WO2000024690A1 - Improved cement composition - Google Patents

Improved cement composition Download PDF

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Publication number
WO2000024690A1
WO2000024690A1 PCT/BE1999/000130 BE9900130W WO0024690A1 WO 2000024690 A1 WO2000024690 A1 WO 2000024690A1 BE 9900130 W BE9900130 W BE 9900130W WO 0024690 A1 WO0024690 A1 WO 0024690A1
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WO
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Patent type
Prior art keywords
acid
wouastonite
cement composition
composition according
component
Prior art date
Application number
PCT/BE1999/000130
Other languages
French (fr)
Inventor
Xiao Wu
Junn Gu
Original Assignee
Vrije Universiteit Brussel
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

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
    • C04B14/04Silica-rich materials; Silicates
    • C04B14/043Alkaline-earth metal silicates, e.g. wollastonite

Abstract

The present invention concerns the field of cement, and relates particularly to phosphate cements. According to one aspect of the present invention there is provided a phosphate cement composition which comprises, in combination, a component A and a component B wherein the component A comprises an acid-treated wollastonite compound, an acid aqueous solution of metal phosphate, and a setting retarder; and component B comprises a setting accelerator.

Description

IMPROVED CEMENT COMPOSITION

The present invention concerns the field of cement, and relates particularly to phosphate cements.

Following abbreviations will be used throughout the text:

US1 = US Patent 3,642,511

US2 = US Patent 4,956,321 US3 = US Patent 4,375,516

Wl = WO 97/19033

Invention = newly developed inventio .

Background information

US1 discloses a method to treat woUastonite by acid, say sulphuric acid and phosphoric acid, to a degree of pH <= 4.0. The aim of the treatment is to have a good opacity properties and low abrasiveness resistance, so that the final product, i.e., acid treated woUastonite, can be used as a pigment for paper industry (column 1, line 41-53).

US2 discloses a method to treat woUastonite by acid, say sulphuric acid, carbonate acid and acetate acid, to a degree that the treated woUastonite has a pH=9-10. The treated woUastonite, called surface-pacified woUastonite in US2, may be used as an inert filler, or in the composition of US3. The aim of treating the woUastonite by the acid is to have a "reaction uniformity" of the woUastonite (column 1, line 19-27), so that the reaction, presumably the quick-setting process of the US3, will not be influenced by the different batches and grades of raw material. As a result, the treated woUastonite has a pH=9-10, which is not fundamentally different from that of the untreated woUastonite of pH=9-10.7 (column 2, line 34-39). This is an indication that US2 seeks to keep the reactivity of the US3 composition. As an evidence, Example 4 of US2 shows a setting time of 1 hour, which is considered as quick-setting in an industrial process. We have tested the Example 2 of US2 to examine its setting process, and the result shows that it has a setting time of less than 10 minutes at 20°C (Table 3).

Wl, our previous invention, discloses a composition comprising an acid metal phosphate solution, a woUastonite compound and an oxy-boron compound as setting retarder. This composition discloses a technique to reduce reactivity of the composition by the setting retarder which results in a long pot life. The woUastonite used in the Wl is an untreated woUastonite having a pH = 9-12. The Wl composition may provide a long pot life. However, its setting will take long time as well at 20 °C because the reactivity of the composition is significantly reduced by the retarder. High temperature curing may be used to accelerate the setting, but there are times when high temperatures are not suitable.

There is a pressing need to develop a technique to accelerate setting reaction of a composition according to Wl, using means other than increased curing temperature, so that a shaped body can be fully cured and obtained in a relatively short period.

It is an object of the present invention to provide a composition which fulfils the above need.

Description of the Invention

The Invention disclosed herein relates to a phosphate cement composition, its method of preparation and resulting products formed therefrom.

Some particular objectives of the Invention are: (1) to reduce pH value of the woUastonite by a treatment so that reactivity of the said component A can be fundamentally reduced, resulting in further extended pot life; and (2) to provide a technique so that setting of the composition become obtainable whenever it is required.

According to one aspect of the present invention there is provided a phosphate cement composition which comprises, in combination, a component A and a component B wherein the component A comprises an acid-treated woUastonite compound, an acid aqueous solution of metal phosphate, and a setting retarder; and component B comprises a setting accelerator.

Preferably the metal phosphate is selected from the group consisting of: aluminium phosphates, zirconium phosphates, magnesium phosphates, zinc phosphates, calcium phosphates, iron phosphates, including derivatives and mixtures thereof.

The setting retarder may be selected from the group consisting of boric acid, alkali metal and, alkaline-earth metal salts of boric acid, amine and ammonium salts of boric acid, including hydrates and mixtures thereof.

The setting retarder may be selected from the group consisting of: boric acid, sodium borate, ammonium borate, calcium borate, including hydrates and mixtures thereof. Preferably said setting retarder is added as a powder or a liquid. Suitable accelerators are be known in the art; one is MgO.

The woUastonite of the said acid-treated woUastonite compound may be a natural or synthetic woUastonite, in calcined or non-calcined state, or a combination thereof.

The acid-treated woUastonite has preferably has a pH value of 6-8 a measured using a woUastonite 10 % water slurry.

The said acid used to treat the woUastonite may be an inorganic acid. For example, the acid used to treat the woUastonite may be sulphuric acid, phosphoric acid, carbonate acid, acetate acid, or a combination thereof.

According of another aspect of the invention there is provided a method of producing acid-treated woUastonite for a cement composition comprising: (1) mixing woUastonite with an inorganic acid aqueous solution in a concentration and quantity sufficient to form an acid/wollastonite mixture having a pH=6-8; and (2) drying the mixture after its pH value becomes stable.

The said acid may be sulphuric acid, phosphoric acid, carbonate acid, acetate acid, boric acid, or a combination thereof. The said acid preferably has a normality of O.03 - 0.05.

According to yet another aspect of the invention there is provided a shaped product formed from cement as hereinbefore described.

According to yet a further aspect of the invention there is provided a shaped product containing the acid treated woUastonite as hereinbefore described.

According to yet another aspect of the invention there is provided a method of making a solid shaped article comprising: providing composition A, forming the composition into a shape, and adding composition C to set the cement in the shape.

In general, the component A has a sufficiently long pot life, while the component B can be added to component at any moment during the pot life to form the cement which sets in relative short period so that a shaped body can be fully cured and produced at circa 20 °C by the Invention.

In general, reducing reactivity of the composition A of the Invention is achieved by treating the woUastonite with acid, to a degree that the treated woUastonite has a pH = 6-8 in woUastonite 10 % water slurry (this method of pH measurement will be used hereafter). When this treated woUastonite of pH = 6-8 meets acid metal phosphate solution, it reacts much slower than that of untreated woUastonite having a pH = 9-12. This results in a more extended pot life for the component A, even compared to that of Wl.

On the other hand, controlling the setting time is realised using a setting accelerator. When this setting accelerator is added to the Invention composition A at any moment during the pot life, a setting mechanism is induced immediately which causes setting and full curing of the Invention composition at ambient temperature condition in a relatively short period.

These techniques have never been developed prior to this Invention, specially for the accelerator. This is because the phosphate cement using woUastonite as primary material has always been known as a quick-setting cement (with the exception of that disclosed in Wl) so no setting accelerator has ever been considered necessary.

Following is a description of some comparative tests illustrating the effectiveness of the compositions of the present invention.

Composition

With respect to composition, the Invention is fundamentally different frown the Wl (Table 1) in the particular woUastonite employed and presence of the setting accelerator. This significantly improves industrial applicability of the technology.

Compared to US2, the composition of the Invention is evidently different not only in the presence of setting retarder and a setting accelerator, but also in the particular woUastonite employed. The Invention woUastonite is a mixture of a calcium salt of the particular acid used in the treatment (calcium sulphate, for instance), a silica gel and an un-reacted woUastonite, characterised by pH = 6-8. The presence of silica gel indicates that woUastonite structure is attacked during the treatment. While the US2 woUastonite is only surface-pacified with a surface-displaceable anion without altering crystal structure, and having a pH = 9-10 (column 3, line 30-38). These therefore are two different materials, to be used for different applications.

Table 1 Composition difference

Figure imgf000011_0001

Setting process

Because of the difference in material composition, setting process of the Invention, US2 and Wl are consequently different, as summarised in the Table 2.

Table 2 Difference in the setting process

Figure imgf000012_0001

*Controllable quick setting in the sense that the setting can be realised by adding setting accelerator.

Comparative tests

Comparative tests has been made, using compositions of the Invention, Wl and US2 to verify their setting process (Table 3). The woUastonite used in the test is very reactive and has a pH=12. The surface-pacified woUastonite used for US2 is obtained by treating it with sulphuric acid having a normality of 0.01, rinsed with de-ionised water and then dried, as required by the Example 2, US2 (column 3, Example 2). The acid treated woUastonite used in the Invention is a mixture comprising calcium sulphate, silica gel and un-reacted woUastonite obtained by treating it with sulphuric acid having a normality of 0.04 and then dried at 60°C.

Table 3 Pot life at 20°C

Figure imgf000013_0001

(1) phosphate to woUastonite ratio (2) maximum pot life, no setting accelerator is used

(3) aluminium phosphate from US2 Example 2, columns 3-4.

The test results show that when the US2 composition is used, it is always quick-setting together with foaming, independent of the pH value of the woUastonite. It demonstrates that the surface-pacified woUastonite cannot provide long pot life. On the other hand, when the Invention composition is employed, the woUastonite of pH = 7 does reduce reactivity of the component A compared to Wl and the US2, indicated by the dramatic increase of pot life.

Field of Application

The field of application and industrial applicability is summarised in the table 4 .

Table 4 properties and field of application

Field of application Industrial suitability

Invention 1. fibre reinforced much improved over composites l

3. cement

4. adhesive

5. foams

Wl 1. fibre reinforced Yes composites

3. cement

4. adhesive

5. foams

US2 1. foams difficult

2. quick-setting applications In view of the difference in composition, setting process and industrial applicability, the Invention has novelty, inventive step and industrial applicability with regard to its composition, method of treating the woUastonite and the resulting products formed from the cement.

Claims

1. A phosphate cement composition which comprises, in combination, a component A and a component B wherein the component A comprises an acid-treated woUastonite compound, an acid aqueous solution of metal phosphate, and a setting retarder; and component B comprises a setting accelerator.
2. A phosphate cement composition according to claim 1 wherein the metal phosphate is selected from the group consisting of: aluminium phosphates, zirconium phosphates, magnesium phosphates, zinc phosphates, calcium phosphates, iron phosphates, including derivatives and mixtures thereof.
3. A phosphate cement composition according to claim 1 or claim 2 wherein said setting retarder is selected from the group consisting of boric acid, alkali metal and, alkaline-earth metal salts of boric acid, a ine and ammonium salts of boric acid, including hydrates and mixtures thereof .
4. A phosphate cement composition according to claim 3 wherein the setting retarder is selected from the group consisting of: boric acid, sodium borate, ammonium borate, calcium borate, including hydrates and mixtures thereof .
5. A phosphate cement composition according to claim 3 or claim 4 wherein said setting retarder is added as a powder or a liquid.
6. A phosphate cement composition according to claim 1 wherein the woUastonite of the said acid-treated woUastonite compound is a natural or synthetic woUastonite, in calcined or non-calcined state, or a combination thereof .
7. A phosphate cement composition according to claim 1 and claim 6 wherein said acid-treated woUastonite has a pH value of 6-8 a measured using a woUastonite 10 % water slurry.
8. A phosphate cement composition according to claim 1 and claims 6 or 7 wherein the said acid used to treat the woUastonite is an inorganic acid.
9. A phosphate cement composition according to claim 1 and any of claims 6 to 8 wherein the acid used to treat the woUastonite is sulphuric acid, phosphoric acid, carbonate acid, acetate acid, or a combination thereof.
10. A method of producing acid-treated woUastonite for a cement composition comprising: (1) mixing woUastonite with an inorganic acid aqueous solution in a concentration and quantity sufficient to form an acid/wollastonite mixture having a pH=6-8; and (2) drying the mixture after its pH value becomes stable.
11. A method according to claim 10 wherein the said acid is sulphuric acid, phosphoric acid, carbonate acid, acetate acid, boric acid, or a combination thereof.
12. A method according to claim 10 or 11 wherein the said acid has a normality of O.03 - 0.05.
13. A shaped product formed from cement according to any of claims 1-10.
14. A shaped product containing the acid treated woUastonite of claim 11 or 12.
PCT/BE1999/000130 1998-10-23 1999-10-22 Improved cement composition WO2000024690A1 (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6518212B1 (en) 2000-09-18 2003-02-11 The University Of Chicago Chemically bonded phospho-silicate ceramics
US7491267B2 (en) 2001-08-10 2009-02-17 Ceratech, Inc. Composite materials and methods of making and using such composite materials
US7517402B2 (en) 2001-10-08 2009-04-14 Xexos Ltd. Composition comprising a phosphate binder and its preparation
US7798287B1 (en) 2005-01-20 2010-09-21 Serious Materials, Inc. Acoustical ceiling panels
US7909136B2 (en) 2004-11-24 2011-03-22 Serious Materials, Inc. Soundproof assembly
US7921965B1 (en) 2004-10-27 2011-04-12 Serious Materials, Inc. Soundproof assembly and methods for manufacturing same
WO2012064194A1 (en) 2010-11-11 2012-05-18 Delft University Of Technology Hot gas handling device and motorized vehicle comprising the device
US8916277B2 (en) 2007-11-16 2014-12-23 Serious Energy, Inc. Low embodied energy wallboards and methods of making same
US9388568B2 (en) 2007-04-06 2016-07-12 Pacific Coast Building Products, Inc. Acoustical sound proofing material with improved fracture characteristics and methods for manufacturing same
US9387649B2 (en) 2007-06-28 2016-07-12 Pacific Coast Building Products, Inc. Methods of manufacturing acoustical sound proofing materials with optimized fracture characteristics

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804651A (en) * 1972-07-21 1974-04-16 Department Of Transportation Lime silico-phosphate cement
US4504555A (en) * 1982-09-07 1985-03-12 Masonite Corporation Composition and process for forming inorganic resins and resulting product
US4956321A (en) * 1988-06-16 1990-09-11 Armstrong World Industries, Inc. Surface pacified wollastonite
WO1996038394A1 (en) * 1995-05-30 1996-12-05 Reslab A/S Curable gypsum-containing composition and method for stabilization of unconsolidated core samples
WO1997019033A1 (en) * 1995-11-17 1997-05-29 Vrije Universiteit Brussel Inorganic resin compositions, their preparation and use thereof
US5773376A (en) * 1994-01-21 1998-06-30 Melcher; Gerhard Process for producing a mainly inorganic foam, and thus produced mass or moulded part

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3804651A (en) * 1972-07-21 1974-04-16 Department Of Transportation Lime silico-phosphate cement
US4504555A (en) * 1982-09-07 1985-03-12 Masonite Corporation Composition and process for forming inorganic resins and resulting product
US4956321A (en) * 1988-06-16 1990-09-11 Armstrong World Industries, Inc. Surface pacified wollastonite
US5773376A (en) * 1994-01-21 1998-06-30 Melcher; Gerhard Process for producing a mainly inorganic foam, and thus produced mass or moulded part
WO1996038394A1 (en) * 1995-05-30 1996-12-05 Reslab A/S Curable gypsum-containing composition and method for stabilization of unconsolidated core samples
WO1997019033A1 (en) * 1995-11-17 1997-05-29 Vrije Universiteit Brussel Inorganic resin compositions, their preparation and use thereof

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6518212B1 (en) 2000-09-18 2003-02-11 The University Of Chicago Chemically bonded phospho-silicate ceramics
US7491267B2 (en) 2001-08-10 2009-02-17 Ceratech, Inc. Composite materials and methods of making and using such composite materials
US7517402B2 (en) 2001-10-08 2009-04-14 Xexos Ltd. Composition comprising a phosphate binder and its preparation
US7736429B2 (en) 2001-10-08 2010-06-15 Xexos Ltd. Composition comprising a phosphate binder and its preparation
US7921965B1 (en) 2004-10-27 2011-04-12 Serious Materials, Inc. Soundproof assembly and methods for manufacturing same
US7909136B2 (en) 2004-11-24 2011-03-22 Serious Materials, Inc. Soundproof assembly
US7798287B1 (en) 2005-01-20 2010-09-21 Serious Materials, Inc. Acoustical ceiling panels
US9388568B2 (en) 2007-04-06 2016-07-12 Pacific Coast Building Products, Inc. Acoustical sound proofing material with improved fracture characteristics and methods for manufacturing same
US9387649B2 (en) 2007-06-28 2016-07-12 Pacific Coast Building Products, Inc. Methods of manufacturing acoustical sound proofing materials with optimized fracture characteristics
US8916277B2 (en) 2007-11-16 2014-12-23 Serious Energy, Inc. Low embodied energy wallboards and methods of making same
WO2012064194A1 (en) 2010-11-11 2012-05-18 Delft University Of Technology Hot gas handling device and motorized vehicle comprising the device

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