres volantes pour beton et mortier a haute resistance a la compression et compositions obtenues
WO2000050362A1 (fr) * 1999-02-22 2000-08-31 Keele University Compositions a base de ciment
WO2001040135A2 (fr) * 1999-11-30 2001-06-07 Engelhard Corporation Fabrication de metakaolin ameliore par broyage et utilisation dans des composites a base de ciment et dans des systemes a activation alcaline
JP2001331094A (ja) 2000-05-22 2001-11-30 Taiheiyo Cement Corp 点字プレート
WO2002081398A2 (fr) * 2001-04-05 2002-10-17 Petracem S.R.L. Additifs destines au secteur du batiment provenant de sous-produits ou dechets industriels et leur procede de production
JP2002321952A (ja) * 2001-04-26 2002-11-08 Taiheiyo Cement Corp セメント混和材
GB2424418A (en) 2005-03-21 2006-09-27 Felix Allen Hughes Cement composition containing amongst other constituents, pozzolanic reaction particles and fibres

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0263723A2 (fr) * 1986-11-28 1988-04-13 Dansk Eternit-Fabrik A/S Procédé de fabrication de produits renforcés par des fibres
US5167710A (en) 1989-06-09 1992-12-01 Saint-Gobain Recherche Process for manufacturing a cement mixture containing reinforcing fibers and products obtained therefrom
WO1997021640A1 (fr) 1995-12-15 1997-06-19 New Jersey Institute Of Technology Procede de preparation de cendres volantes pour beton et mortier a haute resistance a la compression et compositions obtenues
WO2000050362A1 (fr) * 1999-02-22 2000-08-31 Keele University Compositions a base de ciment
WO2001040135A2 (fr) * 1999-11-30 2001-06-07 Engelhard Corporation Fabrication de metakaolin ameliore par broyage et utilisation dans des composites a base de ciment et dans des systemes a activation alcaline
JP2001331094A (ja) 2000-05-22 2001-11-30 Taiheiyo Cement Corp 点字プレート
WO2002081398A2 (fr) * 2001-04-05 2002-10-17 Petracem S.R.L. Additifs destines au secteur du batiment provenant de sous-produits ou dechets industriels et leur procede de production
JP2002321952A (ja) * 2001-04-26 2002-11-08 Taiheiyo Cement Corp セメント混和材
GB2424418A (en) 2005-03-21 2006-09-27 Felix Allen Hughes Cement composition containing amongst other constituents, pozzolanic reaction particles and fibres

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010007534A3 (fr) * 2008-07-18 2010-04-29 Lafarge Formulations aqueuses
WO2014066736A1 (fr) * 2012-10-25 2014-05-01 Hanson Pipe & Precast Llc Béton renforcé de fibres et compositions de formation associées

Also Published As

Publication number Publication date
ITMI20071269A1 (it) 2008-12-23
EP2173682A1 (fr) 2010-04-14

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