US20220267212A1 - Inorganic polymers and use thereof in composite materials - Google Patents

Inorganic polymers and use thereof in composite materials Download PDF

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US20220267212A1
US20220267212A1 US17/629,547 US202017629547A US2022267212A1 US 20220267212 A1 US20220267212 A1 US 20220267212A1 US 202017629547 A US202017629547 A US 202017629547A US 2022267212 A1 US2022267212 A1 US 2022267212A1
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calcium aluminate
waterglass
concrete
water
aggregates
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Hossein Ehsaei
Bernd Spangenberg
Sidon Futterknecht
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Agemos Ag
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Definitions

  • the invention is situated in the field of inorganic chemistry and relates to an inorganic polymeric material based on a modified waterglass that can be used, for example, as a concrete substitute or ceramic substitute, to a method for producing it, and to composite materials which can be produced from it.
  • Concrete is a very widespread building material which has for a long time been used for a whole swath of different applications.
  • the concrete and its properties vary here in accordance with the applications. It may be necessary, for instance, to use particularly chemically stable varieties of concrete for the building, for instance, of harbor installations exposed to salt water; concrete can be used in applications where dynamic cyclical stresses are particularly severe, such as heavy-load traffic sections, railroad ties, airport taxiways, etc.; severe flexural and/or compressive stresses have to be countered in the construction of span bridges and high-rise buildings, etc.
  • option D has not yet reached a sufficient state of technical development; see Ellis Gartner, Tongbo Sui, “ Alternative cement clinkers ”, Cement and Concrete Research 114 (2016) 27-39.
  • CO 2 neutrality by 2050 is unachievable with Portland cement, and with the alternative variants thereof that are currently under discussion by the experts.
  • geopolymers alkali-activated cements
  • geopolymers which can be formed from fly ash or granulated slag in conjunction with waterglass Portland cement-like binders.
  • new, negatively charged Al(IV) centers tetrahedrally coordinated
  • Geopolymers therefore are not formed automatically at room temperature. It is instead necessary to supply heat for the formation of the negative Al centers.
  • ceramics are commonly understood to be shaped from an unfired material at room temperature and to acquire their desired, typical materials properties thereafter, as a result of a temperature treatment at usually above 800° C. Shaping occasionally takes place at an elevated temperature as well, or even by way of melt flow with subsequent crystallization.
  • WO 1997 006120 A1 discloses a method for rapid curing of lightweight concrete containing aggregates, e.g., EPS, Styropor, expanded day, pumice or the like, where a curing fluid, consisting of waterglass or of mixtures of waterglass and water, is applied to or introduced into the layer of lightweight concrete.
  • aggregates e.g., EPS, Styropor, expanded day, pumice or the like
  • a curing fluid consisting of waterglass or of mixtures of waterglass and water
  • WO 2003078349 A1 discloses a fly ash-based, geopolymeric binder for the production of slurries, mortars and concretes or for fixation of waste, said binder containing 70 to 94 percent by weight of power station fly ash with a measured surface area of 150-600 m 2 /kg and 5 to 15 percent by weight of an alkaline activator, the activator consisting of a mixture of alkaline hydroxide and alkaline silicate, waterglass for example, with this activator containing 5 to 15 percent by weight of Me 2 O and having an SiO 2 /Me 2 O ratio in the range from 0.6 to 1.5, where Me is Na or K.
  • EP 0641748 B1 (SCHANZE) relates to a waterglass-based material for securing wall plugs, threaded rods and the like in cavities, especially drilled holes, in concrete, stone and brick masonry, with at least one finely particulate, high-activity coreactant, such as SiO 2 and/or Al 2 O 3 , for example, more particularly from waste materials, and also with fillers, such as finely ground quartz and/or silica sand, for example, the material being characterized in that the waterglass, more particularly potassium waterglass, has a molar ratio of SiO 2 to alkali metal oxide of greater than 1.4, preferably 1.45-1.60, but in any case less than 2, and in that the material additionally contains, per 100 parts by weight of waterglass, 10 to 40, preferably 20 to 30 parts by weight of a curing agent in the form of a compound which neutralizes the alkali metal of the waterglass with elimination of an acid which is stronger than silicic acid.
  • coreactant such as SiO 2
  • One of the desired qualities is for the provision of a material which can be used as a substitute for concrete, having at least the strength of concrete, while being superior to concrete in terms of temperature stability and CO 2 balance, and enabling the use of desert sand and fine sand as aggregate material.
  • the problem addressed by the present invention was therefore critically that of providing substitute materials for the above-stated applications and also for further fields of use such as 3D printing, the eco-friendly binding of dusts, salts and pollutants, the production of coating materials for renovation purposes, for example, or building materials for interior finishing.
  • a first subject of the invention relates to an inorganic polymer containing Si, Al, Ca, alkali metal and O, which is distinguished by the fact that in a 27 Al MAS-NMR spectrum of the solid, compared with the 27 Al MAS-NMR spectrum of calcium aluminate, there is an additional signal whose chemical shift lies between that of the main peak of calcium aluminate and the calcium aluminate peak next upfield to the main peak.
  • the inorganic polymer is distinguished more particularly by the additional fact that in a solid-state IR spectrum it has a band at about 950-910 cm ⁇ 1 .
  • the concrete substitute of the invention is produced from waterglass, calcium aluminate, water and alkali metal hydroxide (preferably NaOH and/or KOH); the material therefore contains Si, Al, Ca, an alkali metal (preferably Na and/or K) and O.
  • alkali metal hydroxide preferably NaOH and/or KOH
  • the inorganic polymer of the invention can be identified via 27 Al MAS-NMR spectroscopy and so distinguished from the starting materials and from conventional geopolymers, etc.
  • 27 Al MAS-NMR spectroscopy and so distinguished from the starting materials and from conventional geopolymers, etc.
  • the literature there are numerous indications regarding the interpretation of such 27 Al spectra, from, for example, C. Gervais, K. J. D. MacKenzie, M. E. Smith, “Multiple magnetic field 27 AL solid state NMR study of the calcium aluminates CaAl 4 O 7 and CaAl 22 O 19 ” in Magn. Reson. Chem. 2001, 39, 23-28; from K. J. D. MacKenzie, I. W. M. Brown, R. H.
  • the present reaction is a covalent bond formation between Al and Si tetrahedra and not a hydration reaction.
  • pure calcium aluminate gives a sharp signal at 78 ppm, which is assigned to the negatively charged Al tetrahedra, and a broader signal at 12 ppm, which is assigned to hexa coordinated Al atoms.
  • the tetrahedron signal of the aluminum at 78 ppm disappears completely in this case, since tetra coordinated aluminum is converted completely into hexa coordinated aluminum.
  • the signal at 12 ppm therefore rises by the same degree as the signal at 78 ppm falls. As stated, with an excess of water, the signal at 78 ppm disappears entirely.
  • the 27 Al MAS-NMR signal of the aluminum tetrahedra used at 78 ppm (to be precise: 77.7 ppm) in conjunction with the signal between 59 and 65 ppm is characteristic.
  • the spectral ratio provides unambiguous characterization of the new bonding species.
  • the ratio of the area values of the signal around 65 ppm (the actual bonding signal from —O—Si—O—Al—O bonds) to the signal at 78 ppm (the signal of the —O—Al—O— bonds) runs from 0 (only —O—Al—O bonds in the calcium aluminate) to more than 10.
  • the figure is bounded in the upper range by the recognition of the signal at 78 ppm for Si/Al ratios close to 1.
  • the signal at 78 ppm becomes very small, possibly close to zero, since almost all of the entire calcium aluminate i/Al ratio will have been consumed by reaction. It is possible here to specify a signal-to-noise ratio of the baseline to a signal at 78 ppm of about 3 as a recognition limit.
  • the main peak at about 78 ppm is characteristic for calcium aluminate and is not found, for example, either in the spectrum of tobermorite or in the spectrum of Roman concrete (see “ Unlocking the secrets of Al - tobermorite in Roman seawater concrete ” by Marie D. Jackson, Sejung R. Chae, Sean R. Mulcahy, Cagle Meral, Rae Taylor, Penghui Li, Abdul-Hamid Emwas, Juhyuk Moon, Seyoon Yoon, Gabriele Vola, Hans-Rudolf Wenk, and Paulo J. M. Monteiro, Cement and Concrete Research, Volume 36, Issue 1, January 2006, pages 18-29).
  • the material of the invention is therefore characterized in that in a 27 Al MAS-NMR spectrum in the range of 0-100 ppm (when using AlCl 3 .6H 2 O as external standard) it has the three peaks of calcium aluminate and additionally a signal between the main peak and the next peak upfield, it being possible for this signal to be present as a shoulder.
  • the formation of new bonds of course changes the relative peak heights as compared with those in the spectrum of calcium aluminate.
  • the IR spectrum of the solid material of the invention preferably displays a characteristic band around 950-910 cm ⁇ 1 .
  • Conventional geopolymers vibrate here at somewhat higher wavenumbers, between 950-1000 cm ⁇ 1 .
  • Also observable in the IR spectrum are two characteristic shifts of the water bands at about 1390 cm ⁇ 1 and at a signal between 2800 and 3000 cm ⁇ 1 (see FIG. 10 ).
  • the inorganic polymers of the invention have the following preferred composition:
  • the material of the invention has a molar ratio of alkali metal cations (generally Na + and/or K + ) to calcium of about 1:1 to about 1:5 and more particularly about 1:2.
  • a further subject of the invention relates to a method for producing the inorganic polymer, comprising or consisting of the following steps:
  • the compensating charge of the negatively charged Al tetrahedra changes from Ca 2+ to the added alkali metal ions (e.g., K + or Na + ).
  • the exchanged calcium ions are released completely in the form of Ca(OH) 2 .
  • the precipitation of the Ca(OH) 2 is the driving force of the reaction, and calcium aluminate is therefore essential for the reaction. It is possible to use more calcium aluminate than is needed for the stoichiometric bonding of the Na + ions by the negatively charged Al tetrahedra. If less calcium aluminate is used, the blocks which are formed no longer remain water-stable.
  • the ratio of Si tetrahedra and Al ⁇ tetrahedra is freely adjustable in an Si/Al range from 1/12 to 1/1.
  • the preselected Si/Al ⁇ ratio determines the amount of Ca aluminate to be used (as source of Al ⁇ tetrahedra) and the amount of waterglass to be used (as the source of Si tetrahedra).
  • the desired compressive and flexural tensile strengths are adjusted.
  • the highest compressive strength is achieved at an Si/Al ⁇ ratio of 1/8.
  • FIG. 1 shows the compressive strengths attained for various Si/Al ⁇ ratios (reaction with sodium waterglass, NaOH, calcium aluminate, and various amounts of finely ground quartz for establishing identical initial viscosities in the reaction mixture).
  • a mixture of this kind consisting of pure waterglass and calcium aluminate, will not react, since the free base for the activation (e.g., NaOH) is missing. Mixtures are therefore reactive only from an Si/Al ratio ⁇ 1.
  • the upper limit for the proportion of alkali is imposed by the viscosity of the alkali (in the form of an aqueous solution).
  • the lower limit on the mixtures which are realizable is situated at a ratio of about Si/Al ⁇ 1:8. Larger amounts of calcium aluminate (for ratios between 1/8 and 1/12) can be mixed homogeneously with the (undiluted) waterglass only if water is added. The result, however, is that the unwanted competing reaction of hydration of the calcium aluminate occurs, leading to less stable products. Ratios therefore make sense only from a ratio of Si/Al ⁇ 0.125 (i.e. 1/8).
  • silicon nanoparticles are among the species suitable as waterglasses or Si tetrahedron sources.
  • SiO 2 nanoparticles (such as Kostrosol 1540) likewise react with calcium aluminate, instead of waterglass. 10 g of Kostrosol, mixed with 3 g of NaOH and 20 g of calcium aluminate, become solid within 3 min.
  • the proportion of inert materials can be increased up to 80%.
  • the percentage ratios listed above therefore fall at most to 1/5 of the above values. Accordingly, the value for the calcium aluminate content does not fall below 5.26% for any mixture.
  • the amount of OH ⁇ ions used determines the reaction rate, as does the amount of Al tetrahedra. If a high concentration of OH ⁇ ions is used, the mixture reacts more quickly than when using a lower OH ⁇ ion concentration. A high concentration of Al tetrahedra has the same effect as a high OH ⁇ ion concentration. Generally speaking, the greater the amount of aluminum tetrahedra and the greater the amount of NaOH in the mixture, the faster the binder cures. The cure times can be set freely between a few minutes (for an Si/Al ratio of 1:12) and several hours (for an Si/Al ⁇ 1).
  • the calcium aluminates used consist generally of 29 wt % CaO and 71 wt % Al 2 O 3 , corresponding approximately to a 3:1 mixture of CA and CA 2 , for which the corresponding empirical formula is (CaO) 4 (Al 2 O 3 ) 5 (C 4 A 5 ) with a molar mass of 734.
  • the reactive aluminates take up the following maximum amounts of water:
  • the present reaction here is a covalent bond formation between Al and Si tetrahedra and not a hydration reaction, in which a solid microstructure with crystal formation is formed. Accordingly, the calcium aluminate need not necessarily have been calcined; it is necessary only for Al tetrahedra to be present with calcium as the counterion! Accordingly, the calcium aluminate to be consumed by reaction may also be prepared wet-chemically at room temperature from sodium aluminate and CaCl 2 or CaSO 4 .
  • Waterglasses are usually produced from sand and Na and/or K carbonate. They consist of readily water-soluble silicates with a negative charge which is compensated by monovalent countercations (M + ).
  • waterglasses which have an organic radical such as a propyl radical (e.g., Protectosil WS808 from Evonik); they may be used alone or in a mixture with purely inorganic waterglasses. Where waterglasses of these kinds with an organic radical are used, it is possible to produce water-repellent surfaces.
  • an organic radical such as a propyl radical (e.g., Protectosil WS808 from Evonik)
  • a propyl radical e.g., Protectosil WS808 from Evonik
  • sodium waterglass sometimes also referred to as sodium silicate
  • potassium waterglass sometimes also referred to as potassium silicate
  • One embodiment comprises a mixture of sodium and potassium waterglass, such as a 90:10 to 10:90 mixture, for example.
  • Waterglasses with s values up to around 8 are known.
  • waterglasses having an s value of 0.4-5 are used.
  • Aqueous solutions of waterglasses are viscous.
  • sodium waterglasses lead generally to a higher viscosity than potassium waterglasses.
  • the inorganic polymer of the invention it is possible to start, for example, from commercial waterglass solutions having a solids content of about 22 to about 52 wt %.
  • the second essential component for producing the material of the invention is an alkali metal hydroxide, preferably NaOH and/or KOH. Commercially available alkali metal hydroxides can be used without purification.
  • a further essential starting material is calcium aluminate; it is possible, for example, to use a commercially available calcium aluminate such as Secar® 71 from Kerneos Inc. or one from Almatis GmbH such as CA-14 or CA-270.
  • a commercially available calcium aluminate such as Secar® 71 from Kerneos Inc. or one from Almatis GmbH such as CA-14 or CA-270.
  • water here, there is no need for distilled or deionized water (though it can be used)—instead, mains water or even salt water can be used, since the reaction for production is alkali-tolerant.
  • first waterglass (or waterglass solution), alkali metal hydroxide and water are brought into contact and then the calcium aluminate is mixed in. It is optionally also possible to mix in one or more aggregates.
  • the aggregates are selected preferably from finely ground rock, coarse broken stone, and sand (e.g., sea sand, river sand, fine sand and desert sand); in the case of conventional cement/concrete, only sharp-edge sand with a mean particle size of >2000 ⁇ m can be used, whereas in the present invention it is also possible to use fine sand and desert sand composed of particles rounded by grinding, with a mean particle size ⁇ 150 ⁇ m (particle size determined by sieving; weight average).
  • additives to be mixed in as well, selected for example from iron phosphate, calcium phosphate, magnesium phosphate, iron oxides, lead oxides, BaSO 4 , MgSO 4 , CaSO 4 , Al 2 O 3 , metakaolin, kaolin, inorganic pigments, wollastonite, rockwool, and mixtures thereof.
  • the supply of heat is not necessary for the reaction, but may—if necessary—be considered for the purpose of accelerating curing. It has been found that curing takes place at between about ⁇ 24° C. and +50° C. and even that curing under water is possible. Curing takes place preferably at temperatures in the range from about 25 to about 40° C.
  • the viscosity of the reaction solutions can be adjusted by varying the amounts of the starting materials in a range from 25 to 700 mPa (at 20° C.).
  • the reaction solutions in the lower viscosity range are also suitable for 3D printing.
  • the cure time may be adjusted between 50 sec and 40 min.
  • the cure time may be adjusted, for example, via the amount of water and the calcium aluminate fraction.
  • the anionic polymer of the invention may both be produced from a medium-viscosity liquid (consisting of waterglass solution and alkali metal hydroxide) and a powder (calcium aluminate and optionally aggregates), mixed for example in a ratio of about 1:1 (the liquid component in this case is stable for at least 5 months), and be produced from a liquid phase (aqueous alkali metal hydroxide; long stability) and a high-viscosity suspension which contains waterglass solution, calcium aluminate and, where appropriate, aggregates (similar to mortar, stable for 1 week) in a ratio, for example, of 1:20 to 1:50, where the method with liquid phase and high viscosity suspension would be suitable for 3D printing. Ultimate hardness is achieved after about 21 days. Where fine sands having a particle diameter of ⁇ 500 ⁇ m are used as aggregate, it has proven advantageous first to mix the fine sand with waterglass and alkali and then to add the calcium aluminate.
  • the figure reported for the proportional CO 2 emissions in the example formulas, based on (present-day) concrete, relates to the CO 2 emissions of waterglass, NaOH and calcium aluminate when they are produced 100% from solar power.
  • the production of the composite materials of the invention as a concrete substitute, conversely, may be produced with up to 70% lower CO 2 emission, relative to an equivalent standard concrete.
  • FIG. 12 shows an overview of possible applications of the VITAN® composite material of the invention in the concrete substitutes segment.
  • the mixtures are foamable and are therefore very generally suitable for upgrading and renovating work around the house, both for professionals and for home improvers.
  • preparations preferably in the form of 2-component systems, may be offered and sold in a cartridge, for example, in the form of spray mortar, troweling compound or fillers, for example.
  • the solid material features temperature stability of well above 1000° C., so making the material suitable, for example, for high-temperature applications (e.g., as a thermal solar store) or as a protective casing for lithium-ion batteries, for example.
  • high-temperature applications e.g., as a thermal solar store
  • protective casing for lithium-ion batteries for example.
  • hybrid materials such as, for example, composites with plastics or metals (e.g., aluminum).
  • the material is notable for compressive strength of up to 180 N/mm 2 and hence achieves levels twice as high as conventional concrete. Furthermore, the flexural tensile strength is up to 17 N/mm 2 (measured according to DIN 1048) and hence achieves approximately three times the level of conventional concrete. Moreover, the material of the invention can be heated to glowing red in the flame from a Bunsen burner (around 1200° C.) and subjected to shock cooling in water without breaking or fracturing. This is true even when the temperature change is frequent and repeated. The material, accordingly, can be regarded as stable to temperature change with temperature changes by more than 100° C., preferably more than 200° C., especially preferably more than 500° C.
  • a rate of temperature change of greater than 100° C./min, preferably greater than 200° C./min, more particularly greater than 500° C./min, very preferably greater than 1000° C./min; the rate of temperature change here is preferably, indeed, greater than 1000° C./30 sec, preferably 1000° C./15 sec.
  • Fibers contemplated include inorganic fibers such as CNTs, glass fibers, metal fibers and mixtures thereof, and also organic materials such as coir, bamboo or sisal.
  • the length of the fibers may be greater than 0.3 mm, preferably more than 1 mm, and preferably less than 5 cm, preferably less than 1 cm.
  • the stated fibers may be embedded in the form of fabrics, in which case the fibers within a fabric may be longer than the stated upper limits, since here there is a small risk of the blocking of pumps, mixers, etc. by excessively long fibers. It may be mentioned that the properties may be improved by the fibers in a manner known per se.
  • the material is also suitable for lightweight construction and dry construction, since high flexural tensile strengths are achieved even with little filling material, and this is conducive to the use of thin structures. For particularly exacting fire protection requirements, there are of course limits on the aggregates.
  • One particular embodiment is obtained with wood or fibers as aggregate, in the form of pressboard panels.
  • the mixture for producing the material of the invention (i.e., the reaction mixture prior to hardening) forms stable mixtures and is therefore also suitable for the bound enclosure of pollutants and radioactive wastes.
  • Lyophilic compounds of the silane type such as octyl triethoxysilane, for example, are capable of lyophilizing the surfaces if they are admixed in amounts of about 0.5 to 3 wt % to the binder. This makes not only the surface but also the entire substance water-repellent. In this way it is possible to carry out sanding without the lyophilized product losing its water-repellent character.
  • the admixing of the waterglasses Rhodarsil R51T (tripotassium methylsilanetriolate, a methyl siliconate) and Protektosil WS 808 (tripotassium propylsilanetriolate, a propyl siliconate) at between a few % to 100% (as a waterglass replacement) enables comprehensive lipophilization of the surfaces.
  • a further subject of the present invention relates to a composite material comprising or consisting of
  • composite material is used synonymously with the terms “solid composition” or “molding”.
  • the aggregates in this case may be selected from the group consisting of sand, coarse broken stone, finely ground quartz, rubber, organic polymers, wood, fibers, salts or pollutants and mixtures thereof.
  • Particularly preferred composite materials are those for which the aggregate is marine sand, desert sand or fine sand having a mean particle diameter of ⁇ 150 ⁇ m.
  • the composite materials are typically notable in that they comprise or consist of
  • the composite material may be an adhesive bonding agent, a coating material, a binder, a material for 3D printing, a ceramic, a concrete substitute or a cement substitute.
  • a further example are fiber composite materials, i.e., composite materials of the inorganic polymers with fibers such as sisal, bamboo, hemp and the like.
  • the fiber composite materials are suitable, for example, for producing components, such as water tanks, which are otherwise commonly produced from plastics.
  • the composite material may also be a wood composite material, as a substitute for pressboard panels, for example.
  • Wood composite materials according to the invention are notable for diverse positive properties; in particular, they are formaldehyde-free, nonflammable, stable to water, and have a fungicidal effect deriving from their alkalinity.
  • a further subject of the invention relates to a method for producing a composite material, comprising or consisting of the following steps:
  • a further subject of the invention relates to the use of the inorganic polymers as described above for producing adhesive bonding agents, coating materials, binders, materials for 3D printing, fiber composites, wood composites, ceramics, concrete substitutes or cement substitutes, preferably in amounts of about 5 to about 80 wt %, preferably about 15 to about 65 wt % and more particularly about 25 to about 50 wt %.
  • the density was determined by determining the volume and the weight of a rectangular specimen and calculating the density as weight/volume.
  • the compressive strength of the samples was measured using a Z250 universal testing machine from Zwick/Roell.
  • the compressive forces (in N) were plotted as a graph against the deformation distance.
  • the maximum pressure reached was placed in relation to the surface area (mm 2 ) of the sample.
  • Examples 5-7 used the following waterglass-water mixtures:
  • WG1 9.92 g of NaOH, dissolved in 20 g of water, mixed with 100.2 g of Na38/40
  • WG2 19.98 g of NaOH, dissolved in 10 g of water, mixed with 100.6 g of Na38/40
  • the concrete substitute was produced from 40 g of Almatis® CA-14 and 19.4 g of WG1; the mixture was solid after 32 min and had a gray color. The density was found to be 2.21 g/cm 3 and the compressive strength 101.3 N/mm 2 . (Sample B1)
  • the concrete substitute was produced from 40 g of Almatis® CA-14 and 9.48 g of WG1; the mixture was solid after 3-4 min and had a white color. (Sample C1)
  • the concrete substitute was produced from 40 g of Almatis® CA-14 and 28.86 g of WG2; the mixture was solid after 20 min and had a gray color. The density was found to be 1.97 g/cm 3 .
  • FIGS. 2-4 The 27 Al MAS-NMR spectra of Examples 5-7 are shown in FIGS. 2-4 .
  • FIG. 1 shows, for comparison, the 27 Al MAS-NMR spectrum of Almatis® CA-14.
  • Tables 1A to 1C below give peak areas, peak heights and also cure times and compressive strengths for inorganic polymers of the invention having different Si/Al ratios:
  • K35 Betolin K35 from Woellner
  • KOH 100 g of KOH
  • Si/Al ratio 0.33 100 g of Na38/40 (Betol 38/40 from Woellner), 10 g of NaOH, 10 g of water, 250 g of calcium aluminate, 125 g of desert sand, solid after 12 min, with a compressive strength of 162 N/mm 2 .
  • Mixtures in accordance with the examples above with rapid curing are ideally suitable for 3D printing.
  • FIG. 1 Compressive strengths attained for different Si/Al ⁇ ratios (reaction with nsodium waterglass, NaOH, calcium aluminate and different amounts of finely ground quartz for setting identical initial viscosities for the reaction mixture).
  • FIG. 2 27 Al MAS-NMR spectrum (Si—Al ratio 0.875) with the binding peak maximum at 59.3 ppm and at 943 cm ⁇ 1 in the IR.
  • FIG. 3 27 Al MAS-NMR spectrum (Si—Al ratio 0.625) with the binding peak maximum at 59.1 ppm and at 940 cm ⁇ 1 in the IR.
  • FIG. 4 27 Al MAS-NMR spectrum (Si—Al ratio 0.375) with the binding peak maximum at 63.4 ppm and at 943 cm ⁇ 1 in the IR.
  • FIG. 5 27 Al MAS-NMR spectrum (Si—Al ratio 0.125) with the binding peak maximum at 65.0 ppm and at 952 cm ⁇ 1 in the IR.
  • FIG. 6 27 Al MAS-NMR spectrum of calcium aluminate (Almatis® C-14)
  • FIG. 7 27 Al MAS-NMR spectrum of the solid obtained in example 5
  • FIG. 8 27 Al MAS-NMR spectrum of the solid obtained in example 6
  • FIG. 9 27 Al MAS-NMR spectrum of the solid obtained in example 7
  • FIG. 10 IR spectrum of calcium aluminate, waterglass+NaOH and end product (after 8 min reaction time and after 80 min reaction time)
  • FIG. 11 a+b Kinetics of polymerization.
  • the figure shows the change over time in the IR absorption spectrum of a mixture of waterglass and calcium aluminate after activation with NaOH. Shown at the top is the change in the IR spectra in transmission between 650 and 2000 cm ⁇ 1 , at the bottom in absorption between 650 and 1200 cm ⁇ 1 . Absorptions above 1300 cm ⁇ 1 come from water. Particularly evident is the transformation of an Si—O—Si bonding into an Al—O—Si bonding with a shift from 995 to 930-960 cm ⁇ 1 as the dominant bonding.
  • FIG. 12 Overview of concrete applications.

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