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EP-4735400-A1 - MULTI-COMPONENT BINDER

EP4735400A1EP 4735400 A1EP4735400 A1EP 4735400A1EP-4735400-A1

Abstract

The invention relates to a multi-component binder which is flowable and solidifiable after the addition of water and forms strengthening phases when hardening. The multi-component binder comprises a first component containing clinker phases and a particulate second component, which has a pozzolanic effect; the second component is present in the form of secondary particles agglomerated from fine primary particles and is BET-surface area reduced with a BET surface area of in particular below 32 m2/g, and has: an aluminum-containing silicate portion and a calcium-containing carbonate portion, which may also be present together in secondary particles; an X-ray amorphous portion of at least 25% and/or a reaction enthalpy according to ASTM C 1897/20 of at least 150 J/g; and bound water.

Inventors

  • MÖLLER, Hendrik
  • HAMM, ANDREAS
  • FYLAK, Marc
  • HINDER, DANIEL
  • NEUMANN, THOMAS

Assignees

  • SCHWENK Zement GmbH & Co. KG

Dates

Publication Date
20260506
Application Date
20240620

Claims (19)

  1. 1. Multi-component binder which is flowable and solidifiable after the addition of water and hardens to form strength-giving phases, with a first component containing clinker phases and a particulate second component with a pozzolanic effect, characterized in that the second component is in the form of secondary particles agglomerated from fine primary particles with a reduced BET surface area and a BET surface area of in particular less than 32 m 2 /g, has an aluminium-containing silicate portion and a calcium-containing carbonate portion also present together in secondary particles, has an X-ray amorphous portion of at least 25% and/or a reaction heat development according to ASTM C 1897/20 of at least 150 J/g, and has bound water.
  2. 2. Binder according to claim 1, in which the second component has an activity index SAI28 according to DIN EN 450-1 of at least 78%, and in particular the SAI 2 8 measured in percent is related to the reaction heat development r measured in J/g in the relationship f r r+65 - t < SAI28 < fr r+65+t, with f r in the range [0.08; 0.14], in particular [0.1; 0.12] and t is 15, preferably 10, in particular 7, and/or the amorphous portion x measured in percent is related to the relationship f x x+65 - 1 < SAI28 < fx-x+65+t, with f x in the range [0.75; 0.85], in particular [0.78; 0.82] and t is 15, preferably 10, in particular 7.
  3. 3. Binder according to claim 1 or 2, in which the second component has a value of less than 1.2 g/100 g in a methylene blue test, and in particular between the methylene blue value m measured in g/100 g and the SAI 2 8 measured in percent, the relationship f m -rn+104 - tm < SAI 2 8 ^ fm m+104+tm applies, with f m in the range [-24; -16], in particular [-22; -18] and tm equal to 20, preferably equal to 16, in particular equal to 12.
  4. 4. Binder according to one of the preceding claims, in which the bound water correlates with a thermogravimetrically determined mass loss from 130°C to 400°C of at least 1%, preferably at least 2%, in particular at least 3%.
  5. 5. Binder according to one of the preceding claims, in which the mass loss w measured in percent is related to the SAI 2 8 measured in percent in the relationship fw-w+70 - tw < SAl28 < fw w+70+tw, with f w in the range [5; 11], in particular [7; 10] and tw equal to 15, preferably equal to 12, in particular equal to 10, and/or with the amorphous portion x measured in percent in the relationship f xw x -0.9 - txw <w< f xw x -0.9+txw, with f xw in the range [0.05; 0.11], in particular [0.06; 0.1] and txw equal to 1.2, preferably equal to 0.8.
  6. 6. Binder according to one of the preceding claims, in which the second component has a proportion of reactive SiC>2 according to DIN EN 197-1 of greater than 12%, preferably greater than 15%, in particular greater than 20%, in particular a proportion of reactive AI2O3 is at least 10%.
  7. 7. Binder according to claim 1, in which the X-ray amorphous portion is an X-ray amorphous portion generated at least in part by an increase in the internal energy of the particles of the second component by means of mechanically induced energy input simultaneously at the same point of action on the silicate portion and the carbonate portion.
  8. 8. Binder according to claim 7, in which the exposure site is an exposure site comprising an attainable volume of at least 2000 l, preferably at least 4000 l, in particular at least 6000 l, of which at least 10%, preferably at least 15%, in particular at least 20% and/or at most 60%, further preferably at most 50%, in particular at most 40% is simultaneously accessible to the material experiencing the energy input.
  9. 9. Binder according to claim 7 or 8, in which the exposure site is a site at which, in addition to the mechanically induced energy input, a fine grinding of the silicate portion and/or carbonate portion takes place starting from a starting material supplied to the exposure site, and in particular is an exposure site with an average residence time of the silicate portion and the carbonate portion which does not exceed one hour, preferably does not exceed 50 minutes, in particular does not exceed 40 minutes.
  10. 10. Binder according to one of claims 7 to 9, in which the exposure site is an exposure site under an atmosphere that is in particular in motion, and/or an exposure site under a temperature of not higher than 250°C, preferably not higher than 170°C, more preferably not higher than 140°C, in particular not higher than 120°C.
  11. 11. Binder according to one of claims 7 to 10, in which the silicate portion as well as the carbonate portion are portions originating from a starting material supplied to the site of action, and the starting material is at least partially and preferably consists predominantly of a clay material, in particular at least 25% by weight, preferably at least 35% by weight and particularly preferably at least 40% by weight of clay minerals including all amorphous constituents of the clay material which belong to the group of kaolinites, illites, smectites, chlorites, pyrophyllites or the vermiculite group, or mixtures thereof.
  12. 12. Binder according to one of claims 7 to 11, wherein the increase in internal energy is at least 50 J per gram of material at the site of action, preferably more than 100 J/g, in particular more than 200 J/g.
  13. 13. Binder according to one of the preceding claims, in which the second component has a weight ratio of carbonate content calculated in [CO2] to a silicate content calculated in [SiO2] of at least 10%, preferably at least 20%, in particular at least 30% and/or at most 2, more preferably at most 1.5, in particular at most 1.
  14. 14. Binder according to claim 13, in which the ratio of carbonate content to silicate content is contributed by an amount of a carbonate material added separately to the clay material of the starting material at least before it reaches the site of action.
  15. 15. Binder according to one of claims 7 to 14, in which the place of action is the grinding chamber of a mill operated in continuous operation, in particular a stirred ball mill of in particular horizontal design, which is operated with an output of at least 100 kW per m 3 of grinding chamber volume, preferably with a throughput of at least 60 kg per hour, and preferably with an energy supply of more than 200 kWh, but preferably also less than 1200 kWh per ton of treated material.
  16. 16. Binder according to one of the preceding claims, in which the first component is contained in a weight proportion of at least 20%, in particular at least 30% and the second component in a weight proportion of at least 5%, preferably of at least 10%, more preferably at least 15%, in particular of at least 20%.
  17. 17. Material which can be used as a cement constituent in the form of the second component of a multi-component binder according to one of the preceding claims.
  18. 18. Deposit comprising a quantity of not less than 2 tonnes, preferably not less than 4 tonnes, in particular not less than 10 tonnes of a material according to claim 17.
  19. 19. Concrete material with a multi-component binder according to one of claims 1 to 16.

Description

MULTI-COMPONENT BINDING AGENT This task concerns a multi-component binder which is flowable and solidifiable after the addition of water and hardens to form strength-giving phases, with a first component containing clinker phases and a particulate second component with a pozzolanic effect. The so-called cement clinker can later form the strength-giving phases, so-called CSH and CASH phases, through hydraulic reactions when the binding agent is used. The clinker phases from Portland cements (worldwide Portland cement demand is around 4 billion tons annually) often represent the main component of such binding agents. Just as Portland cements thus form clinker phases such binders, multi-component binders such as composite cements have additional components in the form of main cement components or secondary components/additives for various purposes. Such additives for e.g. cements, concretes or other hydraulic binders or building materials are widely known in technology and serve to improve individual or multiple properties of the building materials in use right up to the parts made from them. They also provide a range of properties in addition to the by-products from other processes such as steel or energy production that are already known in the historical development of building material systems based on such building materials and have long been and will continue to be used. Bulk raw materials are available for the provision of such multi-component binders, such as natural (trass, pumice, etc.) or artificial pozzolans (fly ash) or slags (granulated blast furnace slag, LD slag, etc.). Their use is regulated by standards. For example, the European cement standard DIN EN 197 is the first European harmonized product standard, which, due to its classifications, still leaves room for numerous different concrete implementations in accordance with the standard. The use of clays is limited for reasons of durability in numerous types of cement, directly or indirectly via their content in limestone powder as a possible main cement component. For example, according to DIN EN 197-1, the clay content in the main cement component limestone powder, determined using the methylene blue method according to DIN EN 933-9, must not exceed a value of 1.20 g/100 g. In addition, German and European regulations limit the clay content in aggregates to be used in concrete production to less than 0.5% and, in special cases, to less than 0.25%. There are also artificially produced substances, e.g. as pozzolanic substances such as typical and commercially available microsilica, which are used as concrete additives or main cement components, with their very high SiO2 contents, e.g. of 97% (e.g. white microsilica Q1 from BCK Bau-Chemie-Kontor Vertriebs-GmbH). A so-called EMC cement was developed at the Lulea University of Technology in Sweden and presented at the ICCC in Montreal in 2006. By grinding a raw material made of Portland cement and silica dust in vibrating mills, an increase in strength lasting for months was achieved, with a compressive strength even up to 100% higher after one day of age. On the other hand, EP 0 517 869 B1 describes how a carbonate donor is added to a Portland cement-based system with the aim of rapidly achieving higher strengths. Additives such as sodium carbonate, sodium sulfate and calcium hydroxide are described in DE 4223494 C2, also for achieving high early strengths. Treated glassy volcanic rocks such as air-dried pumicete can also act as additives or substitutes, but with significantly longer treatment times than suggested in DD 141788 A1 in connection with increasing the solubility of aluminum oxide from clays, namely preferably in the range of 8 to 16 hours, which eliminates the disadvantage of an otherwise very limited binding capacity of volcanic glasses and thus opens the way for such volcanic glasses to be used as cement additives, as described in DE 2816322. Slags are also proposed as usable residual materials from other processes. For example, EP 3 322 534 B1 describes a process for the fine grinding of LD steelworks slag. The grinding process with subsequent sifting is intended to release belite and alite surfaces of the finely ground slag particles. In addition, the pressure crushing that takes place increases the reactive surface and leads to increased hydraulic reactivity. Similarly, US 66,30,022 B2 paves the way for crushed sands as a cement additive, which are generated during the production of granite gravel and would otherwise have to be disposed of as waste. EP 2 253 600 A1 proposes to supplement cement clinker with calcined clays, such as metakaolin. In the temperature range between 600°C and 920°C, the clay mineral kaolinite is converted into a highly reactive pozzolanic substance, which can be classified as natural tempered pozzolan (Q). This is also considered to have a more favourable CO2 balance, because if one tonne of cement clinker (which correlates with a release of 800 kg