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WO2000020354A2 - Method of impregnating porous, stony objects - Google Patents

Method of impregnating porous, stony objects Download PDF

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Publication number
WO2000020354A2
WO2000020354A2 PCT/NL1999/000615 NL9900615W WO0020354A2 WO 2000020354 A2 WO2000020354 A2 WO 2000020354A2 NL 9900615 W NL9900615 W NL 9900615W WO 0020354 A2 WO0020354 A2 WO 0020354A2
Authority
WO
WIPO (PCT)
Prior art keywords
resin
objects
porous
stony
synthetic resin
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.)
Ceased
Application number
PCT/NL1999/000615
Other languages
French (fr)
Other versions
WO2000020354A3 (en
Inventor
Armand François Victor MATHIJS
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of WO2000020354A2 publication Critical patent/WO2000020354A2/en
Publication of WO2000020354A3 publication Critical patent/WO2000020354A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4811—Condensation polymers of aldehydes or ketones
    • C04B41/4815—Melamine-formaldehyde condensation products
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/83—Macromolecular compounds

Definitions

  • the invention relates to a method of impregnating porous, stony objects with a synthetic resin by introducing the resin in the as yet uncured state into the porous object and then causing the resin to cure.
  • the object is subjected to a vacuum, so that moisture and air are removed from the porous object. Then the object is immersed under positive pressure in the as yet uncured resin, so that the resin penetrates the pores of the object. Then the resin is cured.
  • the object of the known method is to obtain stony objects having improved weatherability and improved mechanical properties.
  • a drawback of the known method is that the impregnated objects thereby obtained will entirely or at least partially lose their natural stone-like appearance and instead will entirely or at least partially assume the appearance of plastic objects. This is highly disadvantageous, certainly in the case of uses for the stony objects where aesthetic aspects of the objects play an important part.
  • This object is achieved, surprisingly, by the synthetic resin used in the method according to the invention being a water-based thermosetting resin. This affords objects which after impregnation not only have better weatherability and improved mechanical properties, but which also have entirely or virtually entirely retained their original appearance.
  • a further advantage of the method according to the invention is that the method can be implemented considerably more simply compared with the known method. Thus it is no longer necessary to remove moisture from the objects before the objects are impregnated, whilst this is a requirement with the known method. Nor is it necessary to apply a vacuum to the object to remove the air therefrom or to introduce the resin into the object under positive pressure, although such a method of the invention is not excluded.
  • a further advantage of the method according to the invention is that the stony objects can be polished, for example with the aid of abrasive paper.
  • the porous, stony objects used in the method according to the invention can be made, for example, of natural stone, marl and sandstone or be ceramic products, such as terracotta products, for example.
  • Very good results are achieved if the objects are made of soft stony materials such as, for example, sandstone, lime sandstone, marl and the like.
  • the objects are made of marl.
  • Objects made of marl afford particularly good results. Not only are very strong and wear-resistant objects obtained, but the objects, having being impregnated with the aid of the method according to the invention, still retain a very beautiful, natural appearance. This matters, for example, if the objects are used in the restoration of old buildings or if the objects serve as artefacts such as, for example, sculptures, artistically inspired items of practical use, etc.
  • thermosetting resins are resins formed by the reaction of an aldehyde, preferably formaldehyde, with a compound containing two or more amino groups per molecule, such as, for example, urea, melamine, thiourea and guanidine.
  • a resin is used which is formed by the reaction of melamine and formaldehyde, hereinafter referred to as melamine resin.
  • the melamine resin used in the method according to the invention can, for example, be prepared by introducing melamine into an aqueous solution of formaldehyde having a concentration of, for example, 20-40 wt%, in a ratio of, for example, 1 part by weight of melamine to 3-6 parts by weight of formaldehyde.
  • the concentration of formaldehyde is 30-40 wt%, more preferably 37 wt%.
  • the ratio of melamine to formaldehyde is preferably 1 part by weight of melamine to 4-5 parts by weight of the 37 % by weight formaldehyde solution.
  • the synthetic resin can be introduced into the object simply by the surface of the object being treated with a composition.
  • the liquid resin penetrates the pores of the object under the influence of capillary forces, so that the object is impregnated with the resin.
  • the synthetic resin can be applied, for example, by means of the object being sprayed, for example with the aid of a spray gun, by the object being immersed in the resin composition, or by the composition being spread onto the object with the aid of a brush.
  • the resin is applied under atmospheric conditions, since this does not require the use of complicated equipment.
  • the resin is applied to the surface of the object until the object is sufficiently saturated with the resin.
  • the quantity of the resin which is applied can readily be established experimentally by those skilled in the art, for example be tailored to the intended use.
  • the object can be brought to an elevated temperature to effect or accelerate the curing of the resin.
  • a suitable temperature if melamine resin is used is, for example, between 90 and 150°C. After the object has been maintained at this temperature for a sufficiently long time, for example 0.5-2 hours, the resin is cured.
  • the object is then gradually cooled, for example at a rate of 0.5-2°C per minute. This prevents internal stresses from building up in the object. Those skilled in the art can determine the correct cooling rate experimentally.
  • the above-mentioned treatment can be repeated a number of times, preferably 2-3 times.
  • objects are obtained with a higher and higher resin content.
  • the objects become very tough.
  • Such objects very readily lend themselves to being machined, for example by turning, milling and sawing, with a possibility of forming objects having extremely delicate and finely formed components.
  • a highly advantageous method according to the invention is achieved if melamine resin containing an acid catalyst is used.
  • curing of the resin after this has been introduced into the object takes place very rapidly. In this case it is usually not even necessary to bring the objects to an elevated temperature.
  • very large objects can readily be treated which cannot easily be put into an oven.
  • objects such as sculptures, for example, to be treated in situ or for objects which, for example, form part of an existing structure, such as a building, to be treated without dismantling the structure.
  • acid catalysts are phosphoric acid, sodium hydrogen sulphate, etc.
  • a resin composition was prepared by 60 g of melamine being introduced into 0.250 1 of a 37% strength formaldehyde solution and being stirred until a clear solution was obtained at a temperature of 90°C.
  • a marl rod having a length of 150 mm, a width of 40 mm and a thickness of 10 mm was immersed in the solution. Then the rod was maintained for 1 hour at 90°C and again for 1 hour at 140°C in a hot-air oven. Then the rod was slowly cooled in air. The rod had increased in weight from 88 g to 99 g. Furthermore, the rod almost wholly retained its original appearance.
  • Example 1 The treatment of Example 1 was repeated with the rod of Example 1. During the second treatment, the rod had increased in weight to 109 g.
  • Example 1 The treatment of Example 1 was repeated with the rod of Example 2. During the third treatment, the rod had increased in weight to 116 g. The rod was very tough. For example, it was no longer possible to break the rod by hand; instead, the rod could only be sawn through with the aid of a iron saw.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Method of impregnating porous, stony objects with a synthetic resin by introducing the resin in the as yet uncured state into the porous object and then causing the resin to cure, the synthetic resin used being a water-based thermosetting resin. Very good results are achieved if the object is made or marl.

Description

Method of impregnating porous, stony objects.
The invention relates to a method of impregnating porous, stony objects with a synthetic resin by introducing the resin in the as yet uncured state into the porous object and then causing the resin to cure.
Such a method is disclosed by EP-A-220448.
In the above-mentioned patent application a method is described in which a porous, stony object, usually a natural stone, is impregnated with a solvent-free synthetic resin, for example an acrylate resin, by the resin in the as yet uncured state being introduced into the object and then being caused to cure.
To this end, the object is subjected to a vacuum, so that moisture and air are removed from the porous object. Then the object is immersed under positive pressure in the as yet uncured resin, so that the resin penetrates the pores of the object. Then the resin is cured. The object of the known method is to obtain stony objects having improved weatherability and improved mechanical properties.
A drawback of the known method is that the impregnated objects thereby obtained will entirely or at least partially lose their natural stone-like appearance and instead will entirely or at least partially assume the appearance of plastic objects. This is highly disadvantageous, certainly in the case of uses for the stony objects where aesthetic aspects of the objects play an important part.
It is an object of the invention to provide a method which does not have the above-mentioned drawback. This object is achieved, surprisingly, by the synthetic resin used in the method according to the invention being a water-based thermosetting resin. This affords objects which after impregnation not only have better weatherability and improved mechanical properties, but which also have entirely or virtually entirely retained their original appearance.
Yet a further advantage of the method according to the invention is that the method can be implemented considerably more simply compared with the known method. Thus it is no longer necessary to remove moisture from the objects before the objects are impregnated, whilst this is a requirement with the known method. Nor is it necessary to apply a vacuum to the object to remove the air therefrom or to introduce the resin into the object under positive pressure, although such a method of the invention is not excluded.
Yet a further advantage of the method according to the invention is that the stony objects can be polished, for example with the aid of abrasive paper.
The porous, stony objects used in the method according to the invention can be made, for example, of natural stone, marl and sandstone or be ceramic products, such as terracotta products, for example. Very good results are achieved if the objects are made of soft stony materials such as, for example, sandstone, lime sandstone, marl and the like. Preferably, the objects are made of marl. Objects made of marl afford particularly good results. Not only are very strong and wear-resistant objects obtained, but the objects, having being impregnated with the aid of the method according to the invention, still retain a very beautiful, natural appearance. This matters, for example, if the objects are used in the restoration of old buildings or if the objects serve as artefacts such as, for example, sculptures, artistically inspired items of practical use, etc.
Examples of objects which can be impregnated with the aid of the method according to the invention include building blocks, bricks, objets d'art, and the like. Examples of water-based thermosetting resins are resins formed by the reaction of an aldehyde, preferably formaldehyde, with a compound containing two or more amino groups per molecule, such as, for example, urea, melamine, thiourea and guanidine. Preferably, a resin is used which is formed by the reaction of melamine and formaldehyde, hereinafter referred to as melamine resin.
The melamine resin used in the method according to the invention can, for example, be prepared by introducing melamine into an aqueous solution of formaldehyde having a concentration of, for example, 20-40 wt%, in a ratio of, for example, 1 part by weight of melamine to 3-6 parts by weight of formaldehyde. Preferably, the concentration of formaldehyde is 30-40 wt%, more preferably 37 wt%. The ratio of melamine to formaldehyde is preferably 1 part by weight of melamine to 4-5 parts by weight of the 37 % by weight formaldehyde solution. The synthetic resin can be introduced into the object simply by the surface of the object being treated with a composition. In the process, the liquid resin penetrates the pores of the object under the influence of capillary forces, so that the object is impregnated with the resin. The synthetic resin can be applied, for example, by means of the object being sprayed, for example with the aid of a spray gun, by the object being immersed in the resin composition, or by the composition being spread onto the object with the aid of a brush. Preferably, the resin is applied under atmospheric conditions, since this does not require the use of complicated equipment. The resin is applied to the surface of the object until the object is sufficiently saturated with the resin. The quantity of the resin which is applied can readily be established experimentally by those skilled in the art, for example be tailored to the intended use.
After the resin has been introduced into the object, the object can be brought to an elevated temperature to effect or accelerate the curing of the resin. A suitable temperature if melamine resin is used is, for example, between 90 and 150°C. After the object has been maintained at this temperature for a sufficiently long time, for example 0.5-2 hours, the resin is cured.
Preferably, the object is then gradually cooled, for example at a rate of 0.5-2°C per minute. This prevents internal stresses from building up in the object. Those skilled in the art can determine the correct cooling rate experimentally.
If required, the above-mentioned treatment can be repeated a number of times, preferably 2-3 times. Thus objects are obtained with a higher and higher resin content. As a result, the objects become very tough. Such objects very readily lend themselves to being machined, for example by turning, milling and sawing, with a possibility of forming objects having extremely delicate and finely formed components.
A highly advantageous method according to the invention is achieved if melamine resin containing an acid catalyst is used. As a result, curing of the resin after this has been introduced into the object takes place very rapidly. In this case it is usually not even necessary to bring the objects to an elevated temperature. Thus, very large objects can readily be treated which cannot easily be put into an oven. Likewise it is possible for objects such as sculptures, for example, to be treated in situ or for objects which, for example, form part of an existing structure, such as a building, to be treated without dismantling the structure. Examples of acid catalysts are phosphoric acid, sodium hydrogen sulphate, etc.
The invention is explained in more detail with reference to the examples without been limited thereto. Example 1.
A resin composition was prepared by 60 g of melamine being introduced into 0.250 1 of a 37% strength formaldehyde solution and being stirred until a clear solution was obtained at a temperature of 90°C.
A marl rod having a length of 150 mm, a width of 40 mm and a thickness of 10 mm was immersed in the solution. Then the rod was maintained for 1 hour at 90°C and again for 1 hour at 140°C in a hot-air oven. Then the rod was slowly cooled in air. The rod had increased in weight from 88 g to 99 g. Furthermore, the rod almost wholly retained its original appearance.
Example 2
The treatment of Example 1 was repeated with the rod of Example 1. During the second treatment, the rod had increased in weight to 109 g.
Example 3
The treatment of Example 1 was repeated with the rod of Example 2. During the third treatment, the rod had increased in weight to 116 g. The rod was very tough. For example, it was no longer possible to break the rod by hand; instead, the rod could only be sawn through with the aid of a iron saw.

Claims

1. Method of impregnating porous, stony objects with a synthetic resin by introducing the resin in the as yet uncured state into the porous object and then causing the resin to cure, characterized in that the synthetic resin used is a water-based thermosetting resin.
2. Method according to Claim 1, characterized in that the resin is formed by the reaction of an aldehyde with a compound which contains two or more amine groups per molecule.
3. Method according to Claim 1 or 2, characterized in that the porous objects are made of natural stone, marl or sandstone or are ceramic products.
4. Method according to Claim 3, characterized in that the objects are made of marl.
5. Method according to any one of Claims 1-4, characterized in that the synthetic resin used is a melamine resin.
6. Method according to any one of Claims 1-5, characterized in that the synthetic resin is introduced into the porous object by treating the surface of the object with the synthetic resin.
7. Method according to Claim 5, characterized in that a melamine resin containing an acid catalyst is used.
PCT/NL1999/000615 1998-10-05 1999-10-04 Method of impregnating porous, stony objects Ceased WO2000020354A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1010248A NL1010248C1 (en) 1998-10-05 1998-10-05 Method for impregnating porous, stony objects.
NL1010248 1998-10-05

Publications (2)

Publication Number Publication Date
WO2000020354A2 true WO2000020354A2 (en) 2000-04-13
WO2000020354A3 WO2000020354A3 (en) 2000-07-06

Family

ID=19767924

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1999/000615 Ceased WO2000020354A2 (en) 1998-10-05 1999-10-04 Method of impregnating porous, stony objects

Country Status (2)

Country Link
NL (1) NL1010248C1 (en)
WO (1) WO2000020354A2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6575986B2 (en) 2001-02-26 2003-06-10 Ethicon, Inc. Scaffold fixation device for use in articular cartilage repair
US6626950B2 (en) 2001-06-28 2003-09-30 Ethicon, Inc. Composite scaffold with post anchor for the repair and regeneration of tissue
US6743232B2 (en) 2001-02-26 2004-06-01 David W. Overaker Tissue scaffold anchor for cartilage repair

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE723203C (en) * 1938-03-10 1942-07-30 Dr Karl Brandt Process for improving the properties of porous building materials and materials
US2333151A (en) * 1942-04-27 1943-11-02 Kewaunee Mfg Company Sandstone product
DE2611501A1 (en) * 1976-03-18 1977-11-10 Chemie Linz Ag Surface treatment of asbestos cement building materials - with amino-triazine-formaldehyde precondensate, to prevent calcareous efflorescence

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6575986B2 (en) 2001-02-26 2003-06-10 Ethicon, Inc. Scaffold fixation device for use in articular cartilage repair
US6743232B2 (en) 2001-02-26 2004-06-01 David W. Overaker Tissue scaffold anchor for cartilage repair
US6626950B2 (en) 2001-06-28 2003-09-30 Ethicon, Inc. Composite scaffold with post anchor for the repair and regeneration of tissue

Also Published As

Publication number Publication date
NL1010248C1 (en) 2000-04-06
WO2000020354A3 (en) 2000-07-06

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