EP2539297A2 - Adhésifs réfractaires pâteux légers et leur utilisation - Google Patents

Adhésifs réfractaires pâteux légers et leur utilisation

Info

Publication number
EP2539297A2
EP2539297A2 EP11712161A EP11712161A EP2539297A2 EP 2539297 A2 EP2539297 A2 EP 2539297A2 EP 11712161 A EP11712161 A EP 11712161A EP 11712161 A EP11712161 A EP 11712161A EP 2539297 A2 EP2539297 A2 EP 2539297A2
Authority
EP
European Patent Office
Prior art keywords
adhesive
silica
binder
fibers
adhesive according
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.)
Withdrawn
Application number
EP11712161A
Other languages
German (de)
English (en)
Inventor
Rainer Angenendt
Heike Meschke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tdh - Technischer Daemmstoffhandel GmbH
Original Assignee
Vatramaxx GmbH
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 Vatramaxx GmbH filed Critical Vatramaxx GmbH
Publication of EP2539297A2 publication Critical patent/EP2539297A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/003Compositions 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 hybrid binders other than those of the polycarboxylate type
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24Compositions 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 alkyl, ammonium or metal silicates; containing silica sols
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/28Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

  • the invention relates to adhesive according to the preamble of claim 1, in particular one-component high-temperature resistant ready-to-use light pasty refractory adhesive with immediate adhesion, which harden when dried and at least one
  • Light filler a binder containing fibers and / or wollastonite and water, for applications up to about 1100 ° C.
  • lightweight fillers are to be understood here as high-melting mineral granules of low density, for example, expanded volcanic ash, expanded perlite, etc.
  • finely divided or fine is not used in the sense of a certain small grain size, but in the sense of “powdery” or “granular” in contrast to “lumpy.” So there is no specific one
  • Bonding of insulation materials for vehicle construction, shipbuilding, aircraft construction, building construction and industry, for bonding against molten metal in foundry technology The main application spectrum is fireproof bonding of mineral wool or other porous insulating materials on various absorbent or non-absorbent substrates, for example in shipbuilding, and in the field of shipbuilding rail vehicle construction. In shipbuilding, aircraft construction and rail vehicle construction is always looking for new lighter materials. In addition to the energy costs that every kilogram of material used consumes, every kilogram of material that is installed above the waterline is problematic, especially in shipbuilding, since this reduces the payload of a ship by one
  • the adhesives according to the invention have, in addition to the adhesive, an insulating (low apparent density 0.250-0.350 g / ml) and optionally a cooling in case of fire
  • Document EP 1 508 602 A1 describes a high-strength assembly adhesive in order to be able to withstand greater loads.
  • the invention has for its object to develop light pasty refractory adhesive of the type mentioned for cost-effective full-surface bonding of insulating areas, which only a very low shrinkage ( ⁇ 1%) and secure fixing of the insulating materials to be mounted or
  • the document EP 1 508 602 A1 describes a mounting adhesive with a creamy consistency on an organic basis with any inorganic fillers. In fact, not all fillers are suitable for this at all. The recipes are kept very vague.
  • a pasty adhesive with hybrid binders wherein the organic fraction is based on an inorganic framework of silica sol grafted, so the organic portion forms a unit with the inorganic portion.
  • the adhesive according to the invention is additionally mixed with binders of pure silica sols and mineral binders of silica which contains finely divided kaolin, the adhesive according to the invention retains its structure even at temperatures up to 1100.degree.
  • Document EP 1 508 602 A1 describes a high-strength assembly adhesive in order to be able to withstand greater loads.
  • an adhesive which is suitable exclusively for fixing lightweight insulating materials or for filling, jointing and coating and whose function is to protect the object in the event of a fire by obtaining the adhesive, coating, etc. Therefore, the content of organic adhesive components is very low (fire class and low energy release) and the inorganic and mineral adhesive components (high
  • the mineral adhesive component kaolin or kaolinite develops its adhesive power completely only at high temperatures of 500 to 1000 ° C, so that the product then obtains its final strength and high fire resistance. At these temperatures, the adhesive according to the
  • the content of fibers and / or wollastonite serves to cohesion of the mass in the wet state.
  • Wollastonite is predestined for combination with microcellular expanded volcanic rocks due to its coarse needle-like structure.
  • the short needles of wollastonite and the microcellular bloated volcanic rocks easily penetrate into open porous layers and thereby reinforce the bond of the surfaces to be bonded together.
  • the hybrid binder (s) provide cohesion after drying at temperatures up to about 200/400 ° C due to the organic constituent and at higher temperatures due to the sintering of the silica particles.
  • the kaolin used and the silica sol are also a binder, which develops its function at elevated temperature. Kaolin is also used at
  • the closed-cell lightweight fillers provide the necessary volume and a very low density compared to the state of the art.
  • the glue can be any suitable material.
  • the kaolin which splits off approximately 14% of water at 550 ° C.
  • Al (OH) 3 is the world's most widely used flame retardant (also known as ATH for "aluminum trihydrate”), which works by splitting off water, which already starts at 150 ° C, cooling and gas-diluting.
  • microcavities are surface treated to protect against water attack in the plastic adhesives, thereby rendering the adhesives shelf stable.
  • Advantageous embodiments of the invention are set forth in the subclaims.
  • the invention relates to the use of the aforementioned adhesive for various advantageous applications according to claim 8.
  • Perlite Korean: perlite
  • volcanic glass obsidian
  • Microcellularly expanded volcanic rocks produced using new environmentally friendly and energy-saving processes, achieve properties and technical values that distinguish them from older, porous expanded volcanic rocks ("expanded perlites").
  • Microcellular expanded volcanic rock is a filler from the group of aluminum silicates and is composed of spherical ("honeycomb"), rod-shaped and flaked particles, resulting in high packing densities and higher bond strengths than conventional hollow microspheres due to mechanical and cohesive bonding forces.
  • the expanded volcanic rock is preferably used in the form of nonporous hollow granules. It is also proposed that the expanded volcanic rocks consist entirely of cellular expanded volcanic rocks. For porous
  • Hollow granules would increase the bulk density, due to the increased need for binders and minerals (infiltrate).
  • the masses would be dull and would be worse to process.
  • the mass after hardening is extremely stable, even at 1000
  • Kaolin also referred to as china clay or aluminum silicate, is a fine, iron-free, white rock containing kaolinite, a weathering product of feldspar, as the major constituent.
  • the kaolin used as a film covers the high-melting light filler and additionally solidifies the structure of the adhesive at 550 ° C and 970 ° C.
  • the strength of the structure and the shrinkage are determined by the ratio
  • Kaolin Siliceous / KieselsoiyAluminiumhydroxyd to the light fillers and their distribution influenced.
  • Another advantage of the used mixture of kaolin / silica sol and / or silica is that the mass after drying in addition to the binder, the fibers and or wollastonite is mechanically stabilized.
  • Binders is used with a binding effect in different temperature ranges.
  • the innovation of the product according to the invention also consists in that suitable, complementary binder systems are used, for.
  • B. the hybrid binder, which adheres the support structures made of fibers and / or wollastonite already during drying under room temperature with the light fillers (microcellular expanded volcanic rock) sufficiently to fix the structure.
  • mineral binders By mineral binders, z.
  • ceramic and / or mineral refractory fibers and / or organic refractory fibers for example carbon fibers, alone or in
  • wollastonite is used.
  • Wollastonite (rarely also tablespar or tablespat) is a frequently occurring mineral with the chemical composition CaSi0 3 , more precisely Ca 3 [Si 3 0 9 ]. From a chemical point of view, wollastonite is a calcium salt of metasilicic acid and therefore belongs to the mineral class of silicates. Based on
  • Crystal structure can explain some macroscopic properties of wollastonite.
  • Monocrystals of wollastonite have a needle-like to fibrous form
  • Oxygen via covalent bonds are interconnected, there is an ionic bond between calcium and oxygen, which is based on a purely electrostatic interaction and thus represents the weaker bond. Due to its fibrous to needle-like crystals and its high melting point (1540 ° C), wollastonite offers a wide range of technical applications (source:
  • Ceramic fibers or ceramic fibers are fibers
  • inorganic, non-metallic material inorganic, non-metallic material.
  • ceramic fibers there are now various polymers, so-called precursors, produced by pyrolysis amorphous fibers, which are referred to by their properties as ceramic fibers.
  • precursors produced by pyrolysis amorphous fibers, which are referred to by their properties as ceramic fibers.
  • amorphous glass fibers which are not counted among the ceramic fibers, is best made possible by the manufacturing process (glass fibers from glass melt, amorphous ceramic fibers from polymeric precursors by pyrolysis).
  • the ceramic fibers are classified into oxidic and non-oxidic.
  • oxide ceramic fibers are fibers based on alumina and
  • Mixed oxide fibers of 85% A1 2 0 3 and 15% Si0 2 are also referred to as mullite fibers. All of these fibers are polycrystalline.
  • Non-oxide, industrially produced fibers (other than carbon fibers) have various types of silicon carbide fibers known.
  • Starting polymers are almost exclusively so-called poly-carbosilanes. These are polymers Hydrocarbons in which individual carbon atoms have been replaced by silicon atoms or silanes in which individual silicon atoms have been replaced by carbon atoms.
  • Additives crosslink the polymers in a curing process, so that they do not simply evaporate after the spinning process during the pyrolysis, but - as in the production of carbon fibers - are converted into an amorphous, usually non-stoichiometric, still free carbon-containing SiC ceramic fiber.
  • Hybrid bonding agent used according to the invention
  • an organic-inorganic hybrid binder is used, which is available under the trade name COL.9 BASF and Inowool W + from the company Inomat.
  • COL 9 contains 50 to 100 nm composite particles containing amorphous silica particles 5 and a polymer 6 based on n-butyl acrylate and methyl methacrylate (see Figure 1). The particles are dispersed in water. Due to the stickiness of the particles due to the polymer content is obtained an excellent binder for low temperatures, up to about 200 ° C. At elevated temperatures, the polymer fraction decomposes and the silica particles remain and thus preserve the structure, wherein the silica particles also forms a solid framework at a correspondingly high temperature.
  • binders have a solids content of about 35 to 60% by weight. proportion, based on the solids content, is 30 to 60 wt .-%.
  • a surface-treated silica is used.
  • Silica is an intimate mixture of finely divided silica and kaolinite.
  • the Neuburg Siliceous Earth is known, which is preferably used according to the invention.
  • the silica is treated with a silane so that the individual particles have a functional hydrophilic surface.
  • Such an activated silica is available under the trade name "AKTISII EM” from Hoffmann Mineral GmbH, Neuburg (Danube), where the silica is treated with 3-epoxypropyloxipropyltrimethoxysilane.This so-called activated silica can be used in powder form the use of a mixture of silica sol and kaolin / kaolinite.
  • the precisely weighed fibers are carefully added to this mixture, teased by stirring (at low speed) and completely wetted with the aqueous solution.
  • the precisely weighed light fillers and minerals are mixed with each other in a free fall mixer. Both premixes are mixed together with uniform slow stirring in a compulsory mixer for about 45 min. High shear forces, pressure and friction are to be avoided as much as possible in order not to damage the microcellular bloated volcanic rocks.
  • the lightweight fillers must be completely wetted to obtain a homogeneous lightweight pasty adhesive.
  • a central customer benefit when using the products according to the invention is the desired goal of more efficient and safe fire protection
  • Mineral wool or other porous insulating materials used on absorbent or non-absorbent substrates.
  • the fields of application are the industrial furnace construction, the foundry technology, the
  • the light pasty refractory adhesive according to the invention for the o. G. Bonding of mineral fiber insulating materials to metal or other non-absorbent and absorbent substrates is particularly well suited.
  • the paste-like, light-weight structure of the adhesive enables it to adhere to almost any surface, while at the same time allowing the adhesive to be incorporated into porous surfaces. Due to the resulting high capillary forces, the light pasty refractory adhesives can also be used on porous and absorbent substrates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des adhésifs réfractaires pâteux légers qui durcissent au séchage et qui contiennent au moins une matière de charge légère, un liant, des fibres et/ou de la wollastonite, ainsi que de l'eau. Les adhésifs selon l'invention sont caractérisés en ce qu'on utilise comme liant un liant organique-inorganique (liant hybride) qui contient de l'acide silicique à fines particules et un polymère organique et en ce que la pâte ou le mortier contiennent du kaolin ou de la kaolinite et un sol de silice, en particulier de la silice.
EP11712161A 2010-02-24 2011-02-23 Adhésifs réfractaires pâteux légers et leur utilisation Withdrawn EP2539297A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201010009145 DE102010009145A1 (de) 2010-02-24 2010-02-24 Leichte pastöse feuerfeste Kleber und ihre Verwendung
PCT/EP2011/000874 WO2011104010A2 (fr) 2010-02-24 2011-02-23 Adhésifs réfractaires pâteux légers et leur utilisation

Publications (1)

Publication Number Publication Date
EP2539297A2 true EP2539297A2 (fr) 2013-01-02

Family

ID=44070736

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11712161A Withdrawn EP2539297A2 (fr) 2010-02-24 2011-02-23 Adhésifs réfractaires pâteux légers et leur utilisation

Country Status (3)

Country Link
EP (1) EP2539297A2 (fr)
DE (1) DE102010009145A1 (fr)
WO (1) WO2011104010A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105859311A (zh) * 2016-04-06 2016-08-17 遵义市恒新化工有限公司 一种高温粘接剂
CN109562997A (zh) 2016-08-19 2019-04-02 瓦克化学股份公司 绝缘灰泥层或绝缘面板形式的多孔模制体

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1508602A1 (fr) * 2003-08-20 2005-02-23 BASF Aktiengesellschaft Adhésif d'assemblage à base d'une dispersion polymère aqueuse

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US4226625A (en) * 1979-06-04 1980-10-07 Nalco Chemical Company Insulating tundish veneer composition useful in casting steel
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US4664712A (en) * 1986-04-01 1987-05-12 Ignacio Cisneros Thermal insulating material and method of production thereof
SU1551700A1 (ru) * 1988-01-15 1990-03-23 Минский научно-исследовательский институт строительных материалов Способ изготовлени теплоизол ционных изделий
US6554893B2 (en) * 2000-12-18 2003-04-29 Georgia-Pacific Corporation Fire door core
CN1583656A (zh) * 2004-05-27 2005-02-23 韩长玉 一种易降解陶瓷材料及其生产方法
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JP2009132558A (ja) * 2007-11-30 2009-06-18 Taiheiyo Material Kk 水硬性モルタル組成物及び硬化体
CN101628819A (zh) * 2008-07-18 2010-01-20 山东鲁阳股份有限公司 无烟无味陶瓷纤维板

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EP1508602A1 (fr) * 2003-08-20 2005-02-23 BASF Aktiengesellschaft Adhésif d'assemblage à base d'une dispersion polymère aqueuse

Non-Patent Citations (1)

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Title
See also references of WO2011104010A2 *

Also Published As

Publication number Publication date
WO2011104010A2 (fr) 2011-09-01
DE102010009145A1 (de) 2011-08-25
WO2011104010A3 (fr) 2011-10-20

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