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Use of a Colloidal Polymer Inorganic Hybrid Material as a Construction Composition Additive

20250136510 ยท 2025-05-01

    Inventors

    Cpc classification

    International classification

    Abstract

    A colloidal polymer inorganic hybrid material is used as an additive for a construction composition comprising a binder system, the binder system comprising a cementitious binder and at least one supplementary cementitious material, wherein the supplementary cementitious material(s) comprise(s) a calcined clay material, the clay material including at least one non-kaolinitic clay material. The hybrid material comprises at least one polyvalent metal cation, at least one polymeric dispersant which comprises anionic and/or anionogenic groups and polyether side chains, at least one anion which is able to form a low-solubility salt with the polyvalent metal cation, wherein the polyvalent metal cation is present in an amount corresponding to the following formula (1):

    [00001] 0 . 1 0 .Math. i z K , i n K , i m D 1 5 ( 1 ) and the anion is present in an amount corresponding to the following formula (2):

    [00002] 0 . 0 1 .Math. l z A , l n A , l .Math. i z K , i n K , i 1 ( 2 ) wherein is the charge density of the polymeric, m.sub.D is the amount of polymeric dispersant, z.sub.K,i is the valency of the polyvalent metal cation, n.sub.K,i is the molar amount of the polyvalent metal cation, z.sub.A,l is the valency of the anion, n.sub.A,l is the molar amount of the anion, the indices i, and l are independent of one another and are an integer greater than 0, i is the number of different kinds of polyvalent metal cations and l is the number of different kinds of anions which are able to form a low-solubility salt with the metal cation. The use of the colloidal polymer inorganic hybrid material allows for an effective slump retention.

    Claims

    1. A method of preparing a construction composition comprising a binder system, the method comprising adding a colloidal polymer inorganic hybrid material to the binder system, the binder system comprising a cementitious binder and at least one supplementary cementitious material, wherein the supplementary cementitious material comprises a calcined clay material, comprising at least 10 wt.-% of calcined clay obtained from a non-kaolinitic clay, the hybrid material comprising at least one polyvalent metal cation selected from Fe.sup.3+, Fe.sup.2+, Zn.sup.2+, Mn.sup.2+, Cu.sup.2+, Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, and mixtures thereof, at least one polymeric dispersant which comprises anionic and/or anionogenic groups and polyether side chains, at least one anion which together with the polyvalent metal cation is able to form a low-solubility salt having a solubility in water under standard conditions of 20 C. and atmospheric pressure less than 5 g/L, wherein the anion is selected from carbonate, oxalate, silicate, phosphate, polyphosphate, phosphite, borate, aluminate, sulfate, and mixtures thereof, wherein the polyvalent metal cation is present in an amount corresponding to the following formula (1): 0.1 .Math. i z K , i n K , i m D 1 5 ( 1 ) and the anion is present in an amount corresponding to the following formula (2): 0.01 .Math. l z A , l n A , l .Math. i z K , i n K , i 1 ( 2 ) wherein is the charge density of the polymeric dispersant in meq/g of solid content, m.sub.D is the amount of polymeric dispersant in g of solid content, z.sub.K,i is the valency of the polyvalent metal cation, n.sub.K,i is the amount of the polyvalent metal cation in mmol, z.sub.A,l is the valency of the anion, n.sub.A,l is the amount of the anion in mmol, the indices i, and l are independent of one another and are an integer greater than 0, i is the number of different kinds of polyvalent metal cations and l is the number of different kinds of anions which are able to form a low-solubility salt with the metal cation.

    2. The method according to claim 1, wherein the polyvalent metal cation and the anion are present in an amount corresponding to the following formula (3): 0 . 2 5 ( .Math. i z K , i n K , i ) 2 ( .Math. l z A , l n A , l ) ( m D ) 7 0 . ( 3 )

    3. The method according to claim 1, wherein the polyvalent metal cation is selected from Fe.sup.3+, Fe.sup.2+, Zn.sup.2+, Mn.sup.2+, Cu.sup.2+, Ca.sup.2+, and mixtures thereof.

    4. The method according to claim 1, wherein the anion which is able to form a low-solubility salt with the polyvalent metal cation is selected from silicate, phosphate, polyphosphate, aluminate, and mixtures thereof.

    5. The method according to claim 1, wherein the charge density of the polymeric dispersant is in the range of 0.510.sup.3 to 5.0 meq/g of solid content.

    6. The method according to claim 1, wherein the polymeric dispersant comprises structural units of the general formulae (Ia), (Ib), (Ic) and/or (Id): ##STR00013## wherein R.sup.1 is H, C.sub.1-C.sub.4 alkyl, CH.sub.2COOH or CH.sub.2COXR.sup.3A; X is NH(C.sub.n1H.sub.2n1) or O(C.sub.n1H.sub.2n1) with n1=1, 2, 3 or 4, the nitrogen atom or the oxygen atom being bonded to the CO group; R.sup.2 is OM, PO.sub.3M.sub.2, or OPO.sub.3M.sub.2; or X is a chemical bond and R.sup.2 is OM; R.sup.3A is PO.sub.3M.sub.2, or OPO.sub.3M.sub.2; ##STR00014## wherein R.sup.3 is H or C.sub.1-C.sub.4 alkyl; n is 0, 1, 2, 3 or 4; R.sup.4 is PO.sub.3M.sub.2, or OPO.sub.3M.sub.2; ##STR00015## wherein R.sup.5 is H or C.sub.1-C.sub.4 alkyl; Z is O or NR; R.sup.7 is H, (C.sub.n1H.sub.2n1)OH, (C.sub.n1H.sub.2n1)PO.sub.3M.sub.2, (C.sub.n1H.sub.2n1)OPO.sub.3M.sub.2, (C.sub.6H.sub.4)PO.sub.3M.sub.2, or (C.sub.6H.sub.4)OPO.sub.3M.sub.2, and n1 is 1, 2, 3 or 4; ##STR00016## wherein R.sup.6 is H or C.sub.1-C.sub.4 alkyl; Q is NR.sup.7 or O; R.sup.7 is H, (C.sub.n1H.sub.2n1)OH, (C.sub.n1H.sub.2n1)PO.sub.3M.sub.2, (C.sub.n1H.sub.2n1)OPO.sub.3M.sub.2, (C.sub.6H.sub.4)PO.sub.3M.sub.2, or (C.sub.6H.sub.4)OPO.sub.3M.sub.2, n1 is 1, 2, 3 or 4; where each M independently is H or a cation equivalent; and structural units of the general formulae (IIa), (IIb), (IIc) and/or (IId): ##STR00017## wherein R.sup.10, R.sup.11 and R.sup.12 independently of one another are H or C.sub.1-C.sub.4 alkyl; Z.sup.2 is O or S; E is C.sub.2-C.sub.6 alkylene, cyclohexylene, CH.sub.2C.sub.6H.sub.10, 1,2-phenylene, 1,3-phenylene or 1,4-phenylene; G is O, NH or CONH; or E and G together are a chemical bond; A is C.sub.2-C.sub.5 alkylene or CH.sub.2CH(C.sub.6H.sub.5); n2 is 0, 1, 2, 3, 4 or 5; a is an integer from 2 to 350; R.sup.13 is H, an unbranched or branched C.sub.1-C.sub.4 alkyl group, CONH.sub.2 or COCH.sub.3; ##STR00018## wherein R.sup.16, R.sup.17 and R.sup.18 independently of one another are H or C.sub.1-C.sub.4 alkyl; E.sup.2 is C.sub.2-C.sub.6 alkylene, cyclohexylene, CH.sub.2C.sub.6H.sub.10, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, or is a chemical bond; A is C.sub.2-C.sub.5 alkylene or CH.sub.2CH(C.sub.6H.sub.5); n2 is 0, 1, 2, 3, 4 or 5; L is C.sub.2-C.sub.5 alkylene or CH.sub.2CH(C.sub.6H.sub.5); a is an integer from 2 to 350; d is an integer from 1 to 350; R.sup.19 is H or C.sub.1-C.sub.4 alkyl; and R.sup.20 is H or C.sub.1-C.sub.4 alkyl; ##STR00019## wherein R.sup.21, R.sup.22 and R.sup.23 independently are H or C.sub.1-C.sub.4 alkyl; W is O, NR.sup.25, or is N; V is 1 if W=O or NR.sup.25, and is 2 if W=N; A is C.sub.2-C.sub.5 alkylene or CH.sub.2CH(C.sub.6H.sub.5); a is an integer from 2 to 350; R.sup.24 is H or C.sub.1-C.sub.4 alkyl; R.sup.25 is H or C.sub.1-C.sub.4 alkyl; ##STR00020## wherein R.sup.6 is H or C.sub.1-C.sub.4 alkyl; Q is NR.sup.10, N or O; V is 1 if Q=O or NR.sup.10 and is 2 if Q=N; R.sup.10 is H or C.sub.1-C.sub.4 alkyl; R.sup.24 is H or C.sub.1-C.sub.4 alkyl; A is C.sub.2-C.sub.5 alkylene or CH.sub.2CH(C.sub.6H.sub.5); and a is an integer from 2 to 350; where each M independently is H or a cation equivalent.

    7. The method according to claim 6, wherein the polymeric dispersant comprises structural units of formulae (Ia) wherein R.sup.1 is H or methyl, X is a chemical bond and R.sup.2 is OM; (Id) wherein R.sup.6 is H or methyl, Q is O and R.sup.7 is H; and (IIa) wherein R.sup.10 and R.sup.12 are H, R.sup.11 is H or methyl, n2 is 0, 1 or 2, E is C.sub.2-C.sub.6 alkylene, G is O, or E and G together are a chemical bond, A is CH.sub.2CH.sub.2 and R.sup.13 is H.

    8. The method according to claim 1, wherein the molar mass of the polymeric dispersant is in the range of 10,000 g/mol to 80,000 g/mol.

    9. The method according to claim 1, wherein the molar mass of the polyether side chains is in the range of 500 g/mol to 8,000 g/mol.

    10. The method according to claim 1, wherein the polymeric dispersant is a polycondensation product which comprises the structural units (III), (IV) and (V): ##STR00021## wherein T is phenyl, naphthyl or heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N, O and S; n3 is 1 or 2; B is N, NH or O, with the proviso that n3 is 2 if B is N and n3 is 1 if B is NH or O; A is C.sub.2-C.sub.5 alkylene or CH.sub.2CH(C.sub.6H.sub.5); a2 is an integer from 1 to 300; R.sup.26 is H, C.sub.1-C.sub.10 alkyl, C.sub.5-C.sub.8 cycloalkyl, aryl, or heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N, O and S; where the structural unit (IV) is selected from the structural units (IVa) and (IVb) ##STR00022## wherein D is phenyl, naphthyl or heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N, O and S; E.sup.3 is N, NH or O, with the proviso that m is 2 if E.sup.3 is N and m is 1 if E.sup.3 is NH or O; A is C.sub.2-C.sub.5 alkylene or CH.sub.2CH(C.sub.6H.sub.5); b is an integer from 0 to 300; M independently is H or a cation equivalent; ##STR00023## wherein V.sup.2 is phenyl or naphthyl and is optionally substituted by 1 or two radicals selected from R.sup.8, OH, OR.sup.8, (CO)R.sup.8, COOM, COOR.sup.8, SO.sub.3R.sup.8 and NO.sub.2; R.sup.7A is COOM, OCH.sub.2COOM, SO.sub.3M or OPO.sub.3M.sub.2; M is H or a cation equivalent; and R.sup.8 is C.sub.1-C.sub.4 alkyl, phenyl, naphthyl, phenyl-C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 alkylphenyl ##STR00024## wherein R.sup.5 is H, CH.sub.3, COOH or substituted or unsubstituted phenyl or naphthyl; R.sup.6 is H, CH.sub.3, COOH or substituted or unsubstituted phenyl or naphthyl.

    11. The method according to claim 1, wherein the binder system comprises a carbonate rock powder selected from calcium carbonate-containing carbonate rock powder, limestone powder, and mixtures thereof.

    12. A construction composition comprising a colloidal polymer inorganic hybrid material as defined in claim 1 and a binder system, wherein the binder system comprises a cementitious binder and at least one supplementary cementitious material, wherein the supplementary cementitious material comprise a calcined clay material, comprising at least 10 wt.-% of calcined clay obtained from a non-kaolinitic clay.

    13. The construction composition according to claim 12, wherein the binder system additionally comprises a carbonate rock powder.

    14. The construction composition according to claim 12, wherein the calcined clay material has a BET value, as measured in accordance with DIN ISO 9277, in the range from 0.1 to 60 m.sup.2/g.

    15. The construction composition according to claim 12, wherein the binder system has a BET value, as measured in accordance with DIN ISO 9277, in the range from 0.1 to 40 m.sup.2/g.

    16. The method according to claim 3, wherein the polyvalent metal cation is selected from Fe.sup.3+, Fe.sup.2+, Ca.sup.2+, and mixtures thereof.

    17. The method according to claim 5, wherein the charge density of the polymeric dispersant is in the range of 0.710.sup.3 to 2.0 meq/g of solid content.

    18. The method according to claim 6, wherein in general formula (IIa) R.sup.10, R.sup.11 and R.sup.12 independently of one another are H or methyl; A is C.sub.2-C.sub.3 alkylene; and a is an integer from 10 to 150.

    19. The method according to claim 6, wherein in general formula (IIa) R.sup.10, R.sup.11 and R.sup.12 independently of one another are H or methyl; A is C.sub.2-C.sub.3 alkylene; and a is an integer from 20 to 100.

    20. The method according to claim 6, wherein in general formula (IIb) R.sup.16, R.sup.17 and R.sup.18 independently of one another are H; A is C.sub.2-C.sub.3 alkylene; L is C.sub.2-C.sub.3 alkylene; a is an integer from 10 to 150; and d is an integer from 10 to 150.

    21. The method according to claim 6, wherein in general formula (IIb) R.sup.16, R.sup.17 and R.sup.18 independently of one another are H; A is C.sub.2-C.sub.3 alkylene; L is C.sub.2-C.sub.3 alkylene; a is an integer from 20 to 100; AND d is an integer from 20 to 100.

    22. The method according to claim 6, wherein in general formula (IIc) R.sup.21, R.sup.22 and R.sup.23 independently are H; A is C.sub.2-C.sub.3 alkylene; and a is an integer from 10 to 150.

    23. The method according to claim 6, wherein in general formula (IIc) R.sup.21, R.sup.22 and R.sup.23 independently are H; A is C.sub.2-C.sub.3 alkylene; and a is an integer from 20 to 100.

    24. The method according to claim 6, wherein in general formula (IId) R.sup.6 is H; A is C.sub.2-C.sub.3 alkylene; and a is an integer from 10 to 150.

    25. The method according to claim 6, wherein in general formula (IId) R.sup.6 is H; A is C.sub.2-C.sub.3 alkylene; and a is an integer from 20 to 100.

    26. The construction composition according to claim 14, wherein the calcined clay material has a BET value, as measured in accordance with DIN ISO 9277, in the range from 1 to 40 m.sup.2/g.

    27. The construction composition according to claim 15, wherein the binder system has a BET value, as measured in accordance with DIN ISO 9277, in the range from 1 to 30 m.sup.2/g.

    Description

    [0224] The invention is described in more details by the accompanying drawings and the subsequent examples.

    [0225] FIG. 1 shows the results of a flow table test according to DIN EN 12350-5 for different mortars with conventional superplasticizers.

    [0226] FIG. 2 shows the results of a flow table test according to DIN EN 12350-5 for different mortars with colloidal polymer inorganic hybrid materials according to the invention.

    EXAMPLES

    Analytical Methods

    Size Exclusion Chromatography (SEC)

    [0227] The polymer solution was dissolved in the SEC eluent indicated below to yield a polymer concentration of 0.5 wt.-%. Subsequently, the solution was filtered through a syringe filter with a nylon membrane having a pore size of 0.45 m to obtain a filtrate. The injection volume of this filtrate was 100 L. The average molecular weights were determined on an SEC instrument from Shimadzu with the model LC-10AD VPCTO-10A VP, with a UV detector (SPD-10ASHIMADZU) and an RI detector (RID-10ASHIMADZU). [0228] Columns: OH-Pak SB-G [0229] Shodex OHpak-SB 804 HQ [0230] Shodex OHpak-803 HQ [0231] Shodex OHpak-802.5 HQ [0232] Eluent: 0.05 M aq. ammonium formate/MeOH mixture (91/9 parts by volume) [0233] Flow rate: 0.65 ml/min [0234] Temperature: 60 C. [0235] Injection: 100 L [0236] Detection: RI and UV (230 nm)

    [0237] The molecular weights of the polymers were measured by external calibration with polyethylene glycols standards from PSS Polymer Standards Service GmbH. Determination took place first of all relative to polyethylene glycol standards from the company PSS Polymer Standards Service GmbH. The masses of the polyethylene glycol standards were 682000, 164000, 114000, 57100, 40000, 26100, 22100, 12300, 6240, 3120, 2010, 970, 430, 194, and 106 g/mol. The molecular weight distribution curves of the standards were determined by the supplier via light scattering.

    Dynamic Light Scattering

    [0238] The particle size distribution was determined using a Malvern Zetasizer Nano ZS (Malvern Instruments GmbH, Rigipsstr. 19, 71083 Herrenberg). The software utilised for measurement and evaluation was the Malvern software package belonging to the instrument. The measurement principle was based on dynamic light scattering, more particularly on non-invasive backscattering. The particle size distribution measured corresponded to the hydrodynamic diameter Dh of the conglomerate composed of comb polymer, i.e., water reducer and inorganic core consisting of cations of the invention and anions of the invention.

    [0239] The results of the measurements were an intensity distribution against the particle size. From this distribution, the software determined an average particle size. The algorithm used was stored in the Malvern software. The samples were measured after 1 to 10 days. For this measurement, 0.1% by weight solutions of the conglomerates composed of water reducer and cation of the invention and anion of the invention were used. The solvent used was Milli-Q water, i.e., ultra-pure water having a resistance of 18.2 m cm. The sample was introduced into a single-use plastic cuvette and subjected to measurement at a temperature of 25 C. 10 runs/measurement and 2 measurements per sample were carried out. The only results evaluated were those which had a sufficiently high data quality, i.e., which corresponded to the standards of the instrument software.

    Pozzolanic Reactivity Test

    [0240] A cement model paste is prepared by mixing 11.11 g of the supplementary cementitious material (SCM), 33.33 g of portlandite (lab-grade, less than 5 wt.-% of CaCO.sub.3), 60 g of deionized water, 0.24 g of potassium hydroxide (lab-grade), 1.20 g of potassium sulfate (lab-grade) and 5.56 g of calcite (lab-grade, d.sub.50 5 to 15 m). All raw materials were preheated at 40 C. overnight before mixing.

    [0241] A calorimeter was set to 40 C. followed by calibration of the heat flow channels. Then, sealed reference flasks (containing approx. 9.4 g of deionized water to match the heat capacity of the samples) were inserted into the calorimeter and the system was left to stabilize (about 2 days). The baseline heat flows (both initial and final baseline) of each channel were determined for 180 min. Approximately 15 g (m.sub.p) of the freshly mixed cement model paste was introduced into heated sample flasks just after the mixing.

    [0242] The heat release is recorded over the course of 7 days. The cumulative heat (Heat) is calculated from 1.2 hours after the beginning of the calorimetry test onwards. The total heat release (H.sub.rescaled) is reported in J/(g SCM) as follows:

    [00007] H rescaled = Heat ( m p 0.0997 ) , [0243] wherein Heat is the cumulative heat in Joule and m.sub.p is the mass of the cement model paste in gram. 0.0997 is the weight fraction of the supplementary cementitious material in the paste sample.

    Mortar Slump Retention

    [0244] The procedure is analogous to DIN EN 12350-2, with the modification that a mini-slump cone (height: 15 cm, bottom width: 10 cm, top width: 5 cm) was used instead of a conventional Abrams cone. 2 L of the aqueous freshly mixed construction composition were filled into the mini-slump cone. The cone was filled completely immediately after mixing. Afterwards, the cone was placed on a flat surface, and lifted, and the slump of the mortar mix was measured. The slump of all mixes was adjusted to 11 cm by adjusting the dosage of the superplasticizer to allow for comparability.

    Early Strength Development for Mortars

    [0245] The adjusted mortar mixes were each filled into mortar steel prisms (16/4/4 cm), and after 24 h at a temperature of 20 C. and relative humidity of 98%, a hardened mortar prism was obtained. The hardened mortar prism was demolded and compressive strength was measured according to DIN EN 196-1.

    Compressive Strength of Concrete

    [0246] Different concrete mixes were prepared containing the same amount of water and 380 kg/m.sup.3 of total binder b).

    [0247] The concretes were mixed for four minutes in a Pemat ZK 50 concrete mixer. Superplasticizer was added after 2 minutes in 20% of the rest water. The required dosages are shown in the legend indicated as % bwob (by weight of binder system based on active matter, relative to the solids content).

    [0248] Compressive strength was measured after 24 h and 28 d after mixing the concrete according to DIN EN 12390-3.

    Concrete Flow and Concrete Slump Retention

    [0249] The flow table test according to DIN EN 12350-5 was used for measuring the flow at different times after concrete mixing.

    Synthesis of Polymeric Dispersants

    [0250] The polymeric dispersant P1 was based on the monomers acrylic acid, maleic acid and vinyloxybutylpolyethylene glycol 2000 g/mol. The molar ratio of acrylic acid to maleic acid was 5.3. Mw=34000 g/mol (determined by SEC). The solids content was 50% by weight. The synthesis of this type of polymer is described in WO 2010/066470.

    [0251] The polymeric dispersant P2 was a blend of two polymers: P2a (58 wt.-%) and P2b (42 wt.-%). P2a was polymeric dispersant P1. P2b was based on the monomers acrylic acid and isoprenyloxypolyethylene glycol 1100 g/mol. Mw=25000 g/mol (determined by SEC). The solids content was 50% by weight.

    [0252] The polymeric dispersant P3 was a condensate of the building blocks phenolpolyethylene glycol 1500 g/mol and phenoxyethanol phosphate. The molecular weight was 19000 g/mol. The synthesis is described in DE102004050395. The solids content was 50%.

    [0253] The polymeric dispersant P4 was based on the monomers acrylic acid and vinyloxybutylpolyethylene glycol 3000 g/mol. Mw=62000 g/mol (determined by SEC). The solids content was 50% by weight.

    [0254] The polymeric dispersant P5 was based on the monomers acrylic acid and vinyloxybutylpolyethylene glycol 3000 g/mol. Mw=43000 g/mol (determined by SEC). The solids content was 46% by weight.

    [0255] The polymeric dispersant P6 was a blend of two polymers: P6a (83 wt.-%) and P6b (17 wt.-%). P6a was polymeric dispersant P1. P6b was based on the monomers acrylic acid, maleic acid and vinyloxybutylpolyethylene glycol 5800 g/mol. The molar ratio of acrylic acid to maleic acid was 10.3. Mw=32000 g/mol (determined by SEC). The solids content was 45% by weight. The synthesis of this type of polymer is described in WO 2010/066470.

    [0256] The polymeric dispersant P7 was a blend of two polymers: P7a (86 wt.-%) and P7b (14 wt.-%). P7a was polymeric dispersant P1. P7b was based on the monomers acrylic acid, maleic acid and isoprenyloxypolyethylene glycol 1100 g/mol. Mw=43000 g/mol (determined by SEC). The solids content was 56% by weight.

    Composition of Calcined Clays

    [0257] XRD composition of two different calcined clays used for concrete testing are provided in Table 1. Amounts are provided in wt.-% of the calcined clay.

    TABLE-US-00001 TABLE 1 Liament .sup.[1] Arginotec .sup.[2] CaCO.sub.3 (calcite) 2.5 1.8 CaMg(CO.sub.3).sub.2 (dolomite) 1.9 0.3 glimmer (sericite/muscovite) clay (illite) 12.3 24.5 kaolinite 0.6 2.0 feldspar 6.0 8.0 gehlenite 2.3 other minerals (oxides) 3.2 1.9 SiO.sub.2 (quartz) 19.7 34.4 amorphous content (slag, fly ash, pozzolans) 51.5 27.1 BET surface area [m.sup.2/g] 4.114 27.797 .sup.[1] Producer: Liapor GmbH und Co. KG .sup.[2] Producer: Arginotec GmbH und Co. KG

    1. Preparation of Hybrid Materials

    [0258] The aqueous solutions of the polymeric dispersants described above were mixed with sodium aluminate (NaAlO.sub.2), calcium nitrate (Ca(NO.sub.3).sub.2), and sodium hydroxide to reach the target pH under stirring. Mixing was carried out in a 1 L glass beaker with magnetic stirrer at 300 rpm, temperature conditioned at 20 C.

    [0259] First, the solution of the polymeric dispersant was diluted with water. Subsequently, sodium aluminate was added and dissolved with stirring. Then, calcium nitrate was added under stirring. The alkaline agent was subsequently added until the target pH was reached. Amounts are indicated in Tables 2 and 3. All amounts are based on the active content.

    [0260] The hybrid materials of the invention proved to be storage stable. In particular, the samples of Tables 2 and 3 were stored for 6 months at 40 C., 20 C. and 4 C. The hybrid materials of the invention, as well as comparative additives A20 and A21, proved to be stable with respect to phase separation and retained their activity as slump retainers. Conversely, comparative additives A18 and A19 were found to be instable, forming a precipitate within 24 h of storage.

    TABLE-US-00002 TABLE 2 side chain charge molecular density solids weight [meq/g, content additive polymer [g/mol] dry] [%] pH A1 P1 2000 0.99 39.12 11.0 A2 P1 2000 0.99 39.35 10.5 A3 P1 2000 0.99 21.65 10.5 A4 P1 2000 0.99 21.27 10.0 A5 P1 2000 0.99 22.57 9.5 A6 P1 2000 0.99 23.33 10.0 A7 P1 2000 0.99 39.22 10.5 A8 P1 2000 0.99 8.50 10.5 A9 P1 2000 0.99 6.01 10.5 A10 P2 mixed, 1100 to 2000 1.34 39.22 10.5 A11 P3 1500 0.62 28.00 10.0 A12 P4 3000 0.73 33.83 10.0 A13 P5 3000 0.85 34.16 10.0 A14 P5 3000 0.85 33.80 9.5 A15 P5 3000 0.85 19.47 10.0 A16 P6 mixed, 2000 to 5800 1.05 23.16 10.5 A17 P7 mixed, 1100 to 2000 1.10 22.54 10.5 A18 P1 2000 0.99 44.59 11.0 A19 P1 2000 0.99 26.75 11.5 A20 P1 2000 0.99 24.38 11.5 A21 P4 3000 0.73 33.64 10.2

    TABLE-US-00003 TABLE 3 polymer metal cation inorganic anion ratio of ratio of ratio of [%, relative to [%, relative to [%, relative to formula formula formula additive solids content] solids content] solids content] (1) (2) (3) A1 36.11 2.60 0.42 0.89 0.26 3.43 A2 36.85 2.15 0.35 0.72 0.26 2.78 A3 19.98 1.44 0.23 0.88 0.26 3.41 A4 19.92 1.16 0.19 0.72 0.26 2.76 A5 20.00 0.28 0.04 0.17 0.26 0.67 A6 19.92 3.15 0.26 1.95 0.14 14.41 A7 33.40 5.71 0.11 2.11 0.03 65.88 A8 5.48 2.60 0.42 5.85 0.26 22.59 A9 2.99 2.60 0.42 10.72 0.26 41.42 A10 21.70 0.75 0.12 0.32 0.26 1.22 A11 20.02 7.50 0.48 3.68 0.10 35.46 A12 29.52 4.11 0.20 2.31 0.08 28.82 A13 29.71 4.11 0.35 1.99 0.14 14.69 A14 29.50 4.07 0.23 1.99 0.09 21.61 A15 15.02 4.11 0.35 3.94 0.14 29.06 A16 20.20 2.74 0.22 1.63 0.13 12.62 A17 19.58 2.74 0.22 1.67 0.13 12.88 A18 * 17.43 23.40 3.76 16.54 0.26 63.91 A19 * 19.92 2.87 3.96 1.59 2.22 0.72 A20 * 19.92 0.50 3.96 0.28 12.75 0.02 A21 * 29.52 4.11 0.02 2.31 0.009 268.02 * comparative examples

    2. Compressive Strength of OPC- and LC3-Based Mortars

    [0261] Table 4 shows two mortars according to DIN EN 196-1, with 1.350 g of sand (norm sand according to DIN EN 196-1) and a water to binder ratio 0.50. In particular, the difference in early compressive strength are examined for an Ordinary Portland Cement (Aalborg Portland, OPC, CEM I 52.5 N) in comparison to an LC3 system which achieves strength class 52.5 at 28 days, comprising OPC (as above), 16 to 18 wt.-% of calcined clay, and 16 to 18 wt.-% of limestone.

    TABLE-US-00004 TABLE 4 water to binder compressive strength cement additive system ratio (24 h, 20 C.) OPC 0.50 28.2 MPa LC3 system 0.50 19.5 MPa

    [0262] It is evident that early strength is significantly diminished in the LC3 system with calcined clay.

    3. Slump, Flow and Compressive Strength of Mortar with and without Inventive Additive

    [0263] Table 5 shows the influence of a traditional additive based on a superplasticizer and a retarder (abbreviated as T1) in comparison to an additive according to the invention on slump, flow and compressive strength. The results were carried out in mortar with the OPC and binder system of the previous experiment (Point 2 of Experimental Section). The sand was a siliceous sand with a granulometry from 0 to 4 mm (origin: Po river; available from Sabbie di Parma Srl). The water to binder system ratio was 0.44 in all three examples.

    [0264] As the traditional additive T1, a mixture of the polymer P2b (side chain molecular weight 1000 g/mol, charge density 1.70 mmol/g (dry), solids content 20 wt.-%) and sodium gluconate (solids content 5 wt.-%) was used. The weight ratio of P2b/sodium gluconate was 4/1. The total solids contents of the additive T1 was 25 weight %.

    [0265] The air entrainment of the mixes was controlled by adding a standard defoamer in an amount of 1 wt.-%, based on the amount of colloidal polymer inorganic hybrid material, relative to the solids content, for all the tests. The air percentage measured according EN 1015-7 was in the range of 3 to 4 vol.-%.

    TABLE-US-00005 TABLE 5 compressive slump/flow slump/flow slump/flow strength # binder system additive 0 min [cm] 30 min [cm] 60 min [cm] (24 h, 20 C.) 5-1 .sup.1 OPC .sup.2 T1 9.5/14.0 6.5/11.0 5.0/10.0 25 MPa 0.20% bwob 5-2 .sup.1 LC3 system .sup.2 T1 9.0/12.0 7.5/11.0 6.0/10.5 17 MPa 0.35% bwob 5-3 LC3 system .sup.2 A2 8.0/12.0 8.5/13.0 8.5/12.5 24 MPa 0.28% bwob 5-4 .sup.1 LC3 system .sup.2 P1 8.5/11.0 6.0/10.0 5.0/10.0 21 MPa 0.25% bwob 5-5 .sup.1 LC3 system .sup.2 A18 8.5/11.0 7.5/10.5 6.5/10.5 23 MPa 0.27% bwob 5-6 .sup.1 LC3 system .sup.2 A20 8.5/11.0 6.0/10.5 5.5/10.0 22 MPa 0.25% bwob .sup.1 comparative example .sup.2 as defined under item 2. bwob: by weight of binder system based on active matter, relative to the solids content mix design: 511 g of binder as indicated and 1460 g of siliceous sand (0 to 4 mm)

    [0266] As can be seen, the hybrid material of the invention significantly improves slump and flow retention after 30 min and after 60 min. Furthermore, the early compressive strength is comparable to that obtained by using OPC. The slump retention of A20 is not improved over the polymeric dispersant P1 (i.e. the polymeric dispersant contained in the colloidal polymer inorganic hybrid material A20), demonstrating the critical importance of formula (2).

    4. Slump, Flow and Compressive Strength of Concrete with and without Inventive Additive

    [0267] Two different calcined clays were used in the study, namely Liament and Arginotec (see Table 1) having different amorphous content and physisorption BET (results provided by XRD Rietveld analysis, BET measurements and laser granulometric measurements). As a limestone source, MS12 limestone powder from SH Minerals (ground limestone; D50: 5.5 m) was used. The calcined clay containing mixes included two different calcium sulfate sources (gypsum and anhydrite).

    [0268] Further, two different superplasticizers additives were used in the tests:

    [0269] Additive A2 as described above was used, i.e., a colloidal polymer inorganic hybrid material according to the invention. Furthermore, a conventional superplasticizer S1 was used, which was a polymer based on the monomers acrylic acid, hydroxypropyl acrylate and isoprenyloxypolyethylene glycol 1000 and 5800 g/mol. The molar ratio of acrylic acid to hydroxypropyl acrylate was 2.1. Mw=38000 g/mol, as determined by SEC. The solids content was 51% by weight).

    [0270] The compositions are given in Table 6, whereas the results are provided in FIGS. 1 and 2, as well as in Table 7.

    TABLE-US-00006 TABLE 6 Limestone Extraneous # Cement Source Calcined Clay Sulfate Source Additive MIX 1 .sup.1 OPC .sup.2 MS12 Liament anhydrite S1 190 kg/m.sup.3 57 kg/m.sup.3 114 kg/m.sup.3 19 kg/m.sup.3 0.26% bwob MIX 2 .sup.1 OPC .sup.2 MS12 Liament FGD gypsum .sup.3 S1 190 kg/m.sup.3 57 kg/m.sup.3 114 kg/m.sup.3 19 kg/m.sup.3 0.26% bwob MIX 3 .sup.1 OPC .sup.2 MS12 Arginotec anhydrite S1 190 kg/m.sup.3 57 kg/m.sup.3 114 kg/m.sup.3 19 kg/m.sup.3 0.52% bwob MIX 4 .sup.1 OPC .sup.2 MS12 Arginotec FGD gypsum .sup.3 S1 190 kg/m.sup.3 57 kg/m.sup.3 114 kg/m.sup.3 19 kg/m.sup.3 0.46% bwob MIX 5 OPC .sup.2 MS12 Liament anhydrite A2 190 kg/m.sup.3 57 kg/m.sup.3 114 kg/m.sup.3 19 kg/m.sup.3 0.30% bwob MIX 6 OPC .sup.2 MS12 Liament FGD gypsum .sup.3 A2 190 kg/m.sup.3 57 kg/m.sup.3 114 kg/m.sup.3 19 kg/m.sup.3 0.30% bwob MIX 7 OPC .sup.2 MS12 Arginotec anhydrite A2 190 kg/m.sup.3 57 kg/m.sup.3 114 kg/m.sup.3 19 kg/m.sup.3 0.65% bwob MIX 8 OPC .sup.2 MS12 Arginotec FGD gypsum .sup.3 A2 190 kg/m.sup.3 57 kg/m.sup.3 114 kg/m.sup.3 19 kg/m.sup.3 0.57% bwob .sup.1 comparative example .sup.2 Mergelstetten CEM I 52.5R .sup.3 gypsum from flue-gas desulphurization bwob: by weight of cement based on active matter, relative to the solids content mix design: 154 L/m.sup.3 water, 1095 kg/m.sup.3 river sand (0-4 mm natural sand and crushed aggregates (2-16 mm) obtained from Piederstorfer (origin: South-East Bavaria).

    [0271] FIG. 1 shows that in all tested mix designs slump and flow are significantly diminished over time when using the conventional superplasticizer S1(w/b=0.41).

    [0272] FIG. 2 shows that slump is maintained when using colloidal polymer inorganic hybrid materials according to the invention (A1, w/b=0.41). The concretes prepared with the colloidal polymer inorganic hybrid materials show similar slump retention independently of which calcium sulfate source (gypsum or anhydrite) and which calcined clay was used. Thus, the robustness of the hybrid material of the invention towards workability retention is far better than with the conventional superplasticizer when mixed into different calcined clay containing concretes.

    TABLE-US-00007 TABLE 7 Compressive Strength [MPa] After 24 h After 28 d MIX 1 12.25 69.95 MIX 5 14.06 80.45 MIX 2 11.62 67.05 MIX 6 13.75 76.65 MIX 3 15.10 62.40 MIX 7 16.85 72.50 MIX 4 13.95 57.50 MIX 8 17.65 67.55

    [0273] Table 7 shows that early strength development (24 h) of mixes containing calcined clay is very low compared to reference mixes 1 and 2 based on Ordinary Portland Cement. However, it was found that all tested LC3 mixes containing the hybrid material of the invention had higher 24 h strength and 28 d strength compared to the mixes with the conventional superplasticizer. Thus, the hybrid material of the invention has a positive impact on early and late strength development in LC3 based concrete mixes.

    5. Concrete Compressive Strength with and without Inventive Additive

    [0274] Additional concrete tests were carried out with the traditional superplasticizer T1 and with the hybrid material A2 of the invention. In Table 8, the mix design is provided for the experiments.

    TABLE-US-00008 TABLE 8 dosage [kg/m.sup.3] binder 300 limestone powder* 80 river sand, 0 to 4 mm** 1107 gravel, 12 to 19 mm*** 738 effective water 171 water to binder system ratio 0.57 *ground limestone (D50: 39.56 m) obtained from Granulati Dolomitici Peroglio Spa (origin: North-East Italy) **sand obtained from Mosole Spa (origin: North-East Italy) ***crushed aggregates obtained from Mosole Spa (origin: North-East Italy)

    [0275] The results are provided in Table 9. In all experiments, initial air entrainment was 1.5%.

    TABLE-US-00009 TABLE 9 compressive additive strength (active dosage based density (24 h, # cement on 100% solids content) [kg/m.sup.3] 20 C.) 5-1 .sup.1 OPC T1 2429 19.7 MPa (0.875 kg/m.sup.3) 5-2 .sup.1 LC3 system .sup.2 T1 2420 10.5 MPa (1.2 kg/m.sup.3) 5-3 LC3 system .sup.2 additive A2 2473 17.0 MPa (0.6 kg/m.sup.3) .sup.1 comparative example .sup.2 as defined under Point 2 of the Experimental Section: Compressive Strength of OPC- and LC3-Based Mortars

    [0276] It is evident that the hybrid material of the invention significantly improves early strength as compared to the LC3 system.