SURFACE-MODIFIED GLASS FIBERS FOR REINFORCING CONCRETE, AND METHOD FOR PRODUCING SAME

Abstract

The invention pertains to the fields of chemistry and construction and relates to surface-modified glass fiber for reinforcing concrete, such as those which can be used in textile-reinforced concrete (textile concrete), for example. The object of the present invention is to provide surface-modified glass fibers for reinforcing concrete, which glass fibers are at least substantially protected against an alkaline attack caused by the calcium hydroxides released during the cement reaction and/or dissolution and leaching processes generated thereby. The object is attained with surface-modified glass fibers for reinforcing concrete which are at least partially covered at least with a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and/or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and/or with a hydrolysis-stable and alkali-resistant polyelectrolyte complex and coupled to the glass fiber surface via a (polyelectrolyte) complex formation process by means of ionic bonding, with the hydrolysis-stable and alkali-resistant polyelectrolyte complex A thereby being formed, wherein at least one additional (co)polymer at least partially covers the polyelectrolyte complex A and is coupled with the polyelectrolyte A via ionic and/or covalent bonds.

Claims

1. Surface-modified glass fibers for reinforcing concrete which are at least partially covered at least with a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and/or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and/or with a hydrolysis-stable and alkali-resistant polyelectrolyte complex and coupled to the glass fiber surface via a (polyelectrolyte) complex formation process by means of ionic bonding, with the hydrolysis-stable and alkali-resistant polyelectrolyte complex A thereby being formed, wherein at least one additional (co)polymer at least partially covers the polyelectrolyte complex A and is coupled with the polyelectrolyte A via ionic and/or covalent bonds.

2. The surface-modified glass fibers according to claim 1 in which a hydrolysis-stable and alkali-resistant polyelectrolyte complex A is present which has been created by a (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant cationic polyelectrolytes; and/or by a (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures; and/or by a (polyelectrolyte) complex formation of the glass fiber surface with hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges, which polyelectrolyte complexes have been produced before being applied to the glass fiber surface.

3. The surface-modified glass fibers according to claim 1 in which the hydrolysis-stable and alkali-resistant polyelectrolyte complex A was formed on the glass fiber surface and covers the glass fiber surface completely or essentially completely, and/or the additional (co)polymer covers the polyelectrolyte complex A completely or essentially completely.

4. The surface-modified glass fibers according to claim 1 in which the following are present as hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture: polyethyleneimine (linear and/or branched) and/or copolymers; and/or polyallylamine and/or copolymers; and/or poly(diallyldimethylammonium chloride) (polyDADMAC) and/or copolymers; and/or polyvinylamine and/or copolymers; and/or polyvinylpyridine and/or copolymers; and/or poly(amide-amine) and/or copolymers; and/or cationically modified poly(meth)acrylate(s) and/or copolymers; and/or cationically modified poly(meth)acrylamide(s) with amino groups, and/or copolymers; and/or cationically modified maleimide copolymer(s), produced from maleic acid (anhydride) copolymer(s) and (N,N-dialkylaminoalkylene)amine(s), wherein alternating maleic acid (anhydride) copolymers are preferably used; and/or cationically modified itaconic imide (co)polymer(s), produced from itaconic acid (anhydride) (co)polymer(s) and (N,N-dialkylaminoalkylene)amine(s).

5. The surface-modified glass fibers according to claim 1 in which the following are present as functionalities on the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture: unmodified primary and/or secondary and/or tertiary amino groups that do not have substituents on the amine nitrogen atom with an additional reactive and/or activatable functional group and/or olefinically unsaturated double bond, and/or quaternary ammonium groups which do not have substituents on the nitrogen atom with an additional reactive and/or activatable functional group and/or olefinically unsaturated double bond, and/or have amino groups and/or quaternary ammonium groups which are at least partially chemically modified on the nitrogen atom via alkylation reactions, with at least one additional reactive and/or activatable functional group and/or at least one olefinically unsaturated double bond, and/or have amino groups and/or quaternary ammonium groups and amide groups which are chemically modified via acylation reactions of amino groups to amide, with at least one additional reactive and/or activatable functional group and/or at least one olefinically unsaturated double bond.

6. The surface-modified glass fibers according to claim 1 in which at least one anionic polyelectrolyte or one anionic polyelectrolyte mixture without and/or with at least one additional reactive and/or activatable functional group different from the anionic group and/or with at least one olefinically unsaturated double bond are present as functionalities on the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture attached to the glass fiber surface.

7. The surface-modified glass fibers according to claim 6 in which the following are present as anionic polyelectrolyte or anionic polyelectrolyte mixture: (a) (meth)acrylic acid copolymers which are present without and/or with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of the (meth)acrylic acid group, and which are preferably water-soluble, and/or (b) modified maleic acid (anhydride) copolymers which are preferably present in the acid and/or monoester and/or monoamide and/or water-soluble imide form, and/or which are present without and/or with residual anhydride groups, and/or which are present without and/or with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of maleic acid (anhydride) groups, and which are preferably water-soluble, and/or (c) modified itaconic acid (anhydride) (co)polymers which are preferably present in the acid and/or monoester and/or monoamide and/or water-soluble imide form, and/or which are present without and/or with residual anhydride groups, and/or which are present without and/or with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of itaconic acid (anhydride) groups, and which are preferably water-soluble, and/or (d) modified fumaric acid copolymers which are preferably present in the acid and/or monoester and/or monoamide form, and/or which are present without and/or with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and or which are present with at least one additional reactive and/or activatable functional group and/or at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of fumaric acid groups, and which are preferably water-soluble, and/or (e) anionically modified (meth)acrylamide (co)polymers which are present without and/or with at least one additional reactive and/or functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of the preferably (meth)acrylamide group, and which are preferably water-soluble, and/or (f) sulfonic acid (co)polymers, such as for example styrenesulfonic acid (co)polymers and/or vinylsulfonic acid (co)polymers in acid and/or salt form, which are present with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or at least one olefinically unsaturated double bond that are coupled via a polymer-analogous reaction/modification of sulfonic acid groups, such as via sulfonic acid amide groups for example, and which are preferably water-soluble, and/or (g) (co)polymers with phosphonic acid groups and/or phosphonate groups, which are for example present such that they are bonded as aminomethylphosphonic acid and/or aminomethylphosphonate and/or amidomethylphosphonic acid and/or amidomethylphosphonate, and/or which are present with at least one additional reactive and/or activatable functional group that was introduced via the copolymerization, and/or which are present with at least one additional reactive and/or activatable functional group and/or with at least one olefinically unsaturated double bond that are coupled via a polymer-analogous (co)polymer reaction/modification, and which are preferably water-soluble.

8. The surface-modified glass fibers according to claim 1 in which the hydrolysis-stable and alkali-resistant cationic polyelectrolytes or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture has a molecular weight under 50,000 dalton, preferably in the range between 400 Da and 10,000 dalton.

9. The surface-modified glass fibers according to claim 1 in which at least one at least difunctional and/or difunctionalized oligomeric and/or macromolecular (co)polymer with functional groups and/or olefinically unsaturated double bonds are present as additional (co)polymer.

10. The surface-modified glass fibers according to claim 9 in which thermoplastics and/or thermosets and/or elastomers are present as additional (co)polymer.

11. The surface-modified glass fibers according to claim 9 in which polyester resins (UP resins), vinyl ester resins and epoxy resins are present as thermosetting (co)polymers, and polyurethane, polyamide and polyolefins, such as polyethylene or polypropylene, and PVC are present as thermoplastic co(polymers), wherein the polyolefins are present such that they are grafted with (meth)acrylic acid derivatives and/or maleic anhydride.

12. Reinforcing materials for textile concrete with surface-modified glass fibers in which a hydrolysis-stable and alkali-resistant polyelectrolyte complex A is present in an at least partially covering manner on glass fiber surfaces without sizing material and silane, which polyelectrolyte complex comprises functional groups and/or olefinically unsaturated double bonds, and which are present such that they are coupled via chemically covalent bonds with additional (co)polymers after a reaction with functional groups and/or olefinically unsaturated double bonds.

13. The reinforcing materials for textile concrete with surface-modified glass fibers according to claim 12 in which at least one at least difunctional and/or difunctionalized oligomeric and/or macromolecular (co)polymer with functional groups and/or olefinically unsaturated double bonds are present as additional (co)polymers.

14. The reinforcing materials for textile concrete with surface-modified glass fibers according to claim 12 in which thermoplastics and/or thermosets and/or elastomers are present as additional (co)polymer.

15. The reinforcing materials for textile concrete with surface-modified glass fibers according to claim 12 in which amino groups, preferably primary and/or secondary amino groups, and/or quaternary ammonium groups are present as functionalities of the adsorbed hydrolysis-stable cationic polyelectrolyte(s) coupled via ionic bonds.

16. A method for producing surface-modified glass fibers, in which method a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and/or a hydrolysis-stable alkali-resistant cationic polyelectrolyte mixture and/or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges is applied from an aqueous solution at a concentration of maximally 5 wt % to the glass fiber surfaces in an at least partially covering manner during or after the production of glass fibers, wherein hydrolysis-stable and alkali-resistant cationic polyelectrolytes and/or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures with a molecular weight under 50,000 dalton and/or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges are used, and at least one additional (co)polymer is subsequently applied in an at least partially covering manner to the hydrolysis-stable and alkali-resistant polyelectrolyte complex A created on the glass surface.

17. The method according to claim 16 in which polyelectrolytes which are not subsequently alkylated and/or acylated and/or sulfamidated after production are used as hydrolysis-stable and alkali-resistant cationic polyelectrolytes, or polyelectrolyte mixtures that are not subsequently alkylated and/or acylated and/or sulfamidated after production are used as hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures.

18. The method according to claim 16 in which the following are used as hydrolysis-stable and alkali-resistant unmodified cationic polyelectrolyte, as a pure substance or substances or in a mixture, preferably dissolved in water: polyethyleneimine (linear and/or branched) and/or copolymers; and/or polyallylamine and/or copolymers; and/or poly(diallyldimethylammonium chloride) (polyDADMAC) and/or copolymers; and/or polyvinylamine and/or copolymers; and/or polyvinylpyridine and/or copolymers; and/or poly(amide-amine) and/or copolymers; and/or cationically modified poly(meth)acrylate(s) and/or copolymers; and/or cationically modified poly(meth)acrylamide(s) with amino groups, and/or copolymers; and/or cationically modified maleimide copolymer(s), produced from maleic acid (anhydride) copolymer(s) and (N,N-dialkylaminoalkylene)amine(s), wherein alternating maleic acid (anhydride) copolymers are preferably used; and/or cationically modified itaconic imide (co)polymer(s), produced from itaconic acid (anhydride) (co)polymer(s) and (N,N-dialkylaminoalkylene)amine(s).

19. The method according to claim 16 in which hydrolysis-stable and alkali-resistant cationic polyelectrolytes and/or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures and/or hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges are used at a concentration of maximally 5 wt % in water or in water with the addition of acid, such as carboxylic acid, for example formic acid and/or acetic acid, and/or mineral acid, without additional sizing material or sizing material components and/or silanes.

20. The method according to claim 16 in which hydrolysis-stable and alkali-resistant cationic polyelectrolytes which are not subsequently alkylated and/or acylated and/or sulfamidated after production and/or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures that are not subsequently alkylated and/or acylated and/or sulfamidated after production are used at a concentration of <2 wt %, and particularly preferably at 0.8 wt %.

21. The method according to claim 16 in which hydrolysis-stable and alkali-resistant cationic polyelectrolytes and/or hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixtures with a molecular weight under 50,000 dalton, preferably in the range between 400 dalton and 10,000 dalton, are used.

22. The method according to claim 16 in which a modified hydrolysis-stable and alkali-resistant cationic polyelectrolyte and/or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture that is/are partially alkylated and/or acylated and/or reacted with carboxylic acid derivatives and/or sulfamidated in a subsequent reaction following production, and is/are thus equipped with a substituent having reactive and/or activatable groups for a coupling reaction, is/are then, having the reactive and/or activatable groups of the covalently coupled substituent, reacted with additional materials to form a composite material via at least one functional group and/or via at least one olefinically unsaturated double bond without crosslinking of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture.

23. The method according to claim 16 in which the partial alkylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is achieved, with substituents having reactive groups thereby being introduced, through haloalkyl derivatives and/or (epi)halohydrin compounds and/or epoxy compounds and/or compounds which enter into a Michael-analogous addition, advantageously such as acrylates and/or acrylonitrile with amines.

24. The method according to claim 16 in which the partial acylation of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or of the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture is achieved, with substituents having reactive groups thereby being introduced, through carboxylic acids and/or carboxylic acid halides and/or carboxylic acid anhydrides and/or carboxylic acid esters and/or diketenes, or if a quasi-acylation is achieved through isocyanates and/or urethanes and/or carbodiimides and/or uretdiones and/or allophanates and/or biurets and/or carbonates.

25. The method according to claim 16 in which the hydrolysis-stable and alkali-resistant cationic polyelectrolytes and/or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and/or the hydrolysis-stable and alkali-resistant polyelectrolyte complexes with an excess of cationic charges are used such that they are dissolved in water, preferably as an ammonium compound, wherein in the case of primary and/or secondary and/or tertiary amino groups carboxylic acid(s) and/or mineral acid(s) are added to the aqueous solution to convert the amino groups into the ammonium form.

26. The method according to claim 16 in which modified glass fiber surfaces that are at least partially, and preferably completely, covered at least with a hydrolysis-stable and alkali-resistant cationic polyelectrolyte or a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and/or a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic or anionic charges are, directly following the production and coating/surface modification thereof and/or at a later point, reacted with additional materials, with chemically covalent bonds thereby being formed.

27. The method according to claim 26 in which the modified glass fiber surfaces are wound and/or intermediately stored as roving and are subsequently reacted with additional materials, with chemically covalent bonds thereby being formed.

28. The method according to claim 26 in which the hydrolysis-stable and alkali-resistant cationic polyelectrolyte or the hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and/or the hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic or anionic charges comprises reactive groups in the form of functional groups and/or olefinically unsaturated double bonds, which groups are reacted with functionalities of the additional materials, with chemically covalent bonds thereby being formed.

29. The method according to claim 16 in which an aqueous solution with a concentration of maximally 5 wt % of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte and/or of a hydrolysis-stable and alkali-resistant cationic polyelectrolyte mixture and/or of a hydrolysis-stable and alkali-resistant polyelectrolyte complex with an excess of cationic charges is applied in an at least partially covering manner to commercially produced and sized glass fiber surfaces, or to glass fiber surfaces without sizing material and silane, wherein cationic polyelectrolytes or cationic polyelectrolyte mixtures with a molecular weight under 50,000 dalton are used.

Description

EXAMPLE 1

[0240] In the glass silk spinning system, E-glass fibers with 100 tex are spun and are surface-modified, wound and dried (glass roving material 1) in the sizing station, which is filled with an aqueous 1.0% PEI solution as a cationic polyelectrolyte (PEI=polyethyleneimine, Aldrich, M.sub.n=10,000).

[0241] The pH-dependent zetapotential measurements on the glass fibers treated in such a manner verify the adsorption of PEI at the surface.

[0242] The detection of coupled amino groups at the surfaces and verification of the uniform coverage of the glass fibers was conducted using the fluorescamine method.

EXAMPLE 1A: SURFACE SEALING WITH EPOXY

[0243] The dried, surface-modified glass roving material 1 is pulled through an impregnation bath with hot-curing epoxy and is thus impregnated with the epoxy resin for the surface treatment, the excess adherent epoxy is separated off by a routing through rubber rollers and, following the shaping, this epoxy-treated glass fiber roving material is then routed through a heating section in which the material is processed such that it is partially crosslinked into a materially bonded, compact pre-preg strand and, after a cooling section, is wound (pre-preg strand material 1). A materially bonded pre-preg strand material 1 surface-modified with a thicker epoxy resin layer is in this form further processed as reinforcing material for textile concrete as follows: The pre-preg strand material 1 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This pre-preg reinforcing material is cured for 1 hour at 165 C. under moderate pressure, wherein during the consolidation process the partially crosslinked epoxy resin of these strands forms at the intersecting points a bond that is stable for handling. After the cooling, a grid network is available as reinforcing material for use in textile cement.

EXAMPLE 1B: SURFACE COATING WITH THERMOPLASTIC POLYURETHANE

[0244] The pre-preg strand material 1 produced in Example 1a from modified glass fiber roving with an epoxy resin seal is in a second stage routed through a nozzle and coated/enveloped with a melt of thermoplastic polyurethane (TPU). During the coating, in addition to the thermal curing of the partially cured epoxy resin, coupling reactions take place in the interface between the epoxy resin and TPU. With the formation of covalent bonds, the TPU is present such that it is chemically coupled with the epoxy as a material bond. After a cooling section, the TPU strand material 1 is wound.

[0245] This TPU strand material 1 is further processed as reinforcing material for textile concrete as follows: The TPU strand material 1 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 30 minutes at 190 C. under moderate pressure, wherein via a fusing of the TPU the strands form at the intersecting points a bond that is stable for handling. After the cooling, this grid network is used as reinforcing material in textile concrete.

EXAMPLE 1C: SURFACE-COATING WITH POLYPROPYLENE GRAFTED WITH MALEIC ANHYDRIDE

[0246] The pre-preg strand material 1 produced in Example 1a is in a second stage routed through a nozzle and coated/enveloped with a melt of polypropylene grafted with maleic anhydride (PP-gMAn). During the coating, in addition to the thermal curing of the partially cured epoxy resin, coupling reactions take place in the interface between the epoxy resin and PP-gMAn. With the formation of covalent bonds, the PP-gMAn is present as a chemical material bond with the epoxy resin. After a cooling section, the PP-gMAn strand material 1 is wound.

[0247] This PP-gMAn strand material 1 is further processed as reinforcing material for textile concrete as follows:

[0248] The PP-gMAn strand material 1 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 30 minutes at 160 C. under moderate pressure, wherein via a fusing of the PP-gMAn the strands form at the intersecting points a bond that is sufficiently stable for handling. After the cooling, this grid network is used as reinforcing material in textile concrete.

EXAMPLE 1D: SURFACE SEALING WITH UP RESIN AND COATING WITH PP-GMAN

[0249] The dried, surface-modified glass roving material 1 is pulled through an impregnation bath with UP resin, to which 5 mass % glycidyl methacrylate (GMA) was added, and in this manner impregnated with the UP resin for surface treatment. The excess UP resin is separated off by a routing through rubber rollers and, following the shaping, this UP resin-treated glass fiber roving material is then routed through a heating section in which the material is processed such that it is crosslinked into a materially bonded, compact strand and, after a cooling section, is wound.

[0250] In a second process step, the strand is routed through a nozzle in which the strand is coated/enveloped with a melt of polypropylene grafted with maleic anhydride (PP-gMAn). During the coating, coupling reactions take place in the interface between the UP resin modified with GMA and the PP-gMAn. With the formation of covalent bonds, the PP-gMAn is present as a chemical material bond with the UP resin surface. After a cooling section, the UP-PP-gMAn strand material 1 is wound.

[0251] This UP-PP-gMAn strand material 1 is in this form further processed as reinforcing material for textile concrete as follows:

[0252] The UP-PP-gMAn strand material 1 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 20 minutes at 160 C. under moderate pressure, wherein via a fusing of the PP-gMAn the strands form at the intersecting points a bond that is sufficiently stable for handling. After the cooling, this grid network is used as reinforcing material in textile concrete.

EXAMPLE 1E: SURFACE SEALING WITH PP-GMAN

[0253] The dried, surface-modified glass roving material 1 is directly coated with a low-viscosity polypropylene grafted with maleic anhydride (PP-gMAn) in an infiltrative and enveloping manner via pultrusion and processed into a narrow tape. During the infiltration and coating, coupling reactions take place in the interface between the glass fibers of the glass roving material 1 and the PP-gMAn. With the formation of covalent bonds, the PP-gMAn is present as a chemical material bond with the glass fibers via the polyelectrolyte complex A. After a cooling section, the material is wound as narrow PP-gMAn tape material 1.

[0254] This PP-gMAn tape material 1 is in this form further processed as reinforcing material for textile concrete as follows:

[0255] The PP-gMAn tape material 1 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 15 minutes at 160 C. under moderate pressure, wherein via a fusing of the PP-gMAn the tapes form at the intersecting points a bond that is sufficiently stable for handling. After the cooling, this grid network is used as reinforcing material in textile concrete.

EXAMPLE 1F: SURFACE SEALING WITH PP-GMAN AND COATING WITH PP

[0256] The dried, surface-modified glass roving material 1 is (as in Example 1e) directly coated with a low-viscosity polypropylene grafted with maleic anhydride (PP-gMAn) in an infiltrative and enveloping manner via pultrusion. During the infiltration and coating, coupling reactions take place in the interface between the glass fibers of the glass roving material 1 and the PP-gMAn. With the formation of covalent bonds, the PP-gMAn is present as a chemical material bond with the glass fibers via the polyelectrolyte complex A. In a second coating system, this strand is then routed through a nozzle and enveloped with a viscous PP material, wherein the two polypropylenes fuse in the interface. After a cooling section, the PP-gMAn-PP strand material 1 is wound.

[0257] This PP-gMAn-PP strand material 1 is in this form further processed as reinforcing material for textile concrete as follows:

[0258] The PP-gMAn-PP strand material 1 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 30 minutes at 170 C. under moderate pressure, wherein via a fusing of the PP-materials of the outer layer the strands form at the intersecting points a bond that is sufficiently stable for handling. After the cooling, this grid network is used as reinforcing material in textile concrete.

EXAMPLE 2

[0259] E-glass fibers with 100 tex are spun in the glass silk spinning system and are surface-modified, wound and dried in the sizing station, which is filled with an aqueous 0.25% polyDADMAC solution as a cationic polyelectrolyte (polyDADMAC=poly(diallyldimethylammonium chloride), Aldrich, Mw<100,000, very low-molecular).

[0260] The pH-dependent zetapotential measurements on the glass fibers treated in such a manner verify the adsorption of polyDADMAC onto the surface.

[0261] Since as a strong cationic polyelectrolyte the polyDADMAC has only quaternary ammonium groups and otherwise no additional olefinically unsaturated double bonds and/or reactive functional groups that are relevant for chemical radical reactions, addition reactions and substitution reactions, direct reactions are not possible. In this case, for further modification, the glass fiber surface-modified with polyDADMAC is treated with an anionic polyelectrolyte that has an additional functional group, which is different from the anionic group, for the chemical coupling and/or compatibilization with the matrix material or at least one component of the matrix material, and a glass fiber surface/polyDADMAC/anionic polyelectrolyte polyelectrolyte complex is formed. This modification variant via the polyelectrolyte complex formation process is preferably used for glass fibers surface-modified with polyDADMAC. For this reason, in an apparatus technically analogous to the sizing station, the glass fiber roving surface-modified with polyDADMAC is, via rewinding by means of a roller, in a second stage treated with a 0.5% propene-alt-maleic acid-N,N-dimethylamino-n-propyl-monoamide solution (produced from propene-alt-maleic anhydride via reaction with N,N-dimethylamino-n-propylamine in water at a 1 to 0.4 ratio of anhydride to primary amino group) for the formation of the glass fiber surface/polyDADMAC/anionic polyelectrolyte polyelectrolyte complex and is wound and dried (glass roving material 2).

EXAMPLE 2A: SURFACE SEALING WITH EPOXY AND COATING WITH PA12

[0262] The dried, surface-modified glass roving material 2 is pulled through an impregnation bath with hot-curing epoxy and is thus impregnated with the epoxy resin for surface treatment, the excess adherent epoxy is separated off by a routing through rubber rollers and, following the shaping, this epoxy-treated glass fiber roving material is then routed through a heating section in which the material is processed such that it is partially crosslinked into a materially bonded pre-preg strand and, after a cooling section, is wound (pre-preg strand material 2).

[0263] In a second stage, this pre-preg strand material 2 is routed through a nozzle and coated/enveloped with a melt of PA12. During the coating, in addition to the thermal curing of the partially cured epoxy resin, coupling reactions take place in the interface between the epoxy resin and PA12.

[0264] With the formation of covalent bonds, the PA12 is present such that it is chemically coupled with the epoxy as a material bond. After a cooling section, the PA12 strand material 2 is wound.

[0265] This PA12 strand material 2 is further processed as reinforcing material for textile concrete as follows:

[0266] The PA12 strand material 2 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 30 minutes at 190 C. under moderate pressure, wherein via a fusing of the PA12 the strands form at the intersecting points a bond that is stable for handling. After the cooling, this grid network is used as reinforcing material in textile concrete.

EXAMPLE 2B: SURFACE SEALING WITH UP RESIN

[0267] The dried, surface-modified glass roving material 2 is pulled through an impregnation bath with UP resin, to which 5 mass % glycidyl methacrylate was added, and in this manner impregnated with the UP resin for surface treatment. The excess adherent UP resin is separated off by a stripper. Following the shaping, this UP resin-treated glass fiber roving material is then routed through a heating section in which the material is processed such that it is partially crosslinked into a materially bonded, compact strand and, after a cooling section, is wound (pre-preg strand material 3).

[0268] This pre-preg strand material 3 is further processed as reinforcing material for textile concrete as follows:

[0269] The pre-preg strand material 3 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 20 minutes at 180 C. under moderate pressure, wherein during the consolidation process the partially crosslinked UP resin of these strands forms at the intersecting points a bond that is stable for handling. After the cooling, a grid network is available as reinforcing material for use in textile cement.

EXAMPLE 2C: SURFACE COATING WITH ABS

[0270] In a second process step, the pre-preg strand material 3 is routed through a nozzle and sheathed with an ABS melt. During the coating, coupling reactions take place in the interface between the partially crosslinked UP resin and the ABS, and the UP resin continues to cure. With the formation of covalent bonds, the ABS is present as a chemical material bond with the UP resin surface. After a cooling section, the ABS-UP resin strand material 2 is wound.

[0271] This ABS-UP resin strand material 2 is further processed as reinforcing material for textile concrete as follows:

[0272] The ABS-UP strand material 2 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 15 minutes at 200 C. under moderate pressure, wherein the UP resin of these strands cures and, via a fusing of the ABS, the strands form at the intersecting points a bond that is stable for handling. After the cooling, a grid network is available as reinforcing material for use in textile cement.

EXAMPLE 3

[0273] Analogously to Example 1, E-glass fibers with 150 tex are spun in the glass silk spinning system and are surface-modified and wound (glass roving material 3) in the sizing station, which is filled with an aqueous 1.0% PEI/polyallylamine solution as a cationic polyelectrolyte (PEI=polyethyleneimine, Aldrich, M.sub.n=10,000, polyallylamine, Aldrich, M.sub.w15,000; PEI/polyallylamine=2/1).

[0274] The pH-dependent zetapotential measurements on the glass fibers treated in such a manner verify the adsorption of PEI/polyallylamine at the surface.

[0275] The detection of coupled amino groups at the surfaces and verification of the uniform coverage of the glass fibers was conducted using the fluorescamine method.

EXAMPLE 3A: SEALING WITH EPOXY AND COATING WITH PA6

[0276] The dried, surface-modified glass roving material 3 is pulled through an impregnation bath with hot-curing resin and in this manner impregnated with the epoxy resin for surface treatment. The excess adherent epoxy is separated off by a routing through rubber rollers and, following the shaping, this epoxy-treated glass fiber roving material is then routed through a heating section in which the material is processed such that it is partially crosslinked into a materially bonded, compact pre-preg strand and, after a cooling section, is wound (pre-preg strand material 3).

[0277] In a second stage, this pre-preg strand material 3 is routed through a nozzle and coated/enveloped with a melt of PA6. During the coating, in addition to the thermal curing of the partially cured epoxy resin, coupling reactions take place in the interface between the epoxy resin and PA6. With the formation of covalent bonds, the PA6 is present such that it is chemically coupled with the epoxy as a material bond. After a cooling section, the PA6 strand material 3 is wound.

[0278] This PA6 strand material 3 is further processed as reinforcing material for textile concrete as follows:

[0279] The PA6 strand material 3 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 10 minutes at 230 C. under moderate pressure, wherein via a fusing of the PA6 the strands form at the intersecting points a bond that is stable for handling. After the cooling, this grid network is used as reinforcing material in textile concrete.

EXAMPLE 3B: SEALING WITH EPOXY AND COATING WITH PE-COAAC IONOMER

[0280] The dried, surface-modified glass roving material 3 is (as in Example 3a) processed into a pre-preg strand material 3.

[0281] In a second stage, this pre-preg strand material 3 is routed through a nozzle and coated/enveloped with a melt of PE-coAAc ionomer (polyethylene-co-acrylic acid ionomer, Surlyn, DuPont). During the coating, in addition to the thermal curing of the partially cured epoxy resin, coupling reactions take place in the interface between the epoxy resin and PE-coAAc ionomer. With the formation of covalent bonds, the PE-coAAc ionomer is present such that it is chemically coupled with the epoxy as a material bond. After a cooling section, the PE-coAAc strand material 3 is wound.

[0282] This PE-coAAc strand material 3 is further processed as reinforcing material for textile concrete as follows:

[0283] The PE-coAAc strand material 3 is cut for a demonstrator trial into strands of 0.5 m, and is placed, arranged crosswise at distances of approx. 4 cm, on a 2-mm thick HNBR plate in a heatable press, onto which plate a 0.125-mm thick PTFE shell foil was placed as a separating layer. A second 0.125-mm thick PTFE shell foil, likewise as a separating layer, and a 2-mm thick vulcanized HNBR plate are positioned thereon. This reinforcing material is pressed for 15 minutes at 120 C. under moderate pressure, wherein via a fusing of the PE-coAAc ionomer the strands form at the intersecting points a bond that is stable for handling. After the cooling, this grid network is used as reinforcing material in textile concrete.