Binder based on activated ground granulated blast furnace slag useful for forming a concrete type material

Abstract

A binder material useful for forming a concrete type material includes, calculated on a dry, water and carbon dioxide free basis, a base component constituting 50-95 wt % of the binder material, the base component having ground granulated blast furnace slag and an activator component constituting 5-50 wt % of the binder material. The activator component includes aluminum sulfate and a sodium hydroxide generating compound. The final binder material includes, calculated on a dry, water and carbon dioxide free basis, ground granulated blast-furnace slag 35-95 wt %, aluminum sulfate AI.sub.2(SO.sub.4).sub.3 1-25 wt %, and sodium hydroxide generating compound 4-35 wt %.

Claims

1. A concrete material, wherein it comprises a binder material and an aggregate material, wherein the binder material comprising, calculated on a dry, water and carbon dioxide free basis; i) a base component constituting 50-95 wt % of the binder material, said base component comprising ground granulated blast furnace slag, wherein the base component comprises at least 20 wt % aluminum oxide, Al.sub.2O.sub.3, calculated on a dry, water and carbon dioxide free basis, and ii) an activator component constituting 5-50 wt % of the binder material, said activator component comprising: a. aluminum sulfate, and b. sodium hydroxide generating compound, said sodium hydroxide generating compound comprising sodium carbonate, Na.sub.2CO.sub.3, and calcium oxide, CaO, wherein the binder material comprises, calculated on a dry, water and carbon dioxide free basis; ground granulated blast furnace slag: 35-95 wt % aluminum sulfate, Al.sub.2(SO.sub.4).sub.3: 1-25 wt % and sodium hydroxide generating compound: 4-35 wt %.

2. The concrete material according to claim 1, wherein the binder material comprises aluminum sulfate, calculated on a dry, water and carbon dioxide free basis, calculated as Al.sub.2(SO.sub.4).sub.3, in an amount of: 10-20 wt %.

3. The concrete material according to claim 1, wherein the binder material comprises sodium carbonate, calculated on a dry, water and carbon dioxide free basis, calculated as Na.sub.2CO.sub.3, in an amount of: 10-20 wt %.

4. The concrete material according to claim 1, wherein the base component comprises at least 15 wt % silicon oxide, SiO.sub.2, calculated on a dry, water and carbon dioxide free basis.

5. The concrete material according to claim 1, wherein the binder material comprises aluminum sulfate, calculated on a dry, water and carbon dioxide free basis, calculated as Al.sub.2(SO.sub.4).sub.3, in an amount of: 5-20 wt %.

6. The concrete material according to claim 1, wherein the binder material comprises sodium carbonate, calculated on a dry, water and carbon dioxide free basis, calculated as Na.sub.2CO.sub.3, in an amount of: 2-25 wt %, and calcium oxide, calculated on a dry, water and carbon dioxide free basis, calculated as CaO, in an amount of: 1.5-5 wt %.

7. The concrete material according to claim 1, wherein the binder material comprises maximum 2 wt % of calcium sulfate, CaSO.sub.4, calculated on a dry, water and carbon dioxide free basis.

8. The concrete material according to claim 1, wherein the binder material further comprises a sodium complex binder.

9. The concrete material according to claim 1, wherein the activator component comprises aluminum sulfate, Al.sub.2(SO.sub.4).sub.3, and sodium hydroxide generating compound in such a relation that a mixture of 1 part by weight of the binder material with 0.3 parts by weight of water results in a pH value of at least 12.5.

10. The concrete material according to claim 1, wherein the base component comprises, in addition to ground granulated blast furnace slag, at least one substance selected from the group consisting of: clay, marl, fly ash, and aluminum oxide.

11. The concrete material according to claim 1, wherein the binder material is ground to a Blaine number of at least 3500 cm.sup.2/g.

12. A method of producing a concrete material, comprising mixing the binder material according to claim 1, with water and an aggregate material, and allowing the mixture to harden to form the concrete material.

13. The method according to claim 12, further comprising mixing 1 part by weight of the binder material with 2-8 parts by weight of the aggregate material, and adding 0.2-1.5 parts by weight of water.

Description

Comparative Example

(1) A Comparative Example concrete material was prepared using a prior art cement. The Comparative Example concrete material comprising the following ingredients: 1) Portland cement, purchased as Portlandzement EN 197-1, Chromatarm, CEII/B-M (S-L) 32.5 R, from the company Zementfabrik Leube, Salzburg Gartenau, AT, calculated on a dry, water and carbon dioxide free basis: 250 parts by weight, 2) CEN Normsand (same type as Example 1): 670 parts by weight, 3) Water: 80 parts by weight,

(2) The total weight of the concrete mixture of the Comparative Example was 100 kg.

(3) The concrete mixture was used to form test samples of the concrete type material made according to the Comparative Example, similar to what was made for Example 2.

(4) Test Results

(5) The test samples prepared in Example 2 and in the Comparative Example 1 were tested in accordance with test standard DIN 1045. The results were the following:

(6) TABLE-US-00004 TABLE 1 Compressive strength of test sample according to Example 2 and according to Comparative Example Characteristic cylinder compres- sive strength (DIN 1045) Comparative [N/mm.sup.2] Example 2 Example Drill core 1 day old 15.8 11.5 Drill core 3 days old 34.8 15.9 Drill core 7 days old 42.9 20.2 Drill core 28 days old 50.8 32.8 Drill core 56 days old 52.3 34.5

(7) From Table 1 it is clear that the concrete type of material of Example 2 has a substantially higher mechanical strength than the prior art material of the Comparative Example, based on Portland cement. For the Drill core having an age of 28 days the concrete type of Example 2 has 54% higher compressive strength than the concrete of the Comparative Example.

Example 3

(8) A binder material according to the above mentioned Example 2 according to the present invention was tested further.

(9) Preparation of the binder paste was done as follows. 500 g of binder was mixed with water in a mortar mixer for 3 minutes at low speed, then filled into a vicat ring and the penetration depth was measured with a vicat instrument. Water was added until a penetration depth of (62) mm between dipstick and base plate had been reached.

(10) Determination of compressive strength in accordance with NORM EN 196-1 (April 2005), was performed. Prisms with a size of 4416 cm were prepared for the test. The mortar was compacted with a vibration table. Then the prisms were stored in humid boxes at 20 C./90% relative humidity. Compressive strength was determined using a universal compression testing machine at a load increase of 2400200 N/s.

(11) Tests were also performed on the material according to the present invention with regards to strength of the cement. Determinations were made in accordance with NORM EN 196-1, par 1, after 1 and 7 days.

(12) TABLE-US-00005 TABLE 2 Test results of test sample according to Example 3. Bending Dimensions tensile Compressive Age of the of specimen Raw density strength strength specimen [mm] [g/cm.sup.3] [N/mm.sup.2] [N/mm.sup.2] 24 hours 40 40 160 2.24 4.0 13.9 .sup.7 days 40 40 160 2.18 5.6 34.2

Example 4

(13) A first binder material according to Example 4 was prepared by using a base component, an activator component and optionally a sodium complex binder.

(14) The base component had the following composition, in wt % of the final binder material:

(15) Ground granulated blast furnace slag (GGBS), in the form of the product AHWZ Gemahlener Httensand, available from the company Firma Bernegger GmbH, Molln, AT, the product having a Blaine number of 5010 cm.sup.2/g, and a residue after sieving through a 45 micrometer sieve of 7.5 wt %, the amount calculated on a dry, water and carbon dioxide free basis:

(16) 75.0 wt %

(17) Metakaolin:

(18) 9.5 wt %

(19) Thus, the base component constituted totally 84.5 wt %, calculated on a dry, water and carbon dioxide free basis, of the final binder material.

(20) Furthermore, the binder material according to Example 4 comprised an activator component. The activator component had the following composition, in wt % of the final binder material:

(21) Sodium carbonate, purchased as Natrium carbonat light, CAS 497-19-8, from Soda Polska Ciech, Inowroclaw, PL, the amount calculated as Na.sub.2CO.sub.3, on a dry, water and carbon dioxide free basis:

(22) 12.5 wt %

(23) Calcium oxide, purchased as Kalkoxyd from Kalkwerk Dullinger, Salzburg-Elsbethen, AT, the amount calculated as CaO, on a dry, water and carbon dioxide free basis:

(24) 3 wt %

(25) Thus, the activator component constituted totally 15.5 wt % calculated on a dry, water and carbon dioxide free basis, of the final binder material.

(26) Optionally, the final binder material may also comprise a sodium complex binder, for example EDTA (Ethylenediaminetetraacetic Acid):

(27) up to 1 wt %

(28) Hence, the composition of the final binder material according to Example 4 may be the following, calculated on a dry, water and carbon dioxide free basis:

(29) TABLE-US-00006 Base component: 84.5 wt % Activator component: 15.5 wt % TOTAL final binder material: 100 wt %

(30) *If the complex binder amounts to less than 1 wt %, or if there is no complex binder at all, the amounts of the base component and the activator component are increased correspondingly.

(31) The base component and the activator component indicated above, but no sodium complex binder, were supplied to a mixer of the type PFT Multimix, available from Knauf PFT GmbH & Co. KG, Iphofen, DE, and where mixed with each other to form a homogenous powder mixture constituting the first final binder material of Example 4.

(32) The first final binder material of Example 4 as described above was then used to prepare a concrete type material. The concrete type material was formed by mixing the following components in a concrete mixer (AL-KO TOP 1402 R) during one hour, the concrete type material comprising the following ingredients: 4) Final binder material (according to Example 1) calculated on a dry, water and carbon dioxide free basis: 250 parts by weight, 5) CEN Normsand, sand according to DIN-EN 196-1, available from the company Normensand GmbH, Beckum, DE: 670 parts by weight, 6) Water: 80 parts by weight.

(33) The total weight of the mixture was about 10 kg.

(34) The pH of the mixture of the final binder material, aggregate and water according to Example 4 was found to be pH 13.

(35) A second binder material according to Example 4 was prepared by using a base component, an activator component and optionally a sodium complex binder according to an embodiment of the present invention.

(36) The base component had the following composition, in wt % of the final binder material:

(37) Ground granulated blast furnace slag (GGBS), in the form of the product AHWZ Gemahlener Httensand, available from the company Firma Bernegger GmbH, Molln, AT, the product having a Blaine number of 5010 cm.sup.2/g, and a residue after sieving through a 45 micrometer sieve of 7.5 wt %, the amount calculated on a dry, water and carbon dioxide free basis:

(38) 70.0 wt %

(39) Amorphous aluminum oxide, as Aluminiumoxyd trocken SO143, obtained from Dadco Alumina Ltd, the facilities at Stade, DE, the amount calculated as Al.sub.2O.sub.3, on a dry, water and carbon dioxide free basis:

(40) 10 wt %

(41) Thus, the base component constituted totally 80.0 wt %, calculated on a dry, water and carbon dioxide free basis, of the final binder material.

(42) Furthermore, the binder material comprised an activator component. The activator component had the following composition, in wt % of the final binder material:

(43) Sodium carbonate, purchased as Natrium carbonat light, CAS 497-19-8, from Soda Polska Ciech, Inowroclaw, PL, the amount calculated as Na.sub.2CO.sub.3, on a dry, water and carbon dioxide free basis:

(44) 17.0 wt %

(45) Calcium oxide, purchased as Kalkoxyd from Kalkwerk Dullinger, Salzburg-Elsbethen, AT, the amount calculated as CaO, on a dry, water and carbon dioxide free basis:

(46) 3 wt %

(47) Thus, the activator component constituted totally 20 wt % calculated on a dry, water and carbon dioxide free basis, of the final binder material.

(48) Optionally, the final binder material may also comprise a sodium complex binder, for example EDTA (Ethylenediaminetetraacetic Acid):

(49) up to 1 wt %

(50) Hence, the composition of the second final binder material according to Example 4 may be the following, calculated on a dry, water and carbon dioxide free basis:

(51) TABLE-US-00007 Base component: 80.0 wt % Activator component: 20.0 wt % TOTAL final binder material: 100 wt %

(52) *If the complex binder amounts to less than 1 wt %, or if there is no complex binder at all, the amounts of the base component and the activator component are increased correspondingly.

(53) The base component and the activator component indicated above, but no sodium complex binder, were supplied to a mixer of the type PFT Multimix, available from Knauf PFT GmbH & Co. KG, Iphofen, DE, and where mixed with each other to form a homogenous powder mixture constituting the final binder material of Example 4.

(54) The final binder material of Example 4 as described above was then used to prepare a concrete type material. The concrete type material was formed by mixing the following components in a concrete mixer (AL-KO TOP 1402 R) during one hour, the concrete type material comprising the following ingredients: 7) Final binder material (according to Example 4) calculated on a dry, water and carbon dioxide free basis: 250 parts by weight, 8) CEN Normsand, sand according to DIN-EN 196-1, available from the company Normensand GmbH, Beckum, DE: 670 parts by weight, 9) Water: 80 parts by weight.

(55) The total weight of the mixture was about 10 kg.

(56) The pH of the mixture of the final binder material, aggregate and water according to Example 4 was found to be pH 13.

(57) The tests in Example 4 show the effect of the aluminium ions used according to the present invention. The tests were also made on formulations with and without aluminion containing material. Determinations of the strength were made in accordance with NORM EN 196-1, par 1, after 1 day.

(58) TABLE-US-00008 TABLE 3 Test results of test sample according to Example 4. Compressive Compressive strength strength Dimensions [N/mm.sup.2] [N/mm.sup.2] Age of the of specimen Formula with Formula without specimen [mm] Aluminium Aluminium 24 hours 40 40 160 13.8 10.2

(59) As can be seen from the results the use of aluminium plays an important role of the strength property when using an alkali activated slag binder as according to the present invention.

(60) It will be appreciated that numerous modifications of the embodiments described above are possible within the scope of the appended claims.

(61) To summarize, a binder material useful for forming a concrete type material comprises, calculated on a dry, water and carbon dioxide free basis, a base component constituting 50-95 wt % of the binder material and comprising ground granulated blast furnace slag, and an activator component constituting 5-50 wt % of the binder material and comprising aluminum sulfate, and a sodium hydroxide generating compound. The final binder material comprises, calculated on a dry, water and carbon dioxide free basis: ground granulated blast-furnace slag: 35-95 wt %, aluminum sulfate, Al.sub.2(SO.sub.4).sub.3: 1-25 wt %, sodium hydroxide generating compound: 4-35 wt %.