WO2020199907A1 - Mortier de réparation sous forme de mélange sec activé en milieu alcalin à faible retrait - Google Patents

Mortier de réparation sous forme de mélange sec activé en milieu alcalin à faible retrait Download PDF

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Publication number
WO2020199907A1
WO2020199907A1 PCT/CN2020/079516 CN2020079516W WO2020199907A1 WO 2020199907 A1 WO2020199907 A1 WO 2020199907A1 CN 2020079516 W CN2020079516 W CN 2020079516W WO 2020199907 A1 WO2020199907 A1 WO 2020199907A1
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WIPO (PCT)
Prior art keywords
approximately
repair mortar
alkali
mix
weight percent
Prior art date
Application number
PCT/CN2020/079516
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English (en)
Inventor
Chung Kong Chau
Xiwen Guan
Shiyin LIU
Man Lung Sham
Wai Pong CHAN
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Optimix Eco Building Material Limited
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Publication date
Application filed by Optimix Eco Building Material Limited filed Critical Optimix Eco Building Material Limited
Priority to CN202080005791.0A priority Critical patent/CN112930329A/zh
Publication of WO2020199907A1 publication Critical patent/WO2020199907A1/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
    • C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • 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
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1037—Cement free compositions, e.g. hydraulically hardening mixtures based on waste materials, not containing cement as such
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/34—Non-shrinking or non-cracking materials
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72—Repairing or restoring existing buildings or building materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to an alkali-activated dry mix repair mortar and, more particularly, to an alkali-activated dry mix repair mortar that exhibits very low shrinkage and excellent chemical resistance to the working environment.
  • repair mortars were based on ordinary Portland cement. However, many of these repair mortars lacked volume stability, chemical resistance, strength and adhesion to the original concrete structures. Newer repair mortars have included various polymers such as epoxy, acrylic, or polyurethane; these may demonstrate increased strength and adhesion. However, volatile organic compounds that emanate from the repair material may cause concern for workers applying the material. Moreover, organic based materials are not compatible with the parent cement-based substrates.
  • repair mortars have special mechanical and chemical resistance requirements.
  • requirements such as volume stability with very low shrinkage, high chemical resistance, and strong bonding to the concrete substrate to be repaired, of the repair mortar, are highly desirable for repair mortars.
  • a dry-mix, alkali-activated repair mortar includes a base material selected from ground granulated blast furnace slag, fly ash, or a mixture thereof in an amount from approximately 32 weight percent to approximately 37 weight percent. Metakaolin is provided in an amount from approximately 3 weight percent to approximately 8 weight percent.
  • modulated potassium silicate is used, with the potassium silicate having been modified by KOH such that a molar ratio of K 2 O to SiO 2 ranges from approximately 1.8 to 2.2.
  • Different kinds of fillers are used in an amount from approximately 50 weight percent to approximately 54 weight percent.
  • the drying shrinkage of the repair mortar is less than or equal to approximately 0.06%and the bond strength of the repair mortar is greater than 0.5 MPa, the chemical resistance measured by a weight loss after 28 days of acid exposure is less than or equal to approximately 3.4 %, and the setting time of the repair mortar is greater than or equal to approximately 60 minutes.
  • the environmentally-friendly repair mortars of the present invention include a base aluminosilicate recycled or waste material.
  • This recycle or waste material may be selected from granulated ground blast furnace slag (or a related slag) or fly ash.
  • Slag is the material left over when a metal has been separated (e.g., smelted) from its respective metal ore.
  • Granulated ground blast furnace slag is produced by quenching of molten iron slag (a by-product of iron and steel-making) from a blast furnace followed by grinding.
  • the main components of granulated ground blast furnace slag are CaO (30-50%) , SiO 2 (28-38%) , Al 2 O 3 (8-24%) , and MgO (1-18%) .
  • Fly ash is the leftover product of coal combustion.
  • the range of components depend on the composition of the coal that was burned and tends to be regionally-specific.
  • the main components of fly ash are silicon dioxide (SiO 2 ) in an amount from 45-60 weight percent, aluminium oxide (Al 2 O 3 ) in an amount from 18-32 weight percent and calcium oxide (CaO) in an amount from 2 to 10 weight percent.
  • the base materials necessarily have variable compositions because they are recycled or waste materials and, as such, come from a wide variety of sources. Therefore, the above compositions are merely exemplary of base material compositions.
  • the GGBS and/or fly ash is present in the repair mortar in an amount from approximately 22 to approximately 33 weight percent.
  • Metakaolin is also used in the repair mortars of the present invention.
  • Metakaolin is formed from calcined kaolin, a clay mineral. It has a low calcium content, being primarily composed of silicon dioxide (SiO 2 ) , about 48-58 weight percent, and aluminum oxide (Al 2 O 3 ) , about 40-50 weight percent, with small amounts of iron oxide, calcium oxide, and titanium dioxide.
  • SiO 2 silicon dioxide
  • Al 2 O 3 aluminum oxide
  • metakaolin that is produced by calcining at temperatures in the range of approximately 750 to 800°C is selected for use in the repair mortars.
  • the metakaolin is present in the repair mortar composition in an amount from approximately 3 to approximately 8 weight percent.
  • Metakaolin has been used as a replacement material in conventional concrete mixes, particularly in environments that may be exposed to chemical attack, as, for example, chemical attack by chloride ions.
  • chemical attack as, for example, chemical attack by chloride ions.
  • metakaolin in the repair mortars contributed to a very low dry shrinkage percentage.
  • a low dry shrinkage percentage allows a repair mortar to be applied to a concrete structure, bond to the region in need of repair, and dry and cure without cracking.
  • metakaolin combined with either GGBS or fly ash, produces a sufficiently strong binder phase, good bonding to the structure to be repaired, and high durability.
  • Metakaolin is an aluminate-rich material.
  • the alkali activation produces SiO 4 and AlO 4 tetrahedral frameworks linked by shared oxygens as poly (sialates) or poly (sialate–siloxo) or poly (sialate–disiloxo)
  • the addition of metakaolin yields an improved structure with a dense amorphous phase including a semi-crystalline 3-D alumino-silicate microstructure.
  • the dense 3-D structure is volumetrically stable and has very low drying shrinkage.
  • Alkali activation of the base materials produces a variety of reaction products that bind together.
  • a reaction occurs involving the dissolution of an aluminosilicate material by the alkaline material. That is, the minerals are “de-polymerized” into their constituent “monomers” by condensation of the alkaline material.
  • the dissolution results in formation of reactive units of covalently bonded Si-O-Si and Al-O-Si units.
  • Aluminum atoms enter the Si-O-Si units, forming aluminosilicate gels. Following the gel formation, a condensed structure is generated with crystallization into a polymeric network. Due to the formation of a polymeric network, some alkali activated materials are referred to as “geopolymers. ”
  • modulated potassium silicate K 2 SiO 3
  • the potassium silicate is modified by potassium hydroxide (KOH) such that a molar ratio of SiO 2 to K 2 O ranges from approximately 1.8 to 2.2.
  • KOH potassium hydroxide
  • the modulated activator is present in a dry powder form, avoiding the many safety hazards associated with the use of liquid alkali activators (transport issues, chemical burn issues, etc. ) .
  • other modulated alkali activators may be used such as sodium-based activators or lithium-based activators.
  • the modulated alkali activator may be present in the repair mortar in an amount from approximately 5 percent to approximately 6 percent.
  • a retarder such as NaHCO 3 may be added in an amount from approximately 0.01 to approximately 0.2 weight percent.
  • the retarder NaHCO 3 achieves a controllable setting time through buffering action in the alkali-activated mortar.
  • NaHCO 3 is a buffering agent to balance the alkalinity for the matrix. It can help to counteract and limit the increase of alkalinity in the matrix and slow down the chemical reaction of the alkali-activation in the early stage. Consequently, the setting and hardening process of the alkali-activated material can be well-controlled.
  • the setting time of the repair mortar can be controlled to be greater than 60 minutes and, in some cases, greater than 90 minutes. A long setting time is important in the repair environment as applied mortar may need to be shaped into complex configurations that require time to be formed.
  • a thickener such as starch ether may be added in an amount from approximately 0 to approximately 0.1 weight percent.
  • a rheology modifier such as hydroxy propyl methyl cellulose (HPMC) may be added in an amount from approximately 0 to approximately 0.01 weight percent.
  • HPMC hydroxy propyl methyl cellulose
  • the rheology may be selected for different applications. For example, the horizontal applications may use a repair mortar that is less viscous than repair mortars for vertical surfaces or overhead applications.
  • Fibers may be added to the repair mortar in an amount from approximately 0 weight percent to approximately 0.2 weight percent. Glass fibers may be used as the fiber additives. Because mortars typically have weak tensile properties, fiber reinforcement may enhance tensile strength. Fibers may help reduce shrinkage and cracking during drying of the repaired structure. Fibers can act as crack arresters as the fibers may prevent cracks from propagating by adhering parts of the repair mortar to each other.
  • the repair mortar of the present disclosure may include sand and/or lightweight aggregate in varying amounts.
  • a total amount of aggregate may range from approximately 50 weight %to approximately 54 weight %. Of this amount approximately 50 to 52 weight %may be sand and approximately 0-2 weight %may be lightweight aggregate. In particular, different grades of sand may be used.
  • graded silica sand having a diameter on the order of 0.5 mm or less may be used in an amount of approximately 20 weight percent to approximately 21 weight percent and graded silica sand having a diameter on the order of approximately 0.5 mm to approximately 1.2 mm may be used in an amount of approximately 30 weight percent to approximately 31 weight percent.
  • the repair mortars of the present invention exhibit excellent chemical resistance, and may be applied to repairs that require corrosion resistance (e.g., resistance to chlorine ions penetration to reduce corrosion of reinforcing steel bars- “rebar” ) .
  • the repair mortars also demonstrate superior acid resistance. Particular applications that require chemical resistance include concrete structures in contact with contaminated acidic chemical sources.
  • the repair mortar further exhibits extremely low drying shrinkage, on the order of approximately lower than 600 microstrain (that is, less than or equal to approximately 0.06%or 0.6 mm/m) .
  • the setting time is controllable and may be controlled to set in approximately 60 minutes or more and, in some embodiments, 90 minutes or more.
  • the inventive repair mortars also demonstrate a high compressive strength, both at 7 days and at 28 day which is 30 MPa and 35MPa, respectively. The strength may be selectively modified depending upon the repair application.
  • the repair mortar of the present invention possesses a good bond strength, on the order of at least approximately 0.5 MPa, more preferably, at least approximately 2.0 MPa.
  • the repair mortars of the present invention may penetrate and chemically react with the concrete substrates being repaired, providing the good bond strength.
  • the alkali-activated dry mix repair mortar in powder form has water added.
  • the mixing water was mixed with dry mortar in a Hobart mixer at a speed of 140 r/min for 120 s. Subsequently, the mixing speed was changed to a higher speed of 285 r/min for another 120 s. Upon completion of the above mixing procedures, the mixture was prepared and ready for casting or testing operations.
  • specimens were demoulded and maintained wrapped by polyethene sheets at the previous temperature and humidity conditions for further curing until the designated testing age.
  • the fresh performances, mechanical and durability properties of the alkali-activated dry mix repair mortar mixtures were measured.
  • Mortar setting times is measure by vicat needle
  • flowability is measured with an ASTM standard flow table
  • compressive strength results at different curing ages of 1, 7 and 28 days and elastic moduli are acquired by a universal testing machine and bonding strength is measured with a pull-off tester.
  • properties such as drying shrinkages are measured according to the linear length changing method and acid resistance is tested by weight loss with cylindrical specimens which were immersed in 5%sulphuric acid solution. Chloride ion penetrability is measured by the rapid electric flux method.
  • Example 4 (Inventive Composition With 6%Metakaolin)
  • Example 1 is a comparative example formulation without metakaolin.
  • the setting time is around 90 min and the compressive strength at 7d and 28d is 29.3 and 30 MPa, respectively.
  • the drying shrinkage at 28 days is as large as 0.333%, which is too large for a repair mortar.
  • the weight loss in acid solution after 28 days is 3.5%, chloride ion penetrability is low and the bonding strength is higher than 0.5 MPa. It is found that without metakaolin in this comparative example repair mortar formulation, drying shrinkage is a serious problem and it is unsuitable for use as a repair mortar.
  • Example 2 is a comparative example formulation with only 2%metakaolin.
  • the setting time is 47 min and compressive strength at 7d and 28d is 43.4 and 46.5 MPa, respectively.
  • the drying shrinkage at 28 days is 0.113%, which, while smaller than in example 1, is still unacceptable for a repair mortar.
  • the weight loss in acid solution after 28 days is 3.6%, chloride ion penetrability is low and bonding strength is higher than 0.5 MPa.
  • the metakaolin has contributed to reducing the drying shrinkage, the level of drying shrinkage is still unacceptable for a repair mortar.
  • Example 3 is a formulation with 3.2%metakaolin.
  • the setting time is 46 min and compressive strength at 7d and 28d is 42.3 and 43.6 MPa, respectively.
  • the drying shrinkage at 28 days is 0.052%, which is acceptable for a repair mortar.
  • a drying shrinkage of less than or equal to 0.06% is needed for a low-shrinkage repair mortar.
  • the weight loss in acid solution after 28d is 3.6%, chloride ion penetrability is low and bonding strength is higher than 0.5 MPa.
  • the higher amount of metakaolin of 3.2%in this low-shrinkage alkali-activated dry mix repair mortar formulation has contributed to further control the drying shrinkage to an acceptable level.
  • Example 4 is a formulation within the range of the present invention with 6%metakaolin.
  • the setting time is 60 minutes and compressive strength at 7d and 28d is 41.4 and 46.8 MPa, respectively.
  • the drying shrinkage at 28 days is only 0.048%.
  • the weight loss in acid solution after 28d is 3.8%, chloride ion penetrability is low and bonding strength is higher than 0.5 MPa.
  • 6%of metakaolin in this low-shrinkage alkali-activated dry mix repair mortar formulation the drying shrinkage is minimized to 0.048%.
  • the workability of the repair mortar may be further enhanced by utilizing other functional admixtures.
  • Example 5 is a formulation of the inventive low-shrinkage alkali-activated dry mix repair mortar. Thickener, rheology modifier and fibers are added in this formulation to adjust the workability and durability properties. The setting time is longer than 90 minutes and compressive strength at 7d and 28d is 34.6 and 36.8 MPa, respectively, which are sufficient for a repair mortar. The 28-day drying shrinkage is only 0.048%, weight loss in acid solution after 28 days is 3.4%, chloride ion penetrability is low and bonding strength is higher than 0.5 MPa.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne un mortier de réparation sous forme de mélange sec sans ciment Portland ordinaire (OPC) activé en milieu alcalin, comprenant un matériau de base choisi parmi des scories de haut fourneau granulées broyées, des cendres volantes ou un mélange de celles-ci en une quantité d'environ 32 pour cent en poids à environ 37 pour cent en poids. Du métakaolin est présent en une quantité d'environ 3 pour cent en poids à environ 8 pour cent en poids. En tant qu'activateur alcalin, du silicate de potassium modulé est utilisé, le silicate de potassium ayant été modifié (par du KOH) de façon telle qu'un rapport molaire de K2O à SiO2 est compris entre environ 1,8 et 2,2. Une charge est utilisée en une quantité d'environ 50 pour cent en poids à environ 54 pour cent en poids. Le retrait au séchage du mortier de réparation est inférieur ou égal à environ 0,06 % et la force de liaison du mortier de réparation est supérieure ou égale à environ 0,5 MPa, la résistance à l'acide mesurée par une perte de poids après 28 jours d'exposition à de l'acide est inférieure ou égale à environ 3,4 % et le temps de prise du mortier de réparation est supérieur ou égal à environ 60 minutes.
PCT/CN2020/079516 2019-04-03 2020-03-16 Mortier de réparation sous forme de mélange sec activé en milieu alcalin à faible retrait WO2020199907A1 (fr)

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CN202080005791.0A CN112930329A (zh) 2019-04-03 2020-03-16 具低收缩率的碱活化干混修补砂浆

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HK19121825 2019-04-03

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CN112876151A (zh) * 2021-03-04 2021-06-01 江苏洋河新城新材料有限责任公司 一种地聚物基快速修补砂浆及其制备方法
CN113387635A (zh) * 2021-05-11 2021-09-14 贵州省公路工程集团有限公司 一种隧道尾料高石粉含量混凝土的制备方法
CN115572103A (zh) * 2022-11-10 2023-01-06 深圳市华越新材料有限公司 一种轻质建筑垃圾再生砂及其生产方法

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CN115572103A (zh) * 2022-11-10 2023-01-06 深圳市华越新材料有限公司 一种轻质建筑垃圾再生砂及其生产方法

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