Dry premixture for flexible concrete and method for its preparation and use thereof

Abstract

The invention relates to a cementitious powder blend comprising, based on total weight—45-90 wt % Portland cement; pref. 50-80 wt %—0-25 wt % siliceous fly ash; pref. 5-20 wt %—0-25 wt % limestone; pref. 5-20 wt %—5-30 wt % polyvinylalcohol, pref. 5-15 wt %. The PVA preferably has—a size distribution with D.sub.10=170-270 μm, D50=370-450 μm. D.sub.90=690-850 μm and D.sub.100=1000-1300 μm; and—an ester value in the range of 1-250 mg KOH/g, as determinable by EN-ISO 3681:1998 and/or wherein the polyvinyl alcohol has a viscosity of a 4% aqueous solution at 20° C. in the range of 1-40 mPa.Math.s, as determinable by EN-ISO 12058-1:2002. A substantial part of the PVA may be present in the form of hybrid particles composed of Portland cement and the polyvinylalcohol. Further, the invention relates to concrete composed of the cementitious powder blend, water and aggregate as well as flexible concrete products made therefrom. The cementitious powder blend is used for—for the preparation of a paving of a road or other infrastructural element; for the preparation of a base course for a road or other infrastructural element; for the manufacture of a floor of a building; for the repair of a concrete structure; for grouting; or—as an injection into a concrete structure.

Claims

1. A cement powder blend comprising, based on total weight 45-90 wt. % Portland cement; 0-25 wt. % siliceous fly ash; 0-25wt. % limestone; and 5-30wt. % polyvinylalcohol, wherein the polyvinylalcohol has a size distribution with D.sub.10=170-270 μm, D.sub.50=370-450 μm, D.sub.90=690-850 μm and D.sub.100=1000-1300 μm; or an ester value in the range of 1-250 mg KOH/g, as determined by EN-ISO 3681:1998; or a viscosity of a 4% aqueous solution at 20° C. in the range of 1-40 mPa.Math.s, as determined by EN-ISO 12058-1:2002.

2. The cement powder blend according to claim 1, comprising 50-80 wt. % Portland cement; 5-20 wt. % siliceous fly ash; 5-20 wt. % limestone; and 5-15 wt. % polyvinylalcohol.

3. The cement powder blend according to claim 1, wherein the polyvinyl alcohol has an ester value in the range of 7-150 mg KOH/g.

4. The cement powder blend according to claim 3, wherein the polyvinyl alcohol has an ester value in the range of 7-10 mg KOH/g.

5. The cement powder blend according to claim 3, wherein the polyvinyl alcohol has an ester value in the range of 130-150 mg KOH/g.

6. A method for preparing a cement powder blend according to claim 1, the method comprising dry-blending the polyvinylalcohol, the Portland cement, the fly ash and the limestone.

7. A construction slurry of the cement powder blend according to claim 1 and water in a weight to weight ratio water to the Portland cement in the range of 0.2-0.7.

8. The construction slurry according to claim 7, wherein the construction slurry is a cement slurry.

9. A hardened construction cement slurry of the cement powder blend according to claim 1.

10. The hardened construction cement slurry according to claim 9, wherein at least a substantial part of the polyvinyl alcohol is present in the form of hybrid particles composed of Portland cement and polyvinylalcohol.

11. The hardened construction cement slurry according to claim 9, having an expansion of 0-25% determined with sample length measurements during curing at 60° C.

12. The hardened construction cement slurry according to claim 9, having a stiffness of 0.5-1.5 N/mm.sup.2 measured by means of direct tensile strength at 28 days.

13. Concrete composed of a cement powder blend according to claim 1, aggregate and water.

14. Concrete according to claim 13, comprising 6-24% wt. of the cement powder blend of claim 1; 4-16% wt. water; 20-50 wt. % fine aggregates (0-4 mm); 35-60 wt. % coarse aggregates (4-20 mm); with the proviso that the total aggregate content is 60-90 wt. %.

15. A product, comprising concrete according to claim 13.

16. Concrete comprising 6-24 wt. % of a cement powder blend; 4-16 wt. % water; 20-50 wt. % fine aggregates (0-4 mm); and 35-60 wt. % coarse aggregates (4-20 mm); with the proviso that the total aggregate content is 60-90 wt. %, wherein the cement powder blend comprises, based on total weight 45-90 wt. % Portland cement; 0-25 wt. % siliceous fly ash; 0-25 wt. % limestone; and 5-30 wt. % polyvinylalcohol.

17. A product comprising concrete according to claim 16.

18. The product according to claim 17, wherein the product is selected from the group consisting of infrastructural elements, a building, a concrete ware, an an elements for pre-fab buildings.

19. The product according to claim 18, wherein the product is a building, comprising a floor made of said concrete.

20. The product according to claim 18, wherein the product is an infrastructural element selected from the group consisting of a road, a parking terrain, an airplane-landing strip, a railway embankment, a sound barrier wall, and a sewer.

21. The product according to claim 18, wherein the product is a building selected from the group consisting of a parking garage, an industrial building, a storage hall, a retail center, and a residential building.

22. The product according to claim 18, wherein the product is a concrete ware that is a concrete pipe.

23. The product according to claim 18, wherein the product is an element for pre-fab buildings selected from the group consisting of a pre-fab wall, a pre-fab floor, and a pre-fab ceiling.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the shrinkage of a cement formulation according to the invention and a reference formulation.

(2) FIGS. 2A and 2B show SEM images of a cured sample of a cement formulation. FIG. 3 shows the ductile fracture behavior for a cement paste of the invention and a reference cement paste.

(3) FIG. 4 shows the stiffness-temperature dependency for a concrete of the invention and a reference concrete.

(4) FIG. 5 shows fatigue behavior for a concrete of the invention.

DETAILED DESCRIPTION OF THE INVENTION

(5) Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

(6) The term “or” as used herein means “and/or” unless specified otherwise.

(7) The term “a” or “an” as used herein means “at least one” unless specified otherwise.

(8) The term“substantial(ly)” or “essential(ly)” is generally used herein to indicate that it has the general character or function of that which is specified. When referring to a quantifiable feature, these terms are in particular used to indicate that it is for at least 75%, more in particular at least 90%, even more in particular at least 95% of the maximum of that feature.

(9) As used herein, percentages are usually weight percentages unless specified otherwise. Percentages are usually based on total weight, unless specified otherwise.

(10) When referring to a “noun” (e.g. a compound, an additive etc.) in singular, the plural is meant to be included, unless specified otherwise.

(11) When referring herein to a particle size distribution ‘Dx’ the x refers to the particle diameter corresponding to x % cumulative (from 0 to 100%) undersize particle size distribution. In other words, if particle size D.sub.x is y μm, x% of the weight in the tested sample is provided by particles smaller than y μm, or the weight percentage of particles smaller than y μ is x %. D.sub.10, D.sub.50, D.sub.90 and D.sub.100 are typical points in particle size distribution analysis.

(12) The term ‘slurry; is generally known in the art to describe mixtures of a fluid in which a particulate (e.g. pulverised) material in dispersed that (in unhardened state) is flowable or pumpable. For ‘cement slurry’, the term ‘cement paste’ is also commonly used in the art, because generally cement slurries are pasty. The cured (hardened) product of the cement slurry or paste is usually referred to as hardened cement slurry or paste, although the adjective ‘hardened’ may be omitted when it is clear from the context that the slurry or paste has solidified.

(13) For the purpose of clarity and a concise description features are described herein as part of the same or separate embodiments, however, it will be appreciated that the scope of the invention may include embodiments having combinations of all or some of the features described.

(14) The cement powder blend preferably contains at least 50 wt. % Portland cement. The Portland cement content of the cement powder blend preferably is 80 wt. % or less, more preferably 75 wt. % or less, in particular 65 wt. % or less, more in particular 60 wt. % or less. Particularly good results have been achieved Portland cement meeting the NEN-EN 197-1 standard of October 2011, of which the contents are incorporated by reference.

(15) The siliceous fly ash content of the cement powder blend usually is at least 5 wt. % preferably at least 10 wt. %. The siliceous fly ash content preferably is 20 wt. % or less. The siliceous fly ash is typically non-coated. This is advantageous because siliceous fly ash —in uncoated state—has pozzolanic properties and thereby contributes to the cementitious properties of the cement powder. As an alternative or in addition calcareous fly ash may be present, with the proviso that the total fly ash content does not exceed 25 wt. %.

(16) The limestone content of the cement powder blend usually is at least 5 wt. %, preferably at least 10 wt. %. The limestone content preferably is 20 wt. % or less. Like Portland cement, limestone contains calcium. In accordance with the invention, it has been found that PVA and a calcium bearing material can react to form a matrix of PVA and the calcium bearing material. In particular, the presence of limestone has been found advantageous to reduce shrinkage of a material according to the invention.

(17) The cement powder blend preferably comprises 25 wt. % PVA or less, more preferably 20 wt. % PVA or less, most preferably 15 wt. % PVA or less. In a particularly preferred embodiment, the PVA content of the cement powder blend is at least 6 wt. %, in particular at least 7 wt. %, more in particular at least 8 wt. %.

(18) The PVA in the cement powder blend or used for preparing the cement powder blend usually has a D.sub.10 of 300 μm or less, preferably in the range of 170-270 μm. D.sub.50 is usually 500 μm or less, preferably in the range of 370-450 μm. D.sub.90 is usually 900 μm or less, preferably in the range of 690-850 μm. D.sub.100 is usually less than 1500 μm, preferably in the range of 1000-1300 μm. The values are measured using laser diffraction (also known as (Near) Forward Light Scattering, Low Angle Laser Light Scattering or Fraunhofer Diffraction).

(19) The PVA usually has an average molecular weight (Mw) in the range of 25000-155000 g/mol. Preferably, the Mw is at least 2 7000 g/mol, in particular at least 29000 g/mol. Preferably the Mw is 150000 g/mol or less, e.g. 145000 g/mol or less. In particularly preferred embodiment the PVA has an Mw in the range of 29,000-32,000 g/mol or in the range of 140,000-150,000 g/mol. The Mw can be determined, for instance with size exclusion chromatography in an aqueous buffer, using Mowiol® as calibration standards. Mowiol® is available from Sigma-Aldrich (a Merck subsidiary). Mowiol® 4-88 represents an Mw of 31000 g/mol; Mowiol® 10-98 represents an Mw of 61000 g/mol; Mowiol® represents an Mw of 130000 g/mol.

(20) The PVA usually has a hydrolysis degree of 99% or less. The PVA usually has a hydrolysis degree of more than 75%, preferably of at least 85%, more preferably of at least 87%. In a particularly preferred embodiment the PVA has a hydrolysis degree in the range of 87-89% or 98-99%. Herein Mowiol® can be used as calibration standards.

(21) The polyvinyl alcohol usually has an ester value in the range of 1-250 mg KOH/g, as determinable by EN-ISO 3681:1998. Preferably, the ester value of the PVA is in the range of 5 160 mg KOH/g., more preferably in the range of 7-150 mg KOH/g, in particular in the range of 7-10 mg KOH/g or 130-150 mg KOH/g.

(22) The PVA usually has a viscosity of a 4% aqueous solution at 20° C., as determinable by EN-ISO 12058-1:2002, in the range of 1-40 mPa.Math.s in particular in the range of 2-30 mPa.Math.s. In particular good results have been achieved with a PVA having a viscosity in the range of 1-6 mPa.Math.s or in the range of 25-30 mPa.Math.s.

(23) As an optional component, the cement powder blend may comprise a plasticizer, usually a polycarboxylic ether plasticizer, preferably a modified polycarboxylic-ether. The content of polycarboxylic ether plasticizer usually is in the range of 0-6 wt. %, preferably in the range of 0.5-5 wt. %, more preferably in the range of 1.0-4 wt. %, based on the weight of the Portland cement.

(24) The cement powder blend can be made be dry-blending the components. This can be done in generally known equipment under ambient conditions.

(25) The construction slurry, in particular the cement slurry, such as the cement paste, can be made from the cement powder blend according to the invention by mixing with water in a manner known per se. The resultant slurry, such as the paste, can thereafter by used in a manner known per se for any application of interest, in particular in the production of a concrete according to the invention, as mortar or for a use specified elsewhere herein. For the production of concrete, typically aggregate is added to the construction slurry, such as the paste. The aggregate may be fine aggregate (particle size <4 mm), coarse aggregate (particle size 4-20 mm) or a combination thereof. It is an advantage of the invention that the concrete can be free of steel reinforcement materials and/or fibrous reinforcement materials (such as polymeric fibres). However, if desired, the concrete can contain such reinforcement material.

(26) In a preferred embodiment, the hardened slurry, such as the hardened cement paste, according to the invention, has an expansion of 0-25% determined with sample length measurements (as described in Example 1) during curing (i.e. hardening) at 60° C.

(27) In a preferred embodiment, the hardened slurry, such as the hardened cement paste, according to the invention has a stiffness of 0.5-1.5 N/mm.sup.2 measured by means of direct tensile strength at 28 days.

(28) The concrete according to the invention preferably is composed of 6-24 wt. % cement powder blend according to the invention.

(29) The concrete according to the invention preferably comprises 4-16 wt. % water.

(30) The concrete according to the invention preferably comprises 20-50 wt. % fine aggregates (0-4 mm) and/or 35-60 wt. % coarse aggregates (4-20 mm), with the proviso that the total aggregate content is 60-90 wt. %.

(31) The invention will now be illustrated by the following examples.

EXAMPLE 1

Formulation with Low Shrinkage

(32) A formulation with 20 wt. % of polyvinyl alcohol with ester value of 8 mg KOH/g, viscosity 28 mPa.Math.s (of a 4% solution in water at 20 ° C.) and D.sub.10=233 μm, D.sub.50=440 μm, D.sub.90=767 μm and D.sub.100=1132 μm combined with 80% CEM I 42.5 cement was prepared. The resultant powder blend was mixed with water (in a weight to weight ratio water to powder blend of 0.6) to form a cement slurry (cement paste) at 60° C. The mixture was fully sealed and with water on the surface and cured. Shrinkage of the hardened cement slurry was determined by means of length change measurements using a micrometer. The results of the test are presented at FIG. 1. Results for a composition according to the invention (top) are compared with the results of CEM I 42.5 (bottom).

EXAMPLE 2

Formulation with Low Stiffness

(33) A formulation with 7 wt. % of polyvinyl alcohol with ester value of 8 mg KOH/g, viscosity 28 mPa.Math.s (of a 4 (N) solution in water at 20 ° C.) and D.sub.10=233 μm, D.sub.50=440 μm, D.sub.90=767 μm and D.sub.100=1132 μm combined with 60 wt. % cement CEM I 42.5, 19 wt. % limestone and 14 wt. % fly ash was prepared. The resultant powder blend was mixed with water (in a weight to weight ratio water to powder blend of 0.6) to form a cement slurry (cement paste) at 20° C. The mixture was fully sealed with water on the surface and cured . up to 28 days. Then the direct tensile strength of the hardened cement slurry was determined (following AASHTO T314-07) and stiffness was calculated from the strain-stress diagrams. The results of the test are presented at Table 1 and compared with the results of CEM I 42.5.

(34) TABLE-US-00001 TABLE 1 Results of stiffness calculation E (N/mm.sup.2) Std CEM I 42.5 1.520 0.11 Formulation with PVA 0.891 0.09

Example 3

Demonstration of Physical Bond Between Cement Calcium Phases and Polyvinyl Alcohol

(35) A formulation with 7 wt. % of polyvinyl alcohol with ester value of 8 mg KOH/g , viscosity 28 mPa.Math.s (of a 4% solution in water at 20 ° C.) and D.sub.10=233 μm, D.sub.50=440 μm, D.sub.90=767 μm and D.sub.100=1132 μm combined with 60 wt. % cement CEM I 42.5, 19% limestone and 14 wt. % fly ash was prepared. The sample was cured after mixing at 60° C. with water (in a weight to weight ratio water to powder blend of 0.6) and fully sealed with water on the surface up to 28 days.

(36) Then the cured sample was examined by means of SEM microscopy. The results are presented in FIGS. 2A and 2B. What is noticed is that there are portlanclite phases bound with polymer phases.

Example 4

Comparison of Cement Paste According to the Invention with a Standard Cement Paste on Properties Relevant for Paving Application

(37) Direct tensile strength (AASHTO T314-07) tests were performed after 28 days of water curing.

(38) Stiffness was determined by means of four point bending test (NEN-EN 12697-26) on concrete samples after 28 days of water curing for three different temperatures T=−10, 5 and 20° C. The test were performed on 50×50×450 mm prisms.

(39) Fatigue was measured by means of four point bending (NEN-EN 12697-24) on concrete samples at 30 Hz, using different strain levels (90,120,180 and 210 microstrain) at 20° C. The tests were performed on 50×50×450 mm prisms.

(40) Leutner shear test was performed on asphalt—concrete samples for two different temperatures according to standard prEN 12697-48:2011 after 28 days of water curing. Test samples were made by casting 6 cm concrete on an asphalt concrete plate and using cores of 10 cm diameter from the combination plate for the test.

(41) Compressive and bending strength was measured on standard cement mortars according to EN 196-1 after 1, 2, 7 and 28 days. The strain-stress diagrams were acquired and stiffness was calculated.

(42) Table 2 shows the Average Results of the direct tensile strength test.

(43) TABLE-US-00002 TABLE 2 Tensile dL at strength Fmax Stiffness (MPa) (mm) (N/mm2) Reference 2.16 0.12 1.4 cement paste according to 2.20 0.26 0.8 the invention (flexible paste)

(44) The results show that cement paste according to the invention exhibits lower stiffness while it can elongate (dL) more than twice as the reference cement paste before failure occurs. This is an indication that the material has a ductile fracture behaviour, which behaviour was confirmed by a plotting a force-displacement diagram (FIG. 3, reference at the left, flexible paste according to the invention at the right).

(45) The diagram in FIG. 4 shows the stiffness-temperature dependency at 8 Hz (reference=top line, concrete according to the invention=bottom line) using the 4 point bending test. The dependency between stiffness and temperature is higher compared to conventional concrete with a difference of approximately 1800 MPa between low temperature (−10° C.) and high temperature (20° C.). Compared to asphalt, the stiffness of a concrete according to the invention varies less as a function of temperature a lower dependency on temperature. In this respect it can thus can be seen as a product category on its own.

(46) An interesting aspect describing the behaviour of the flexible concrete according to the invention in fatigue is that there was an initial drop in stiffness after only a few cycles. Thereafter the samples endured many more cycles until the test was stopped without significant change in stiffness. The sample after this test was intact and no cracks were detected. This behaviour is illustrated for a sample tested at 120 micro-strain in FIG. 5.

(47) The Leutner shear test results showed an average shear strength of 2.01 MPa at 10° C. and of 1.53 MPa at 20° C. The two layers had a good adhesion and the shear strength was higher than the requirement for thin coating; i.e. a tensile strength at 10° C. of 1.5 MPa.

(48) In summary, from the results of the various tests it was concluded that a flexible concrete according to the invention (made using a powder blend according to the invention) has a ductile behaviour in all different mixes tested: paste, mortar and concrete. This property distinguishes the flexible concrete from normal concrete mixes. The ductility presented can have an effect in how a road is constructed and allow for less or no joints that will increase driving comfort. This property will not compromise the environmentally friendly aspect of concrete roads as the material remains a cement based material.

(49) Another important property of the flexible concrete is that the ductility is not directly connected to its strength which allows strength optimization without sacrificing the ductile character. This is also not common for normal concrete where there is a relationship between mechanical properties and elasticity. The flexible concrete presented an excellent fatigue performance which indicates that a pavement can withstand a lot of cycles of loading and unloading before failure occurs. This means that the flexible concrete has good durability allowing less repairs. A combination of this property with high durability expected due to cementitious character of the flexible concrete makes it an excellent option for pavements.

(50) The stiffness of the flexible concrete lies in the area of asphalt instead in that of concrete and there is some dependency with temperature and frequency but it is less strong than for asphalt. This means that Flexible concrete will be less sensitive to temperature variation.

(51) Usage of this material can vary as it has a good affinity both with concrete and with asphalt. This would allow usage in different pavement layers on top of already existing layers as a combination layer or even as a repair material.