WO2002090287A1 - Waterproofed cementitious compositions and method of making the same - Google Patents

Waterproofed cementitious compositions and method of making the same Download PDF

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Publication number
WO2002090287A1
WO2002090287A1 PCT/EP2002/004940 EP0204940W WO02090287A1 WO 2002090287 A1 WO2002090287 A1 WO 2002090287A1 EP 0204940 W EP0204940 W EP 0204940W WO 02090287 A1 WO02090287 A1 WO 02090287A1
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WO
WIPO (PCT)
Prior art keywords
weight
group
general formula
carbon atoms
emulsion
Prior art date
Application number
PCT/EP2002/004940
Other languages
French (fr)
Inventor
Michael Langdon
Rowland Arthur Jones
Original Assignee
Construction Research & Technology 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 Construction Research & Technology Gmbh filed Critical Construction Research & Technology Gmbh
Priority to EP02724306A priority Critical patent/EP1390318A1/en
Publication of WO2002090287A1 publication Critical patent/WO2002090287A1/en
Priority to IL153588A priority patent/IL153588A/en
Priority to NO20030070A priority patent/NO20030070L/en

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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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/42—Organo-silicon compounds
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients

Definitions

  • This invention relates to the waterproofing of porous cementitious materials and to admixtures for waterproofing.
  • cementitious materials such as cement and concrete and various artificial building stones based on these are frequently made into walls, floors, roofs and the like, where they will be exposed to water. As such materials are always inherently porous, water can penetrate them. Although appropriate formulation can do much to reduce this inherent porosity, it can never completely get rid of it. There is therefore a substantial industry that seeks to provide waterproofing to such cementitious surfaces.
  • the internal methods involved adding a waterproofing substance to a fluid cementitious mix before hardening.
  • the materials that have been most commercially successful in this regard have been known water-repellent, fatty acid-based materials, typically stearates and oleates. However, relatively large quantities of such materials are needed.
  • the external treatments have involved coating the surface of the hardened cementitious material with a waterproofing substance.
  • a waterproofing substance contain materials that are highly water repellent and are of low viscosity, to allow them to penetrate into the cementitious material.
  • Particularly successful types of waterproofing materials are those based on organosilicon materials. Aqueous emulsions are most frequently encountered, but solvent- based preparations and even organosilicon materials that are inherently sufficiently fluid have also been used. Multiple applications are needed for best effect, and the cost of applying such treatment to large structures can be very high.
  • organosilicon materials as admixtures to cementitious mixes, in an attempt to utilise the good waterproofing properties of the surface- applied materials to the convenience of use of the stearates and oleates.
  • the materials used have been aqueous hydroly sable silane emulsions.
  • the invention therefore provides a method of conferring water impermeability on a hardened cementitious composition which is formed from a fluid cementitious mix, by the addition to the mix of an aqueous emulsion of organosilicon material, which material comprises from 0.25-4.5% by weight of the emulsion of an alkoxysilane and from 0.1-2.0% of an alkoxysiloxane.
  • the invention also provides a waterproof hardened cementitious composition comprising internally an alkoxysilane and an alkoxysiloxane, which had been added as an admixture to a cementitious mix from which the hardened composition was formed.
  • the emulsion is one that contains
  • R ⁇ is an alkyl group with 3 to 12 carbon atoms; and R 2 is a methyl or ethyl group;
  • R 3 is an alkyl group with 1 to 6 carbon atoms, a is 0.8 to 1.2 and b is 0.2 to 1.2;
  • some of the water may be replaced by from 0.001-0.5% by weight of an emulsifier, 0.001% by weight of filler with an effective surface area of at least 40M 2 /g.
  • the emulsion contains
  • R 1 is an alkyl group with 1 to 16 carbon atoms
  • R 2 is an alkyl group with 1 to 4 carbon atoms
  • R 2 has the meaning already given, and R 3 is an aminoalkyl group with 1 to 6 carbon atoms or a group of the general formula
  • n is a whole number from 1 to 5
  • the ratio of bl to b2 being such that more than 1 and up to 3 OR 2 groups of compound bl correspond to one SiOH group of compound b2,
  • materials suitable for preparing aqueous emulsions for use in this invention include products such as RHEOMIX® 790 ex Feb MBT. Such materials typically have solids contents of 30% or more and have to be diluted to make a composition for use in this invention.
  • the emulsions are added to a cementitious mix at a rate of from 0.1 - 2.0%, preferably from 0.5 - 1.5% by weight emulsion by weight of cement.
  • the hardened cementitious product containing the emulsion as admixture has a waterproofing performance that is noticeably superior to anything currently available.
  • a B C dosage (% by weight 1.8 NA 1.1 on cement) capillary 0.13 4.0 0.1 absorption (mg/mm 2 )
  • the stone according to the invention was superior to the stones which used stearate and sprayed siloxane.

Abstract

A method of conferring water impermeability on a hardened cementitious composition which is formed from a fluid cementitious mix, by the addition to the mix of an aqueous emulsion of organosilicon material, which material comprises from 0.25-4.5% by weight of the emulsion of an alkoxysilane and from 0.1-2.0% of an alkoxysiloxane.

Description

WATERPROOFED CEMENTITIOUS COMPOSITIONS AND METHOD OF MAKING THE SAME
This invention relates to the waterproofing of porous cementitious materials and to admixtures for waterproofing.
Cementitious materials such as cement and concrete and various artificial building stones based on these are frequently made into walls, floors, roofs and the like, where they will be exposed to water. As such materials are always inherently porous, water can penetrate them. Although appropriate formulation can do much to reduce this inherent porosity, it can never completely get rid of it. There is therefore a substantial industry that seeks to provide waterproofing to such cementitious surfaces. Up to now, there have been two alternative methods, internal and external. The internal methods involved adding a waterproofing substance to a fluid cementitious mix before hardening. The materials that have been most commercially successful in this regard have been known water-repellent, fatty acid-based materials, typically stearates and oleates. However, relatively large quantities of such materials are needed.
The external treatments have involved coating the surface of the hardened cementitious material with a waterproofing substance. Such substances contain materials that are highly water repellent and are of low viscosity, to allow them to penetrate into the cementitious material. Particularly successful types of waterproofing materials are those based on organosilicon materials. Aqueous emulsions are most frequently encountered, but solvent- based preparations and even organosilicon materials that are inherently sufficiently fluid have also been used. Multiple applications are needed for best effect, and the cost of applying such treatment to large structures can be very high.
More recently, it has been proposed to add organosilicon materials as admixtures to cementitious mixes, in an attempt to utilise the good waterproofing properties of the surface- applied materials to the convenience of use of the stearates and oleates. The materials used have been aqueous hydroly sable silane emulsions.
It has now been found that it is possible to give hardened cementitious materials enhanced water impermeability by use of particular organosilicon materials. The invention therefore provides a method of conferring water impermeability on a hardened cementitious composition which is formed from a fluid cementitious mix, by the addition to the mix of an aqueous emulsion of organosilicon material, which material comprises from 0.25-4.5% by weight of the emulsion of an alkoxysilane and from 0.1-2.0% of an alkoxysiloxane.
The invention also provides a waterproof hardened cementitious composition comprising internally an alkoxysilane and an alkoxysiloxane, which had been added as an admixture to a cementitious mix from which the hardened composition was formed.
Although such emulsions are well known for external application to porous cementitious surfaces for waterproofing, it is surprising to find that, not only do they work when added to fluid mixes as admixtures, but they also work exceptionally well, better than the same material externally applied.
In a preferred embodiment of the invention (hereinafter "preferment 1"), the emulsion is one that contains
1. 0.25 to 2.5% by weight of an alkoxysilane of the general formula
R1 -Si(OR2)3
wherein
Rα is an alkyl group with 3 to 12 carbon atoms; and R2 is a methyl or ethyl group;
2. 0.2 to 2% by weight of an alkoxysiloxane of the general formula
Ra 3-Si(OR2)b
Figure imgf000003_0001
wherein R3 is an alkyl group with 1 to 6 carbon atoms, a is 0.8 to 1.2 and b is 0.2 to 1.2; and
3. water to 100%.
More preferably, some of the water may be replaced by from 0.001-0.5% by weight of an emulsifier, 0.001% by weight of filler with an effective surface area of at least 40M2/g.
In another preferred embodiment (hereinafter "preferment 2"), the emulsion contains
a) 0.5 to 4.5% by weight of an alkoxysilane of the general formula
R1-Si-(OR2)3
wherein
R1 is an alkyl group with 1 to 16 carbon atoms, and R2 is an alkyl group with 1 to 4 carbon atoms,
b) 4.5 to 0.5% by weight of a mixture consisting of a
bl) silane of the general formula
R3-Si-(OR2)3
wherein
R2 has the meaning already given, and R3 is an aminoalkyl group with 1 to 6 carbon atoms or a group of the general formula
H2N-(CH2)x R4 -(CH2)y-, in which R represents an oxygen, sulphur, -NH- or -NH-CH2-CH -NH group and
x>2 and y>2, or a group of the general formula
(R O)3 Si-(CH2)X-NH-(CH2)X-,
wherein R2 and x are defined as above,
-CΛH2„-O-CH2-C: :CH2 or
O
Figure imgf000005_0001
n is a whole number from 1 to 5,
and
b2) is a polysiloxane of the general formula
Figure imgf000005_0002
wherein R is a methyl or phenyl group, with the proviso that at least 90% of the R groups are methyl groups, and m=20 to 250,
the ratio of bl to b2 being such that more than 1 and up to 3 OR2 groups of compound bl correspond to one SiOH group of compound b2,
c) 0.05 to 1% by weight of an O/W emulsifier or emulsifier mixture; and
d) water to 100%.
Commercially-available materials suitable for preparing aqueous emulsions for use in this invention include products such as RHEOMIX® 790 ex Feb MBT. Such materials typically have solids contents of 30% or more and have to be diluted to make a composition for use in this invention.
The emulsions are added to a cementitious mix at a rate of from 0.1 - 2.0%, preferably from 0.5 - 1.5% by weight emulsion by weight of cement.
The hardened cementitious product containing the emulsion as admixture has a waterproofing performance that is noticeably superior to anything currently available.
The invention is further described by reference to the following non-limiting example.
The materials used are as follows:
A. commercially-available aluminium stearate.
B. RHEOMIX® 790 emulsion, applied by spraying, according to manufacturer's instructions.
C. RHEOMIX® 790, diluted by adding 9 parts of water to 1 part of emulsion (to give a material according to preferment 1 above), and added as an admixture to the mix. The test material is Lancaster stone, an architectural cast stone. All of A,B and C are tried on the stone, A and C being added to samples of the mix used to make the stone and B being applied to a sample of the hardened stone by spraying. The actual quantity of B is not precisely known, but it is sprayed according to the manufacturer's instructions, at a rate of about 5m2/L. The stone samples are then tested according to a number of recognised British Standards. The results are as follows:
(a) Capillary absorption test (BS 1217). The maximum allowable is 1.0mg/mm2.
A B C dosage (% by weight 1.8 NA 1.1 on cement) capillary 0.13 4.0 0.1 absorption (mg/mm2)
It can be seen that the performance according to the invention (C) is equivalent to that of the stearate (A), considering the lower quantity used, and much superior to that of the surface- applied siloxane B.
(b) ISAT (Initial surface absorption) test. A maximum of 0.25ml/M2/10 min. according to BS 1881, and 0.10ml/TVΪ2/60 min according to BS 1217 are allowed.
(c) The same stone and the same admixtures in the same dosages were used. The results are as follows:
B
ISAT (10 min) 0.11 0.10 0
ISAT (60 min) 0.40 0.03 0
In this case, the stone according to the invention was superior to the stones which used stearate and sprayed siloxane.

Claims

Claims:
1. A method of conferring water impermeability on a hardened cementitious composition which is formed from a fluid cementitious mix, by the addition to the mix of an aqueous emulsion of organosilicon material, which material comprises from 0.25-4.5% by weight of the emulsion of an alkoxysilane and from 0.1-2.0% of an alkoxysiloxane.
2. A method according to claim 1 in which the emulsion is one which contains
1. 0.25 to 2.5% by weight of an alkoxysilane of the general formula
R1 -Si(OR2)3
wherein
Ri is an alkyl group with 3 to 12 carbon atoms; and R2 is a methyl or ethyl group;
2. 0.2 to 2% by weight of an alkoxysiloxane of the general formula
Ra 3-Si(OR2)b I
O4-(a+b) 2
wherein R3 is an alkyl group with 1 to 6 carbon atoms, a is 0.8 to 1.2 and b is 0.2 to 1.2; and
3. water to 100%.
3. A method according to claim 1, in which the emulsion contains a) 0.5 to 4.5% by weight of an alkoxysilane of the general formula
R^SHOR2^
wherein
R1 is an alkyl group with 1 to 16 carbon atoms, and R2 is an alkyl group with 1 to 4 carbon atoms,
b) 4.5 to 0.5% by weight of a mixture consisting of a
bl) silane of the general formula
R3-Si-(OR2)3
wherein
R2 has the meaning already given, and R3 is an aminoalkyl group with 1 to 6 carbon atoms or a group of the general formula
H2N-(CH2)X R4 -(CH2): y '
in which R4 represents an oxygen, sulphur, -NH- or -NH-CH2-CH2-
NH group and
x>2 and y>2; or a group of the general formula
(R2O)3 Si-(CH2)X-NH-(CH2)X-, wherein R and x are defined as above,
-C„BbB-O-CH2-CH 7— yCHa or
Figure imgf000010_0001
n is a whole number from 1 to 5,
and
b2) is a polysiloxane of the general formula
Figure imgf000010_0002
wherein R5 is a methyl or phenyl group, with the proviso that at least 90% of the R5 groups are methyl groups, and m=20 to 250,
the ratio of bl to b2 being such that more than 1 and up to 3 OR groups of compound bl correspond to one SiOH group of compound b2,
c) 0.05 to 1% by weight of an OAV emulsifier or emulsifier mixture; and d) water to 100%.
4. A method according to any one of claims 1-3, in which some of the water is replaced by from 0.001-0.5% by weight of an emulsifier, 0.001% by weight of filler with an effective surface area of at least 40M2/g.
5. A waterproof hardened cementitious composition comprising internally an alkoxysilane and an alkoxysiloxane which had been added to a cementitious mix from which the hardened composition was formed as an admixture by a method according to any one of claims 1-4.
PCT/EP2002/004940 2001-05-08 2002-05-03 Waterproofed cementitious compositions and method of making the same WO2002090287A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP02724306A EP1390318A1 (en) 2001-05-08 2002-05-03 Waterproofed cementitious compositions and method of making the same
IL153588A IL153588A (en) 2001-05-08 2002-12-22 Waterproofed cementitious compositions and method of making the same
NO20030070A NO20030070L (en) 2001-05-08 2003-01-07 Cement-containing compositions made waterproof and method of making the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0111145.9A GB0111145D0 (en) 2001-05-08 2001-05-08 Admixture
GB0111145.9 2001-05-08

Publications (1)

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Country Status (7)

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EP (1) EP1390318A1 (en)
GB (1) GB0111145D0 (en)
IL (1) IL153588A (en)
NO (1) NO20030070L (en)
WO (1) WO2002090287A1 (en)
YU (1) YU703A (en)
ZA (1) ZA200300162B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007009935A2 (en) 2005-07-15 2007-01-25 Dow Corning Corporation Hydrophobing minerals and filler materials
DE102008063965A1 (en) 2008-12-19 2010-06-24 Evonik Goldschmidt Gmbh Hydrophobic cementitious compositions
DE202008018525U1 (en) 2008-12-19 2016-02-01 Evonik Degussa Gmbh Hydrophobic cementitious compositions

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPH0570203A (en) * 1991-09-10 1993-03-23 Shin Etsu Chem Co Ltd Cement composition containing alkoxysilanes for extrusion molding
US5556915A (en) * 1991-12-20 1996-09-17 Toyo Ink Manufacturing Co., Ltd. Water-based organosilicon composition
US5702509A (en) * 1995-12-22 1997-12-30 Minnesota Mining And Manufacturing Company Masonry treatment composition

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GB9605706D0 (en) * 1996-03-19 1996-05-22 Dow Corning Method for hydrophobing gypsum
GB9614978D0 (en) * 1996-07-17 1996-09-04 Dow Corning Gypsum mixture containing hydrophobic additive and method for hydrophobing gypsum
US6403163B1 (en) * 2000-06-27 2002-06-11 Chemrex, Inc. Method of treating surfaces with organosilicon water repellent compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570203A (en) * 1991-09-10 1993-03-23 Shin Etsu Chem Co Ltd Cement composition containing alkoxysilanes for extrusion molding
US5556915A (en) * 1991-12-20 1996-09-17 Toyo Ink Manufacturing Co., Ltd. Water-based organosilicon composition
US5702509A (en) * 1995-12-22 1997-12-30 Minnesota Mining And Manufacturing Company Masonry treatment composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 017, no. 391 (C - 1087) 22 July 1993 (1993-07-22) *
See also references of EP1390318A1 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007009935A2 (en) 2005-07-15 2007-01-25 Dow Corning Corporation Hydrophobing minerals and filler materials
WO2007009935A3 (en) * 2005-07-15 2007-04-05 Dow Corning Hydrophobing minerals and filler materials
JP2009501123A (en) * 2005-07-15 2009-01-15 ダウ・コ−ニング・コ−ポレ−ション Hydrophobized minerals and filler materials
AU2006271743B2 (en) * 2005-07-15 2012-03-15 Dow Corning Corporation Hydrophobing minerals and filler materials
US8142856B2 (en) 2005-07-15 2012-03-27 Dow Corning Corporation Hydrophobing minerals and filler materials
DE102008063965A1 (en) 2008-12-19 2010-06-24 Evonik Goldschmidt Gmbh Hydrophobic cementitious compositions
EP2202210A2 (en) 2008-12-19 2010-06-30 Evonik Goldschmidt GmbH Hydrophobic cementitious composition
US7931747B2 (en) 2008-12-19 2011-04-26 Evonik Goldschmidt Gmbh Hydrophobized cement-containing compositions
DE202008018525U1 (en) 2008-12-19 2016-02-01 Evonik Degussa Gmbh Hydrophobic cementitious compositions
DE102008063965B4 (en) * 2008-12-19 2017-05-18 Evonik Degussa Gmbh Hydrophobic cementitious compositions
DE102008063965C5 (en) 2008-12-19 2019-02-21 Evonik Degussa Gmbh Hydrophobic cementitious compositions

Also Published As

Publication number Publication date
IL153588A (en) 2009-09-22
EP1390318A1 (en) 2004-02-25
IL153588A0 (en) 2003-07-06
YU703A (en) 2005-11-28
NO20030070D0 (en) 2003-01-07
GB0111145D0 (en) 2001-06-27
NO20030070L (en) 2003-03-10
ZA200300162B (en) 2004-03-10

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