IE50568B1

IE50568B1 - Fire-proof,adhesive,water-proof binding material

Info

Publication number: IE50568B1
Application number: IE21680A
Authority: IE
Original assignee: Diffusion Rech Tech Financ
Priority date: 1979-02-02
Filing date: 1980-02-04
Publication date: 1986-05-14
Also published as: MA18722A1; EP0015236B1; DE3070694D1; FR2461686A1; IE800216L; FR2461686B1; EP0015236A1; CH639051A5; DK40580A

Abstract

1. An adhesive, incombustible and waterproof binder composition comprising two distinct parts, the first part comprising at least one alkaline silicate in aqueous solution and the second part, in the dry powder state, comprising at least one setting reagent which allows to form a silica gel, said composition being characterized by the fact that the two parts are plasticized, the first part, the weight of which represents between 30 and 85 % of the whole weight of the binder, being constituted of silicate and of at least one liquid plasticizing agent which represents 2 to 20 % by weight of said whole first part, and the second part comprising from 5 to 15 % by weight, in respect of the weight of the silicate, of a plasticizer constituted by one or more of the following products : casein, starch, carboxymethylcellulose, the amount of silicate being comprised between 24 and 83 % by weight of the whole binder.

Description

The present invention relates to a composition of an adhesive, fire-proof, water-proof binding material.

This can be used with several different types of material and consequently constitutes the basic element for the 5 manufacture of the following products: - Impregnation products intended for the stabilization of pulverulent ground and sands, for the hardening of asbestos particles and rock fibres and for the protection of wood against insects, rodents and 10 cryptogams - Glues resisting very high temperatures (+1000°C) for the assembly of all materials, except for certain plastic materials - Anti-corrosive, fire-proof decorative paints - Insulating, thermal, acoustic, Fire-proof coatings/ plasters - Fire-proof sheets and panels.heat-proof, reinforced or not, which can be moulded into form or flat -3- Blocks of all shapes and sizes, particularly intended for the building Industry - Differently shaped elements, into which electrical heating resistances can be incorporated There are a large number of known procedures using the hardening of alkaline silicates In order to obtain a binding material for different uses.

The procedures used 1n order to obtain this hardening can be put into two categories: 1. Hardening and water-tightness obtained by a large increase in temperature (200°C and more). This is the case of French Patent 2.136.862 which uses heating of the alkaline silicates to ensure the bonding between expanded mineral granules. This is also the case for the Japanese Patent 76.99,125. 2. Hardening and water-tightness obtained by chemical reaction. This is the case for the Czech Patent 147.594 which uses the acid reaction of lime and cement on alkaline silicates and Japanese Patents 73.14.729 and 76.91.935 which use the reaction of fluorine (fluosilicates) on alkaline silicates. The same reaction is used in the Soviet Patent mentioned in Chemical abstracts Vol. 83-1975, page 314. It is also the case for French Patent 2.295.103 which uses, metallic oxides, aluminium 0S68 -4hydroxide or barium sulphate, in order to obtain this reaction.

The two procedures described above have been known for a long time now, as far as the heating at high temperature is concerned as well as the chemical reaction in the presence of acids.

In 1841, Mr. Kuhlmann showed that by sprinkling soft, porous acid stones with potassium silicate, they could be made very hard, frost-proof and water-proof. He himself manufactured paint by incorporating metallic oxides in alkaline silicates.

From the beginning of the twentieth century until 1940, many firms have manufactured paint with a base of alkaline silicates with metallic oxides; these were, for example; RANSONNE in England, KAULBACH in Germany, SILEXORE in France. French Patent Application 2.378.076 describes an adhesive compound in two distinct packages, consisting of an aqueous component and a dry, gritty component, comprising a setting and an insolubility reagent and a gritty filler. It is also mentioned that 2 to 4% of a plasticizer may be added to the aqueous component.

According to the invention there is provided an adhesive, incombustible and waterproof binder composition comprising two distinct parts, the first part comprising at least one alkaline silicate in aqueous solution and the second part, -5in the dry powder state, comprising at least one setting reagent which allows formation of a silica gel, said composition being characterized by the fact that the two parts are plasticized, the first part, the weight of which represents between 30 and 85% of the whole weight of the binder composition, being constituted of silicate and of at least one liquid plasticizing agent which represents 2 to 20% by weight of said first part, and the second part comprising from 5 to 15% by weight, with respect to the weight of the silicate, of a plasticizer constituted by one or more of the following products: casein, starch, carboxymethyleellulose, the amount of silicate being comprised between 24 and 83% by weight of the binder composition.

The invention also provides a method of fabricating a binder from a composition according to the invention, wherein both parts of said composition are mixed before use, the amount of setting reagent remaining below 10% of the weight of silicate.

The binding compound according to the invention comprises a first component in liquid form and a second one in the form of a powder, separated in different packages, ensuring their -6unlimited shelf-life inside the packages. The compound is characterized in that the two components are plasticized, the first component representing between 30 and 85% of the total weight of the binder and consisting of a silicate and at least one plasticising agent, which represents 2 to 20% by weight of the first component, and the second component comprising between 5 to 15% by weight, in relation to the weight of the silicate, of a plasticizing filler, consisting of one or more of the following products: casein, starch, carboxymethylcellulose, the silicate content lying between 24 to 83% of the total weight of the binder.

Variants of the present invention refer to the use of acrylic resins in dispersion or to anionic bituminous emulsions mixed with alkaline silicates.

Only the patent registered by KOPPERS COMPANY INC. in the U.S.A. under No. 3.297.616, describes the use of acrylic resin aqueous dispersion mixed with alkaline silicates, for a treatment for metal surfaces. The modification of alkaline silicates by acrylic resins, by resols or anionic bituminous emulsions is also quoted in tbe French Patent Application 2.378.076. But the surface film formed by the resin prevents the reaction in the presence of CO2 of the atmosphere, for the acrylic resins are, with difficulty pervious to carbonic gas. Moreover, without the addition of aromatic solvents (which is not foreseen in this patent), the polymerisation of the resins in the mixture is difficult. 80568 -7The procedure of the Invention foresees the addition of aromatic solvents together with the acrylic resins or anionic bituminous emulsion which allows a good polymerisation and a swelling of the latter.

The first component is a plasticized mineral binding material in aqueous solution, which consists of a sodium, potassium or lithium silicate or the mixture of two or three of these silicates according to the application to which is added preferably 2 to 15% by weight depending on the weight of the silicate of a plasticizer such as glycerine, a derivative of glycol like ethyleneglycol or others, this is to limit shrinking during setting and to lower the lower limit of the working temperature (4° instead of 8°C).

The plasticization of these alkaline silicates can profit15 ably be modified by the addition of acrylic resins in dispersion; thus, for example, the acrylic resin known under the commercial name ACRONAL 290.D manufactured by the firm “RHONE-POULENC, by the addition of anionic bituminous emulsions of siliconates, of vegetable oils, for example linseed oil. The overall proportion of these plasticizers in the mixture varies according to the quality of the product desired; it is 2 to 20% depending on the case.

In the case of a thin coating (paint or plaster) a greater proportion of plasticizer, 15 to 20% is preferable.

These plasticizers can be used on their own or in a mixture. In the case of the use of acrylic resin as a plasticizer, it -8is recommended to pre-mix, 24 hours in advance, resins with an aromatic solvent, like toluene or benzene, in a proportion of 3 to 5% by weight of the resin; this is in order to allow a good polymerisation of the resins in the mixture and to lower the temperature of the filmformation of the resins, from 20°C to 8°C. The addition of preferably 1% to 2% of ammonia to the 1% to 5% resin/toluene mixture assists in preventing the formation of lumps.

With the anionic bitumen emulsions it would also be pref10 erable to pre-mix with 3 to 5% of an aromatic solvent, toluene or benzene, before mixing with the alkaline silicates.

With vegetable oils, it would be profitable to pre-mix the oil with 3 to 5% of oil of turpentine.

The incorporation of siliconates (silicones in aqueous phase) in the silicates could be done without any special precautions; the proportion of siliconates in the silicates will be the function of the desired aim; thus a proportion of 15% in a plaster/coating will make the latter totally 20 water-repellent, therefore providing better thermal insulation. The presence of siliconates is not indispensable for example in a coating for stabilizing sands.

-QThe mixture of the plasticizers with the alkaline silicates will be made profitably with the help of a blade or vane mixer turning at about 800 to 1000 revolutions/ per minute.

The alkaline silicates chosen will be preferably those whose silica/sodium, potassium or lithium ratio is above 3; The silicates of this type available in the trade have a weight ratio lying between 3.5 and 3.75. The sodium silicate will generally be preferred due to its price; nevertheless, metals will preferably always be covered with a primary coat based on potassium silicates.

The first component thus defined accounts for a proportion of 30 to 85% of the total weight of the finished product, according to the application.

The second component is in a dry state, thoroughly mixed and finely ground; it comprises: A. Setting reagents, which enter for 2 to 30% by weight of the silicates, according to the type of application described further on. There are two kinds of setting reagents, which must be used separately, according to the aim and type of application desired: 1. Slow setting reagents, used for glues, paintwork, plaster/coatings. These are zinc, sodium, calcium, -10magnesium or barium fluosilicates. The proportion of these slow reagents should not exceed 15%, preferably 10% by weight of the silicates. A good average proportion will be 5 to 7%. 2. Fast setting reagents, used for coatings, certain projected coatings/plasters separate from outlets, blocks panels and sheets.

These fast setting reagents are: calcium, sodium, potassium, magnesium or ammonium chlorides; acids such as powdered boric acid; zinc, copper, ammonium, barium sulphates; calcium, ammonium, sodium potassium phosphates. The proportion of these fast reagents would advantageously lie between 5 and 25% by weight of the silicates. A good proportion would be 10 to 20%.

B. Active fillers. These fillers have the aim of favouring the carbonization of the mixture and the conversion of COg into COgCA in combination with air.

The proportion of these active fillers in the mixture will be, according to the applications, from 1 to 55%, preferably from 1 to 25% by weight of the alkaline silicates; these are, for example: 1. Clays like bentonite and kaolin; 2. Carbonates, like lime carbonate; 3. Lime, sodium, potassium or ammonium bicarbonates; 4. Magnesium silicate or talc; 80568 -115. Metallic oxides, such as zinc, barium, lead, titane, iron or copper oxide.

These active fillers could be used alone or in a mixture. It must be noted that, in the case of bicarbonates, the proportion in the mixture should not exceed 5%.

C. Plasticizing fillers, which play a mechanical role in the mixture, rendering the binding material less breakable after drying and making it possible, in the case of paintwork and plaster/coatings manufactured according to the procedure of the invention, to avoid fissures and cracking. These plasticizing fillers are, for example: 1. Casein; 2. Starch; 3. Carboxymethylcellulose The proportion of these plasticizing fillers will be the function of the desired quality of the product; by way of example, a good proportion for the manufacture of paintwork will be 5 to 15% by weight of the silicates.

The fact should be borne in mind that since carboxymethyIcellulose, has a swelling power and an increased ability to re-absorb water, its use as a plactizer should preferably be limited to a proportion lying between 1 and a maximum of 10% by weight of the silicates. The flexibility of the film thus realised after application -12varies in function with this proportion. The three plasticizers described above can be used alone or in a mixture. These plasticizing fillers have moreover the advantage of increasing the adhesive power of the mixture.

D. Neutral fillers. These play a secondary role of reinforcement of the mixture and give a certain hardness to the latter. These are: 1. Small fibres, the length of which may vary between 0,5 and 10mm, of different origins: rock, glass fibres, different synthetic fibres, vegetable and animal.

Their role is to reinforce the tensile strength and to avoid fissures. 2. Silica, glass, crystal powders, finely ground.

Their role is to increase the hardness of the mixture as well as the resistance to abrasion.

According to the result and the final product desired, the proportion of neutral fillers in the mixture will be from 2 to 10% by weight compared to the weight of the silicates.

E. Component fillers whose addition is determined by the type of product· one wants to manufacture from the binding material. -13There can be two kinds of component fillers: 1. Fire-proof fillers, of mineral origin. These are, for example, expanded perlite, expanded mica, expanded clay, diatoms, expanded glass, pozzolana and pumice-stone; the charges described above will be used in order to obtain insulating and fire-proof products. These are, by the way, sand and fine gravel, different ground-down rocks; these latter fillers will be constituent parts in the making of different types of concrete. 2. Combustible fillers, such as sawdust and straw, flax, sisal, coconut, reed, sugar cane, rag waste; these fillers, used with the binding material, absorb the silicates in aqueous phase; consequently, in 15 the presence of high temperatures (600 to 1000°C), the transformation of the cellulose is carried out by pyrolisis and yields cokes; the product thus obtained is therefore not inflammable.

The application of the binding material according to the 20 invention can be carried out according to three different procedures, dictated by the proportion and the choice of the setting reagents (A). These three application procedures are as follows: a) First application procedure: b) c) -14The two components are mixed before the application, manually or with the help of a blade or spiral mixer.

In this case, the total proportion of the setting reagents should not exceed 10% by weight of the silicates. A good proportion will be 5%; the pot lifetime of the product thus obtained being fortyfive minutes. The product, paint, plaster/coating or moulding paste, could be applied with a brush, a roller or gun (for paint and plaster/coatings); a paste could oe poured directly into the mould.

Second application procedure: The proportion of the setting reagents in the second component lies between 5 and 25%; in this case, the extremely fast setting of the components does not allow previous mixing. A projection tool will then be used, allowing the projection of the two components separately or simultaneously. This procedure will be used for plaster/coatings or for filling moulds; in this latter case, the unmoulding could occur very rapidly.

Third application procuedure: The proportion of the setting reagents will be as high as in the previous case; the two components will -15then admixed with water, i.e. 80% of water in the first component and 90% in the second component (which contains only those setting reagents, which are soluble). They are then projected separately beginning either with the first component, or with the second component. It is important to leave the component applied first to dry at least partially, in order to avoid (above all in the case of absorbent supports) surface warping due to the presence of a large quantity of water. This type of application will be used for the stabilisation of sands, ground, asbestos particles and rock fibres, as well as for the impregnation of wood and all pulverulent materials. The impregnation could be effected by soaking or spraying.

By way of example, some formulae of binding material adapted to the above application procedures are given in the following.

Formula for an insulating plaster/coating First component: Sodium silicate 500 grs Potassium silicate 500 grs Glycerine 50 grs Ethylene glycol 50 grs Siliconate grs -16Second component: Zinc fluosilicate 150 grs Talc 50 grs Expanded mica 200 grs 5 Small rock fibres 100 grs Calcium carbonate 30 grs Bentonite 100 grs Bicarbonate of soda 20 grs Carboxymethyl cellulose 50 grs 10 Expanded perlite 180 grs The product formulated above will be projected machine of the type used for the projection of icles. Formula for a metal paint ί 5 First component: Potassium silicate 1000 grs Glyceri ne 50 grs Linseed oil (diluted with 5% of turpentine) 100 grs 20 Si 1i conate 50 grs Second component: Zinc oxide 200 grs Zinc fluosilicate 50 grs Bentoni te 150 grs S0868 Calcium carbonate 100 grs Talc 100 grs Casein 75 grs Carboxymethylcellulose 75 grs Ground silica 50 grs This last formula allows the preparation of paint which could be applied, either with a brush, a roller, or a gun, on metal supports. It would serve as a primary coat before the projection of a fire10 proof plaster/coating such as that described before.

Formula for insulating coating/plaster First component: Sodium silicate 1000 grs Ethyleneglycol 50 grs Acrilic resin with aromatic solvent 51,5 grs Siliconate 3,5 grs Second component: Bentoni te 100 grs Calcium carbonite 50 grs Expanded perlite 150 grs Carboxymethylcellulose 50 grs Sodium fluosilicate 100 grs Small rock fibres 50 grs -18Such a piaster/coating, pre-mixed, could be applied either with a machine or by hand, its pot lifetime will be about one hour.

Formula for a glue for panels made up of particles First component: Sodium silicate 500 grs Potassium silicate 500 grs Glycerine 50 grs Acrilic resin with aromatic 10 solvent (2,5 grs) and ammonia (2,5 grs) 55 grs Second component: Bentoni te 150 grs Calcium carbonate 50 grs 15 Talc 150 grs Carboxymethylcellulose 80 grs Zinc fluosilicate 50 grs Casei n 20 grs Starch 20 grs 20 The two components of such a glue are mixed until an oily paste is obtained which can be used for app roximately one hour.

Claims

Claims:

1. An adhesive, incombustible and waterproof binder composition comprising two distinct parts, the first part comprising at least one alkaline silicate in aqueous 5 solution and the second part, in the dry powder state, comprising at least one setting reagent which allows formation of a silica gel, said composition being characterized by the fact that the two parts are plasticized, the first part, the weight of which represents Ίθ between 30 and 85% of the whole weight of the binder composition, being constituted of silicate and of at least one liquid plasticizing agent which represents 2 to 20% by weight of said first part, and the second part comprising from 5 to 15% by weight, with respect to the weight of 15 the silicate, of a plasticizer constituted by one or more of the following products: casein, starch, carboxymethylcellulose, the amount of silicate being comprised between 24 and 83% by weight of the binder composition.

2. The composition according to claim 1, wherein said liquid 20 plasticizing agent comprises glycerin and/or a glycol derivative and constitutes from 2 to 15% by weight of the alkaline silicate.

3. The composition according to claim 2, wherein said liquid plasticizing agent is ethylene glycol. • · -204. The composition according to claim 1, wherein said liquid plasticizing agent comprises an anionic bituminous emulsion with an aromatic solvent constituting 3 to 5% by weight of said emulsion.

4. 5 5. The composition according to one of the claims 1 to 4, wherein said liquid plasticizing agent comprises moreover at least one acrylic resin in a dispersion with an aromatic solvent constituting 3 to 5% by weight of the acrylic resin and with ammonia constituting 1 to 5% 10 by weight of the acrylic resin.

5. 6. The composition according to one of the claims 1 to 5, wherein said liquid plasticizing agent comprises moreover at least one vegetable oil which is mixed with 3 to 5% of its weight of turpentine oil. 15

6. 7. The composition according to one of the claims 1 to 6, wherein said liquid plasticizing agent comprises moreover siliconates.

7. 8. The composition according to claim 1, wherein the alkaline silicates are chosen in the group of sodium 20 silicate, potassium silicate and lithium silicate, said composition being characterized by the fact that the weight ratio silica/sodium or potassium or lithium is higher than 3. 80568 -219. The composition according to one of the claims 1 to 8, wherein the setting reagent comprises one or more of the following products: fluosilicate of zinc, of sodium, of calcium, of magnesium or of barium; calcium-, sodium-, 5 potassium-, magnesium- or ammonium chloride; powdered boric acid; zinc-, copper-, ammonium- or barium-sulphate; calcium-, ammonium-, sodium- or potassium-phosphate.

8. 10. Method of fabricating a binder from a composition according to one of the claims 1 to 9, wherein both parts 10 of said composition are mixed before use, the amount of setting reagent remaining below 10% of the weight of silicate.

9. 11. Method of fabricating a binder from a composition according to one of the claims 1 to 9, wherein both parts 15 of said composition are projected separately and simultaneously, the amount of setting agent being comprised between 5 and 25% of the weight of silica.

10. 12. Method of fabricating a binder from a composition according to one of the claims 1 to 9, wherein both parts 20 of said composition are projected separately and one after the other, the amount of setting agent being comprised between 5 and 25% of the weight of silica.

11. 13. An adhesive, incombustible and waterproof binder composition substantially as hereinbefore described with 505S8 -22reference to the examples.

12. 14. A method of fabricating a binder substantially as hereinbefore described with reference to the examples