WO2023211268A1 - Béton activé par un alcali pour traverse de chemin de fer précontrainte - Google Patents

Béton activé par un alcali pour traverse de chemin de fer précontrainte Download PDF

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Publication number
WO2023211268A1
WO2023211268A1 PCT/NL2023/050215 NL2023050215W WO2023211268A1 WO 2023211268 A1 WO2023211268 A1 WO 2023211268A1 NL 2023050215 W NL2023050215 W NL 2023050215W WO 2023211268 A1 WO2023211268 A1 WO 2023211268A1
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WIPO (PCT)
Prior art keywords
alkali
concrete
prestressed
particle size
railway sleeper
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PCT/NL2023/050215
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English (en)
Inventor
Guang YE
Timo DIJKSTRA
Hua Dong
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Technische Universiteit Delft
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Publication of WO2023211268A1 publication Critical patent/WO2023211268A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/08—Slag cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • E—FIXED CONSTRUCTIONS
    • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
    • E01B—PERMANENT WAY; PERMANENT-WAY TOOLS; MACHINES FOR MAKING RAILWAYS OF ALL KINDS
    • E01B3/00—Transverse or longitudinal sleepers; Other means resting directly on the ballastway for supporting rails
    • E01B3/28—Transverse or longitudinal sleepers; Other means resting directly on the ballastway for supporting rails made from concrete or from natural or artificial stone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]

Definitions

  • the present invention is in the field of concrete mixtures, in particular an alkali- activated concrete, which can be used for a prestressed railway sleeper, a method of forming said concrete, and a prefabricate, such as pre-stressed elements, pre-cast elements, structural building elements, such as floors, walls, ceilings, supports, and frames.
  • the prefabricate has improved characteristics and for production, less carbon dioxide is required.
  • Concrete is a composite construction material composed primarily of aggregate, cement and water, with mortar being similar thereto, however using finer aggregates.
  • the aggregate is generally coarse gravel or crushed rocks such as limestone, or granite, along with a fine aggregate such as sand.
  • the cement commonly Portland cement, and other cementing materials such as fly ash, blast furnace slag, ground calcium carbonate, etc. serve as a part of a binder for the concrete. Typically further additives are present.
  • Admixtures are ingredients other than water, fine aggregates, (hydraulic) cement, and fibres that are added to the concrete batch immediately before or during mixing, in order to change certain characteristics of the concrete, when set.
  • the present invention is specifically related to adding further ingredients.
  • the mixed cement-based composition comprising further ingredients, or the composition itself, may have unfavourable characteristics, such as sub-optimal rheology, ductility, mixing properties, etc., whereas a cured cement-based composition may suffer from sub- optimal elasticity, compressive strength, autogenous shrinkage, internal water availability, ductility, and morphology.
  • alkali-activated concrete has drawn more attention.
  • the alkali-activated concrete is not to be confused with geopolymer cement, which is a binding system that hardens at room temperature.
  • geopolymer cement is a binding system that hardens at room temperature.
  • geopolymer chemistry is only based on aluminosilicate as precursors. Both are a more environmentally friendly alternative to conventional Portland cement. They rely on minimally processed natural materials or industrial by-products, such as blast furnace slag from steelmaking industry, to significantly reduce the carbon footprint of cement production, while also being highly resistant to many common concrete durability issues.
  • WO 2013/172497 Al recites a concrete composition using bottom ash and blast furnace slag as a cement-free binder, a rail tie using same, and a method for manufacturing same, and more specifically, provided is a concrete composition in which cement is completely substituted by mixing low-strength bottom ash with appropriate ratios of blast furnace slag, alkaline minerals and sodium silicate, inducing polymerization therein via an activator and thus attaining strength and usability.
  • Rail ties made with such a concrete composition are environment-friendly and are high-strength, allowing a compressive strength of 60MPa or higher.
  • the present invention relates in particular to an improved concrete for a prefabricate and various aspects thereof which overcomes one or more of the above disadvantages, without jeopardizing functionality and advantages.
  • the present invention relates in a first aspect to an alkali-activated concrete in particular for prefabricated production, with limited environmental impact, such as overall CO2 release, increased durability, and increased service life.
  • the alkali activator (AA) is a typical component, such as a combined silicate/alkaline solution or slurry. In the slurry the ratio SiO2:Na2O is typically > 1.25 and ⁇ 1.45, whereas in the solution it typically is >1.45, such as up to 1.95, in particular 1.6-1.85.
  • Experimental results of the present concrete show that it meets the requirements for fresh and hardened concrete. The results of the other mechanical properties are similar or better to the concrete mixes, e.g. used nowadays to produce sleepers.
  • the present binder is capable of meeting the mechanical requirements, and shows good workability.
  • the compressive strength values are comparable to those of high-strength concrete.
  • the alkali-activated concrete prestressed railway sleeper comprises as main components 350-550 kg granulated blast furnace slag, in particular 400-500 kg slag, 35-70 kg of at least one alkaline activator (AA), the AA comprising an alkali component, a silicate, and as a remainder water, in particular 35-50 kg AA, the AA comprising 5-45 kg of an alkali component, 5-45 kg of a silicate, and as a remainder water, 1200-1800 kg of an aggregate, in particular 1300- 1700 kg aggregate, wherein amounts are based on 1 m 3 concrete.
  • AA alkaline activator
  • the present concrete is particularly suited for prefabricated production, such as prestressed elements, pre-cast elements, and structural building elements.
  • the slag such as that of Ecocem (ECO2CEM) typically has a basicity coefficient of 0.8-1.0, in particular 0.9- 0.95, such as 0.925-0.93.
  • the Blaine fineness is typically 350-750 m 2 /kg, and the specific density is typically 2500-3500 kg/m 3 , in particular 2700-3200 kg/m 3 , more in particular 2800-3000 kg/m 3 , such as 2850-2900 kg/m 3 .
  • the present invention relates to a method of producing an alkali-activated concrete for prefabricated production according to any of claims 1-15, comprising providing 350-550 kg grounded blast furnace slag, 35-60 kg of at least one alka- line activator (AA), though higher amounts may be considered which are in view of costs typically not used, the AA comprising an alkali component, a silicate, and as a remainder water, 1200-1800 kg of an aggregate wherein amounts are based on 1 m 3 concrete, thoroughly dry-mixing sand, and pebbles forming a dry-mix, adding an aqueous alkaline activator solution to the dry-mix and mixing said aqueous alkaline activator solution through the drymix forming a wet-mix, and adding the ground blast furnace slag to the wet mix forming a fresh mix.
  • AA alka- line activator
  • the aqueous alkaline activator solution is preferably prepared by mixing the alkali compound, such as a hydroxide, such as sodium hydroxide, the silicate, such as sodium silicate, in water. Typically the water is provided first, and then the silicate, and thereafter the hydroxide. Mixing typically takes at least five minutes. After mixing the solution is preferably homogenized, such as for 30-120 minutes, such as for 60 minutes. Preferably relatively fresh aqueous alkaline activator solution is used, such as less than one day old solution.
  • alkali compound such as a hydroxide, such as sodium hydroxide
  • the silicate such as sodium silicate
  • the present invention relates to a prefabricated product obtained by the present method, or obtainable by a similar method, in particular wherein the prefabricated product is selected from pre-stressed elements, pre-cast elements, structural building elements, such as bridge girders, floors, walls, ceilings, supports, and frames.
  • the present invention provides a solution to one or more of the above- mentioned problems.
  • alkali-activated concrete for a prestressed railway sleeper comprises as further component water, in particular 100-200 kg water.
  • the present alkali -activated concrete for a prestressed railway sleeper has the proviso that no other slag is present.
  • the AA comprises 15-30 kg of an alkali component, in particular 16-25 kg of an alkali component, and/or 10-40 kg of a silicate, in particular 20-30 kg of a silicate.
  • a weight ratio of the silicate to the alkali is in a range of 2: 1 to 3 : 1 ; wherein the alkali component is selected from OH', and O 2 '.
  • the fineness of blast furnace slag is 4,000-7,500 cm 2 /g, in particular 5,000-6,000 cm 2 /g.
  • the blast furnace slag comprises 35-40 wt.% CaO, 30-38 wt.% SiO2, 5-10 wt.% MgO, 8-18 wt.% AI2O3, 0.1-3 wt.% Fe2O3, 0.1-3 wt.% MmOi, 0.1-3 wt.% Na2O, wherein weight percentages are determined on an oxygen basis.
  • the blast furnace slag comprises >90 wt.% amorphous material, in particular > 95% amorphous material.
  • the AA is in solid or in fluid form.
  • the silicate has a modulus of 1-3, preferably 1.5-2.5, in particular from 1.8-2.2, wherein the modulus is defined as the ratio SiO2/X2O, wherein X is selected from monovalent cations, such as from Li, Na, K, and combinations thereof.
  • the ratio z:y is ⁇ 1.2, preferably ⁇ 1.0, in particular from 0.8-0.98, more in particular from 0.86-0.97, such as 0.90-0.92.
  • the silicate is selected from crystalline and amorphous cyclic and single chain silicate (SiCh+n 211 ’), a pyro silicate (Si2O?
  • a branched silicate and a component that forms a silicate, and combinations thereof, such as from nesosilicates [SiC ] 4- , such as olivine, from sorosilicates [Si2O?] 6_ , such as epidote, from cyclosilicates [Si n O3n] 2n ⁇ , such as tourmaline, from inosilicates with single chains [Si n O3n] 2n ⁇ , such as pyroxene, from inosilicates with double chains [Si4nOnn] 6n ⁇ , such as amphibole, from phyllosilicates [Si2nO5n] 2n ⁇ , such as mica and clay minerals; and from tectosilicates.
  • nesosilicates [SiC ] 4- such as olivine
  • sorosilicates [Si2O?] 6_ such as epidote
  • the aggregate comprises as major components 30-60 wt.% sand, in particular ⁇ 4mm sand, more in particular dry sand, 40-70 wt.% pebbles, such as pebble aggregate, in particular mixed pebbles selected from 20-35 wt.% 4-8 mm pebbles and 20-35 wt.% 8-16 mm pebbles, wherein all wt.% are based on the total weight of the aggregate.
  • an average particle size of the slag is 16 ⁇ 2pm, and wherein three times the standard deviation ranges from 1-60 pm.
  • an average particle size of the sand is 580 ⁇ 20pm, and wherein three times the standard deviation ranges from 100 pm -7 mm.
  • an average particle size of the 4-8 mm pebbles is 6.8 ⁇ 1mm, and wherein three times the standard deviation ranges from 1-12 mm.
  • an average particle size of the 8-16 mm pebbles is 10.2 ⁇ 1mm, and wherein three times the standard deviation ranges from 1-20 mm.
  • an average particle size of dry-mix is 1.5 ⁇ 0.2mm, and wherein three times the standard deviation ranges from 2 pm -15 mm.
  • the average particle size of 8-16 mm pebbles is 15-30 times the average particle size of the sand, in particular 18-22 times the average particle size of the sand.
  • the average particle size of 4-8 mm pebbles is 8-12 times the average particle size of the sand, in particular 9-11 times the average particle size of the sand.
  • the average particle size of sand is 20-30 times the average particle size of the slag, in particular 24-26 times the average particle size of the sand, wherein the average particle size and standard deviation are based on a cumulative volume, and wherein particle sizes are measured using laser diffraction, such as by using a Malvern Mastersizer 3000.
  • the water/solids ratio is from 0.35-0.45: 1, in particular from 0.38- 0.43: 1, such as 0.39: 1.
  • the 1-day strength is >10 MPa, in particular >30 MPa (1 day curing @ 25°C, measured according to EN12390-3.
  • the strength class is C45/55 (@ ambient temperature curing after 7 days curing in mould at 25°C, measured according to EN12390-3).
  • the elastic modulus is >20 GPa, in particular >30 GPa (after 28 days, measured according to EN12390-3).
  • the consistency class is S3 (slump-flow 100-200 mm, measured according to EN206-1).
  • the compressive strength after 28 days is >60 MPa [[(@ ambient temperature curing after 1 day curing in mould at 25°C, measured according to EN12390-3],
  • the electrical resistivity is >120 Q*m, in particular >400 Qm, more in particular > 500 Qm [using a Wenner-probe], At values above 120 Qm almost certain no corrosion is to be expected.
  • the present concrete provides values far above these already safe values.
  • Fig. 1 shows a track structure of a ballasted track, including the stress distribution under a lOOkN wheel load.
  • Figs. 2a-b show compressive strength and slump mix of mixtures 17-19, respectively.
  • An inverted procedure of mixing is used, inverting the sequence of addition of activator and slag.
  • the gravel and sand are mixed for 1 minute to assure a homogeneous distribution of all particles.
  • the activator is added.
  • the mix has a muddy consistency.
  • the slag is added.
  • the particles quickly agglomerate around the aggregates. After two minutes, the aggregates agglomerate. Two things could happen: If the saturation of the sand and gravel was lower than calculated, the agglomerated aggregates form a stiffer plaque of concrete. If this is the case, the mixer is not able to distribute the concrete evenly to mix it properly anymore. This will make the mixer bounce under the weight of the falling plaque.
  • the samples will now be placed in the fog room until a curing age of 28 days.
  • the fog room has a 99% RH and a temperature of 20 °C.
  • One exception to this curing regime is the samples used for the freeze and thaw testing: In that case, the samples stay only seven days in the fog room and 21 days in a climate chamber according to the standard.
  • the slag particles float in the activator solution, and the dissolution of oxides in the slag particles now occurs over the whole surface area. This is in contrast to the situation in the regular mixing procedure.
  • the slag particles are only partly in contact with the solution and partly in contact with the aggregate.
  • the dissolution of oxides occurs only from the surface area in contact with the solution .
  • the start of the CASH gel formation occurs at the interface transition zone.
  • the slag particles are already adhered to the surface of the aggregates, making them sticky already before adding the activator solution.
  • the aggregates form a sponge, filled with activator solution. This improves the quality of the interface transition zone.
  • the optimal silica modulus was expected to be between 1 and 1.5. However, the 19 trial mixes indicate the optimal silica modulus in terms of workability is lower: around 0.8 to 0.9.
  • the hardened concrete was evaluated on compressive and tensile strength.
  • the durability of the designed concrete is tested in three different ways. In agreement with the product specification, the concrete integrity after a freeze-thaw attack is assessed. Next to the freeze-thaw assessment, carbonation is also assessed. Finally, because of the presence of stray current induced by the traction power system and the railway safety system, the electrical resistivity of the concrete is assessed. There is no standard for the evaluation of the electrical resistance of concrete, in a four-point alternating current test setup. Therefore, a setup similar to those frequently used in literature is adopted. This test setup involves a handheld device called a four-probe resistivity meter.
  • This device is also called the Wenner probe [using EN 50522], It features four electrodes, which will be pressed against the concrete. Using wet sponges, this device transfers an alternating current to the concrete while measuring the resistivity of the material. The probe is placed on all non-trowelled sides of a concrete prism an d pressed against the concrete until the values measured become steady. The average of the three measurements per prism forms the electrical resistivity of this prism.
  • the air content of the mixes is from 1.7-2.0%, the density about 2325 kg/m 3 , which is slightly lower than the calculated density.
  • the NaOH can be obtained from Brenntag Nederland BV in 50% aqueous solution, and the waterglass from PQ silicates BV in a 48% aqueous solution with a silica modulus of 2.0.
  • a typical chemical composition of the grounded blast furnace slag is (on an oxide basis): CaO SiO2 MgO AI2O3 Fe20s MmCh Na2O Others LOI
  • the slump retention decreases over time(90 minutes) to about 100 mm.
  • the flexural bending strength is from 6.5-7.0 N/mm 2 for the above mixtures.
  • the tensile splitting strength is from 3.2-4.5 N/mm 2 for the above mixtures.
  • the secant modulus of elasticity (Young’s modulus) is from 41000-42000 MPa for the above mixtures.
  • the mass loss following the NTN-018 method is from 2200-2500 gr/m 2 for the above mixtures.
  • the electrical resistivity is from 0.55-0.70 kQm for the above mixtures.
  • the carbonation increases from 5mm to 10 mm for the above mixtures in a time period from 200-1000 hours.
  • the mixtures designed have a water to binder ratio of 0.39, a binder content varying between 500 and 400 kg/m 3 and contain pH elevating alkaline activators.
  • Regular concrete used for the production of NS90 sleepers has a water to cement ratio of 0.375, a cement content of 400 kg/m 3 and contains 2.4 kg superplasticizer.
  • the present invention has found the alkali-activated bin der system to be suitable to con struct the NS90 sleeper. It has also been found that the environmental impact is reduced by doing so. Specific attention has to be drawn towards freeze-thaw resistance and decarbonation. The electrical resistance is proven to be equal or better compared to regular concrete. The following conclusions are drawn based on these findings:
  • the water to binder ratio plays a vital role in the strength development of the alkali- activated concrete.
  • the formation of CASH-gel is significantly delayed if a higher water to binder ratio is used since the pH of the activator solution is reduced. This becomes apparent when comparing the strength development of a mix with the strength development of another mix. Similar bin der and activator content but a significantly lower water to binder ratio has led to a faster hardening of the concrete in an exemplary mix. The importance of the water to binder ratio has also been demonstrated.
  • Alkali-activated slag concrete has a disconnected pore structure. Nevertheless, CO2 can penetrate the concrete with relative ease. As shown CO2 can penetrate the concrete with relative ease. It is important to note that the rate of ingress decreases over time. The CO2 ingress is almost equal for every mix type, but the higher binder content and lower air volume and thus porosity seems to make mix A resist carbonation better. When the natural carbonation is compared to regular CEM in/ B concrete, the values lie closer together. CEM III/ B concrete, however, has a higher carbonation resistance.
  • the electrical resistivity of concrete depends on two concrete properties: The pore structure’s degree of connection and the pore solution’s contents. Based on the literature review, the driving factors attributing to electrical conductivity are the connectivity of the pore structure an d the contents of the pore solution. A clear tipping point in electrical resistivity can be observed in the results. It can thus be concluded, based upon the literature review and the mix ingredients, either the pore solution contains significantly more free ions, conducting the electrical energy better or the degree of pore connectivity is higher.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
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Abstract

La présente invention concerne le domaine des mélanges de béton, en particulier un béton activé par un alcali, qui peut être utilisé pour une traverse de chemin de fer précontrainte, un procédé de formation dudit béton, et un préfabriqué, tel que des éléments pré-contraints, des éléments préfabriqués, des éléments de construction structuraux, tels que des planchers, des murs, des plafonds, des supports et des cadres. Le préfabriqué présente des caractéristiques améliorées et moins de dioxyde de carbone est nécessaire pour la production.
PCT/NL2023/050215 2022-04-28 2023-04-21 Béton activé par un alcali pour traverse de chemin de fer précontrainte WO2023211268A1 (fr)

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NL2031726A NL2031726B1 (en) 2022-04-28 2022-04-28 Alkali-activated concrete for a prestressed railway sleeper
NL2031726 2022-04-28

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013172497A1 (fr) 2012-05-17 2013-11-21 한국건설기술연구원 Composition de béton contenant un liant exempt de ciment comprenant du laitier de haut fourneau et des cendres résiduelles, traverse de rail l'utilisant et son procédé de fabrication
WO2022245201A1 (fr) * 2021-05-17 2022-11-24 Technische Universiteit Delft Béton autocompactant activé par les alcalis pour la production de préfabriqués

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013172497A1 (fr) 2012-05-17 2013-11-21 한국건설기술연구원 Composition de béton contenant un liant exempt de ciment comprenant du laitier de haut fourneau et des cendres résiduelles, traverse de rail l'utilisant et son procédé de fabrication
KR20130128560A (ko) * 2012-05-17 2013-11-27 한국건설기술연구원 고로슬래그 및 바텀애시로 구성되는 무시멘트 결합재를 포함하는 콘크리트 조성물, 이를 이용한 침목 및 그 제조방법
WO2022245201A1 (fr) * 2021-05-17 2022-11-24 Technische Universiteit Delft Béton autocompactant activé par les alcalis pour la production de préfabriqués

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MANJUNATH R ET AL: "Studies on development of high performance, self-compacting alkali activated slag concrete mixes using industrial wastes", CONSTRUCTION AND BUILDING MATERIALS, vol. 198, 3 December 2018 (2018-12-03), pages 133 - 147, XP085582821, ISSN: 0950-0618, DOI: 10.1016/J.CONBUILDMAT.2018.11.242 *
PROVIS JOHN L ET AL: "RILEM TC 247-DTA round robin test: mix design and reproducibility of compressive strength of alkali-activated concretes", MATERIALS AND STRUCTURES, SPRINGER NETHERLANDS, DORDRECHT, vol. 52, no. 5, 10 September 2019 (2019-09-10), XP037175567, ISSN: 1359-5997, [retrieved on 20190910], DOI: 10.1617/S11527-019-1396-Z *
SHOJAEI MOHAMMAD ET AL: "Application of alkali-activated slag concrete in railway sleepers", MATERIALS AND DESIGN, vol. 69, 2 January 2015 (2015-01-02), pages 89 - 95, XP029164905, ISSN: 0261-3069, DOI: 10.1016/J.MATDES.2014.12.051 *

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