High-strength water-resistant anti-freezing putty and preparation method thereof

Abstract

The invention belongs to the technical field of building materials, and particularly discloses high-strength waterproof anti-freezing putty and a preparation method thereof. The high-strength waterproof anti-freezing putty provided by the invention is prepared from the following components in a specific weight ratio: high-free-calcium belite sulphoaluminate clinker, granulated blast furnace slag powder, gypsum, filler, latex powder and a water-retaining agent. Through the raw material design of the high-strength water-resistant anti-freezing putty, the high-free calcium belite sulphoaluminate clinker and the granulated blast furnace slag powder have a synergistic effect, so that the types, the composition and the microstructure of hydration products of a gypsum-based material can be improved, and the water-resistant and high-strength hydration products ettringite and C-(A)-S-H gel are increased; meanwhile, the dihydrate gypsum is compactly coated by the two materials; and a dense microstructure is constructed by the putty powder and other components in the formula, such as latex powder and a water-retaining agent, so that the high strength, water resistance and frost resistance of the putty are improved.

Description

Technical Field

[0001] This invention belongs to the field of building materials technology, specifically relating to a high-strength, water-resistant, and frost-resistant putty and its preparation method. Background Technology

[0002] Gypsum-based putty is a premixed dry powder putty made primarily of building gypsum as the binder, compounded with fillers and modified additives. It is widely used due to its advantages such as being environmentally friendly, crack-resistant, having high construction efficiency, and low cost. However, the hydration product of gypsum-based putty is dihydrate gypsum, which has high solubility and does not produce colloidal hydration products. This characteristic directly leads to poor water resistance and low strength. Prolonged contact with water or exposure to high humidity environments can easily cause quality problems such as powdering and peeling. Currently, the bonding strength of mainstream gypsum-based putty on the market is typically between 0.5MPa and 0.8MPa, far lower than that of cement-based putty, and its durability is also poor. Furthermore, its frost resistance is difficult to adapt to the complex and ever-changing environmental requirements. Therefore, gypsum-based putty is generally only suitable for leveling and finishing walls in dry indoor environments and is not suitable for outdoor use, damp areas (such as kitchens, bathrooms, and basements), or occasions with specific requirements for mechanical properties.

[0003] Gypsum-based putty suffers from poor water resistance, low strength, and poor frost resistance. Furthermore, current application research largely focuses on single-variety gypsum such as desulfurized gypsum-based building gypsum, phosphogypsum-based building gypsum, anhydrite, α-high-strength gypsum, or fluorogypsum, with few putty technologies compatible with these various gypsum types. These problems significantly limit its application scope. Therefore, developing a comprehensive gypsum-based putty with high strength, water resistance, frost resistance, and compatibility with various gypsum raw materials has become a critical need urgently needing to be met by the industry. Summary of the Invention

[0004] To address the shortcomings of existing gypsum-based putty technology, this invention provides a high-strength, water-resistant, and freeze-resistant putty and its preparation method. This method optimizes the putty raw material formulation, utilizing the synergistic effect of high-free-calcium belite sulfoaluminate clinker and granulated blast furnace slag powder to regulate the types, composition, and microstructure of hydration products in gypsum-based materials. This promotes the formation of water-resistant, high-strength hydration products—ettringite and C-(A)-SH gel—while simultaneously achieving a dense coating of dihydrate gypsum by both. This effectively solves the core problems of poor water resistance, low strength, and poor freeze-resistant properties in gypsum-based putty. Furthermore, the high-strength, water-resistant, and freeze-resistant putty provided by this invention is compatible with various gypsum raw materials, offering a new technical pathway for the efficient recycling of industrial by-product gypsum.

[0005] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted: In a first aspect, the present invention provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4%~8.5% high-free-calcium belite sulfoaluminate clinker, 24.6%~52.1% granulated blast furnace slag powder, 21%~43% gypsum, 21%~31% filler, 1.0%~3.0% latex powder, and 0.2%~0.5% water-retaining agent; The high-free-calcium belite sulfoaluminate clinker comprises the following mineral components by weight percentage: 25.31%~33.27% anhydrous calcium sulfoaluminate, 14.82%~19.71% free calcium oxide, 6.55%~12.26% free calcium sulfate, 27.27%~33.87% belite, and 3.04%~6.08% iron phase; The belite comprises dicalcium silicate; the iron phase comprises tetracalcium aluminoferrite.

[0006] Compared to existing technologies, the high-strength, water-resistant, and frost-resistant putty provided by this invention utilizes high-free-calcium belite sulfoaluminate clinker and granulated blast furnace slag powder to synergistically regulate the types, composition, and microstructure of gypsum hydration products. This allows for the directional induction of hydration products with excellent water resistance (AFt and C-(A)-SH gel) to grow around dihydrate gypsum, blocking external moisture from contacting dihydrate gypsum and inhibiting its dissolution. Consequently, the putty's water resistance and mechanical properties are significantly improved, even achieving a curing strength in standard water that is greater than that in standard dry air.

[0007] In this invention, the dihydrate gypsum crystals generated by the hydration of externally added gypsum are synergistically encapsulated by AFt microcrystals and C-(A)-SH gel to achieve a double-density coating. Even with a high gypsum content, it effectively prevents the easily water-soluble dihydrate gypsum from dissolving in water, fundamentally solving the problems of poor water resistance, significant strength reduction, and insufficient freeze-thaw resistance in gypsum-based putty caused by the high solubility of dihydrate gypsum. Simultaneously, as the putty's microstructure becomes denser, its porosity decreases accordingly, and its mechanical strength gradually increases.

[0008] Preferably, the high free calcium belite sulfoaluminate clinker further includes 5.12% to 7.66% mixed mineral components.

[0009] For example, based on the mass content of high free calcium belite sulfoaluminate clinker as 100%, the mixed mineral components include 2% to 4% periclase, 0.85% to 2.55% perovskite, and 0.5% to 1.5% alkali metal sulfates.

[0010] Preferably, the high-free-calcium berit sulfoaluminate clinker comprises the following oxides by weight percentage: 55%~58% CaO, 14%~18% Al2O3, 9.5%~11.8% SiO2, 8%~11% SO3 and 1%~2% Fe2O3.

[0011] For example, the hybrid oxide includes at least one of TiO2, MgO, K2O or Na2O.

[0012] The preparation method of high free calcium berit sulfoaluminate clinker described in this invention includes the following steps: Limestone, bauxite and gypsum are mixed and ground to obtain raw meal; the raw meal is calcined at 1200℃~1300℃ to obtain high free calcium berite sulfoaluminate clinker; The mass ratio of limestone, bauxite and gypsum is (60~71):(17~23):(12~19); The chemical components in the raw material satisfy the following conditions: ([CaO]-1.87×[SiO2]-1.05×[Fe2O3]-0.7×[TiO2]-0.55×[Al2O3]-0.7×[SO3]) / (100%-α)=14.82%~19.71% Formula 1; (1.7×[SO3]-0.45×[Al2O3]+0.28×[Fe2O3]) / (100%-α)=6.55%~12.26% Formula 2; In the above formula, α represents the loss on ignition of the raw meal.

[0013] It should be noted that in this invention, [CaO] represents the mass percentage of CaO in the raw meal, [SiO2] represents the mass percentage of SiO2 in the raw meal, [Fe2O3] represents the mass percentage of Fe2O3 in the raw meal, [TiO2] represents the mass percentage of TiO2 in the raw meal, [Al2O3] represents the mass percentage of Al2O3 in the raw meal, and [SO3] represents the mass percentage of SO3 in the raw meal; α = ∑ mass percentage of each chemical component in the raw meal × loss on ignition of each chemical component.

[0014] By limiting Formula 1, this invention ensures that the content of free calcium oxide in the obtained clinker meets the requirements. By limiting Formula 2, it ensures that the content of free calcium sulfate in the obtained clinker meets the requirements.

[0015] The raw material has a particle size of less than 15% residue after passing through a 0.08mm square hole sieve.

[0016] For example, calcination is carried out in a rotary kiln, and the time from entering the kiln to exiting it is 30 to 60 minutes. The specific calcination time can be adjusted according to the specific conditions of different rotary kilns.

[0017] For example, after calcination, the process also includes cooling and grinding to obtain powdered high-free-calcium belite sulfoaluminate clinker.

[0018] Preferably, the filler includes at least one of talc powder, quartz powder, or dolomite powder.

[0019] Preferably, the high-strength, water-resistant, and frost-resistant putty further comprises the following components by weight percentage: 0-1% amorphous calcium aluminate, 0-0.4% water-reducing agent, 0-0.05% starch ether, 0-0.26% retarder, 0-0.2% waterproofing agent, and 0-6% pigment.

[0020] Preferably, the amorphous content of the amorphous calcium aluminate is ≥99.0%, and the specific surface area is ≥500 m². 2 / kg.

[0021] The amorphous calcium aluminate selected by this invention has high hydration activity and can react completely within 5 minutes.

[0022] This invention demonstrates a significant synergistic hydration effect between high-free-calcium beritol sulfoaluminate clinker, amorphous calcium aluminate, and granulated blast furnace slag powder. Specifically, the free calcium oxide in the clinker provides a moderately alkaline environment for the system. Under the synergistic activation of amorphous calcium aluminate, it efficiently activates the glassy phase in the granulated blast furnace slag powder. Simultaneously generated AFt microcrystals further induce the dissolution of active components in the glassy phase, driving the hydration reaction to continue. Ultimately, this results in a water-resistant, high-strength hydration product system primarily composed of ettringite (AFt) and C-(A)-SH gel. This system, together with other components in the formulation (such as latex powder and water-retaining agents), constructs a dense microstructure, thereby improving the high strength, water resistance, and freeze-thaw resistance of the putty. This invention provides a high-strength, water-resistant, and freeze-thaw-resistant putty that utilizes the alkaline regulation ability of high-free-calcium clinker, the strong activation activity of amorphous calcium aluminate, and the potential gelling properties of slag powder. Through alkaline environment-activation-product enhancement, the functions of each component are complementary and their effects are synergistic.

[0023] For example, the gypsum includes at least one of wet phosphogypsum, wet desulfurized gypsum, phosphogypsum-based building gypsum, desulfurized gypsum-based building gypsum, dried desulfurized gypsum, dried phosphogypsum, dihydrate gypsum, fluorogypsum, anhydrite, or α-high-strength gypsum. In this invention, desulfurized gypsum, phosphogypsum, and fluorogypsum should meet the requirements of GB / T 21371-2019 "Industrial By-product Gypsum Used in Cement," and phosphogypsum should also meet the requirements of GB / T 23456-2018 "Phosphogypsum"; desulfurized gypsum-based building gypsum and phosphogypsum-based building gypsum should meet the requirements of GB / T 9776-2022 "Building Gypsum"; α-high-strength gypsum should meet the requirements of JC / T 2038-2010 "α-type High-strength Gypsum"; anhydrite and dihydrate gypsum should meet the requirements of GB / T 5483-2024 "Natural Gypsum." Dry-cured desulfurized gypsum is obtained by drying wet desulfurized gypsum, and dry-cured phosphogypsum is obtained by drying wet phosphogypsum. When this invention uses two or more types of gypsum in a compound formulation, there are no requirements regarding the dosage of different gypsum types.

[0024] Because the difficulty of processing different types of gypsum varies greatly, especially the processing of phosphogypsum, which is a major challenge in China, many current gypsum processing technologies are mostly designed for processing single types of gypsum. However, this invention is applicable to almost all types of gypsum, especially industrial by-product gypsum, without requiring specific limitations on the type of gypsum, and features energy efficiency, high performance, and wide applicability.

[0025] For example, in this invention, the granulated blast furnace slag powder is grade S95.

[0026] For example, the water-reducing agent includes at least one of melamine water-reducing agent, lignin water-reducing agent, naphthalene-based water-reducing agent, polycarboxylate water-reducing agent, or melamine-based high-efficiency water-reducing agent.

[0027] For example, the latex powder is a redispersible latex powder, specifically including at least one of vinyl acetate polymer powder, acrylic polymer powder, ethylene-vinyl chloride copolymer powder, styrene-acrylate copolymer powder, vinyl acetate-ethylene copolymer powder, or butadiene-styrene copolymer powder.

[0028] Preferably, the water-retaining agent includes at least one of hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxyethyl methyl cellulose, or hydroxypropyl methyl cellulose.

[0029] For example, the starch ether includes at least one of hydroxyethyl starch ether (HES), hydroxypropyl starch ether (HPS), or carboxymethyl starch ether (CMS).

[0030] For example, the retarder includes at least one of tartaric acid, sodium gluconate, sodium citrate, zinc carbonate, citric acid, or gypsum retarder.

[0031] For example, the waterproofing agent includes at least one of paraffin emulsion water-repellent agent, organosilicon penetrating crystalline waterproofing agent, or stearate water-repellent agent.

[0032] For example, the pigment includes at least one of titanium dioxide, iron oxide red, ultramarine, iron oxide black, chromium oxide green, Prussian red, manganese oxide, chromium oxide, iron oxide yellow, ochre, mica, or cobalt blue.

[0033] Preferably, the compressive strength of the high-strength, water-resistant, and frost-resistant putty after 28 days of standard underwater curing is 15.4 MPa to 31.3 MPa.

[0034] Preferably, the compressive strength of the high-strength, water-resistant, and frost-resistant putty after 28 days of dry-air standard curing is 11.8 MPa to 28.3 MPa.

[0035] Preferably, the high-strength water-resistant putty has a bonding strength of 0.78MPa~2.31MPa after 10 freeze-thaw cycles.

[0036] The industry standard JCT 2514-2019 Gypsum Putty (JC / T 2514-2019) requires the bonding strength of gypsum-based putty to be ≥0.5MPa. The bonding strength of existing products is generally 0.5MPa~0.8MPa, and the bonding strength of existing cement-based putty is generally 0.8MPa~1.2MPa. The high-strength, water-resistant, and frost-resistant putty of this invention has a bonding strength of up to 1.17MPa~2.05MPa after 14 days of standard curing.

[0037] In the frost resistance test of the industry standard "Putty for Building Exterior Walls", the frost resistance grade of putty is only F5, while the frost resistance grade of the high-strength frost-resistant putty of this invention can reach F10 or above.

[0038] Cement-based putty has high shrinkage and is prone to cracking. According to the standard JGJ / T70-2009 "Standard for Test Methods of Basic Performance of Building Mortar", the shrinkage value generally exceeds 0.21%. The high-strength water-resistant and frost-resistant putty of this invention has a shrinkage of only 0.063%~0.098%, which is far lower than the shrinkage value of cement-based putty. This significantly reduces the risk of cracking and greatly improves its durability.

[0039] Secondly, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty. The preparation method includes the following steps: taking each component of the high-strength water-resistant and frost-resistant putty according to the design ratio, adding water and mixing, controlling the water-to-material ratio to be 0.32~0.38, to obtain the high-strength water-resistant and frost-resistant putty.

[0040] The method for preparing high-strength, water-resistant, and frost-resistant putty provided by this invention can balance the workability, strength, and volumetric deformation of the putty by limiting the water-to-material ratio. It should be noted that the amount of water used in this invention is calculated based on the water-to-material ratio and is not included in the raw materials of the high-strength, water-resistant, and frost-resistant putty; the strength, frost resistance rating, and other performance data of the aforementioned high-strength, water-resistant, and frost-resistant putty are test results after mixing with water and curing for a certain period of time.

[0041] The present invention has the following beneficial effects: The high-strength, water-resistant, and frost-resistant putty provided by this invention utilizes high-free-calcium belite sulfoaluminate clinker and granulated blast furnace slag powder in a synergistic effect to regulate the types, composition, and microstructure of gypsum hydration products. This allows for the directional induction of hydration products with excellent water resistance (AFt and C-(A)-SH gel) to grow around dihydrate gypsum, blocking the contact between external moisture and dihydrate gypsum, inhibiting its dissolution, and thus significantly improving the water resistance and mechanical properties of the putty. It can even achieve the effect of curing strength in standard water exceeding that in standard dry air.

[0042] Furthermore, high-free-calcium belite sulfoaluminate clinker, amorphous calcium aluminate, and granulated blast furnace slag powder also exhibit synergistic hydration effects. The free calcium oxide in the clinker provides a suitable alkaline environment, which, under the synergistic activation effect of amorphous calcium aluminate, can activate the glassy structure in the granulated blast furnace slag powder. The generated AFt microcrystals induce the dissolution of substances within the glassy structure. Under the induction of AFt microcrystals, [Al(OH)4] can be dissolved from the granulated blast furnace slag powder. - and Ca 2+ It reacts with the externally added gypsum to continue generating AFt, which fills the pores; the remaining Ca in the granulated blast furnace slag powder 2+ and SiO3 2- It also gradually dissolves, and the AFt microcrystals generated in the early clinker reaction are Ca. 2+ and SiO3 2- The reaction generates C-(A)-SH gel, providing growth sites and accelerating its formation. Furthermore, the C-(A)-SH gel can create an encapsulation effect on the surface of gypsum dihydrate crystals. In addition, the C-(A)SH gel has a low calcium-to-silica ratio, resulting in a denser microstructure and better encapsulation of gypsum dihydrate. As the microstructure gradually becomes denser, the porosity of the high-strength, water-resistant, and freeze-resistant putty gradually decreases, thereby gradually increasing its mechanical strength. The water-resistant, high-strength hydration product system formed in this invention, primarily composed of ettringite (AFt) and C-(A)-SH gel, can further combine with other components in the formulation (such as latex powder and water-retaining agents) to construct a dense microstructure, thereby achieving improved high strength, water resistance, and freeze-resistance of the putty.

[0043] Compared to traditional gypsum-based putty, the high-strength, water-resistant, and frost-resistant putty provided by this invention has significantly improved water resistance, strength, and frost resistance. The high-strength, water-resistant, and frost-resistant putty of this invention exhibits a bonding strength of 1.51 MPa to 2.05 MPa after 14 days of standard curing, and a bonding strength of 0.78 MPa to 2.31 MPa after 10 freeze-thaw cycles, demonstrating high frost resistance. Ordinary gypsum-based putty has poor water resistance, with a softening coefficient (the ratio of water-cured strength to dry-cured strength) typically below 0.5. In contrast, the high-strength, water-resistant, and frost-resistant putty of this invention exhibits excellent water resistance. In Examples 1 to 28 of this invention, the 28-day dry compressive strength of the high-strength, water-resistant, and frost-resistant putty reaches 11.8 MPa to 28.3 MPa, and the 28-day wet compressive strength reaches 13.9 MPa to 31.3 MPa. The ratio of wet compressive strength to dry compressive strength after 28 days of water curing exceeds 100%. This not only improves strength but also solves the problem that the water strength of traditional gypsum-based putty is far lower than its dry-cured strength. Furthermore, the shrinkage value of the high-strength, water-resistant, and frost-resistant putty of the present invention is 0.063%~0.098%, which is much lower than that of cement-based putty, significantly reducing the risk of cracking and greatly improving its durability. Attached Figure Description

[0044] Figure 1 This is an electron microscope image of the high-strength, water-resistant, and frost-resistant putty in Example 1 of the present invention after 28 days of curing; Figure 2 This is an electron microscope image of the high-strength, water-resistant, and frost-resistant putty after 28 days of curing in Example 2 of this invention; Figure 3 This is an electron microscope image of the gypsum-based putty in Comparative Example 3 of the present invention after 28 days of curing. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0046] In the embodiments of this invention, the amorphous calcium aluminate has no crystalline phase and a density of 2.95 g / cm³. 3 Specific surface area is 551 m² 2 / kg, purchased from Anhui Qiming New Materials Co., Ltd.; desulfurized gypsum-based building gypsum purchased from Luanxian Fuyou Renewable Resources Co., Ltd.; fluorogypsum purchased from Anhui Jinyang Fluorochemical Co., Ltd.; phosphogypsum-based building gypsum purchased from Shandong Shantian Chemical Technology Co., Ltd.; anhydrite purchased from Anhui Huantai New Materials Co., Ltd.; desulfurized gypsum purchased from Qian'an Yangang; α-high-strength gypsum purchased from Pingyi Yuantong Gypsum Products Co., Ltd.; wet desulfurized gypsum purchased from Qian'an Yangang; phosphogypsum purchased from Qinhuangdao Huaying Phosphoric Acid Co., Ltd.; wet phosphogypsum purchased from Qinhuangdao Huaying Phosphoric Acid Co., Ltd.; dried phosphogypsum was obtained from wet phosphogypsum through... The desulfurized gypsum was prepared by drying wet desulfurized gypsum; S95 grade granulated blast furnace slag powder was purchased from Qian'an Shengjiu Building Materials Co., Ltd.; S75 grade granulated blast furnace slag powder was purchased from Yunnan Xinping Yongfu Environmental Protection Co., Ltd.; 100-200 mesh quartz powder was purchased from Qinhuangdao Punai Quartz Sand Co., Ltd.; 120-180 mesh dolomite powder was purchased from Xubang Mineral Products Processing Co., Ltd.; and LN-888 talc powder was purchased from Beijing Lanning Science and Trade Co., Ltd.; P·W32.5 grade white silicate cement was purchased from Jiangxi Yinsong White Cement Co., Ltd.; and the waterproofing agent was selected from ELOTEX® SEAL80, a highly active redispersible silane hydrophobic agent. The redispersible latex powder was selected from Mitsubishi 7400P or Wacker 328; the water-retaining agent was selected from 40000 PFV hydroxyethyl methyl cellulose purchased from Dow Chemical (China) Investment Co., Ltd. or HPMC 2W hydroxypropyl methyl cellulose purchased from Hubei Zhaojia Materials Co., Ltd.; the starch ether was selected from ELOSET 542 purchased from ELOSET Asia Pacific Group and Casucol S301 purchased from Avebe GmbH, Netherlands; the pigment S313 iron oxide yellow was purchased from Shanghai Yipin Pigment Co., Ltd.; other products without specified manufacturers were all products that could be obtained commercially.

[0047] Example 1 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 8.5% high-free-calcium belite sulfoaluminate clinker, 29% desulfurized gypsum-based building gypsum, 39.52% S95 grade granulated blast furnace slag powder, 21% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The high-free-calcium belite sulfoaluminate clinker comprises the following mineral components by weight percentage: 33.29% belite, 25.84% anhydrous calcium sulfoaluminate, 15.39% free calcium oxide, 12.14% free calcium sulfate, 5.78% iron phase, and 7.56% mixed mineral components. The high-free-calcium belite sulfoaluminate clinker comprises, by weight percentage, oxides: 11.60% SiO2, 14.20% Al2O3, 55.20% CaO, 10.50% SO3, 1.90% Fe2O3, and 6.60% mixed oxides. Its preparation method is as follows: S1. Take limestone, bauxite and gypsum in a mass ratio of 60.5:21.0:18.5, mix them and grind them. After passing through a 0.08mm square hole sieve, 13% residue is obtained to obtain raw material. The chemical components in the raw material satisfy the following: ([CaO]-1.87×[SiO2]-1.05×[Fe2O3]-0.7×[TiO2]-0.55×[Al2O3]-0.7×[SO3]) / (100%-α)=15.39%; (1.7×[SO3]-0.45×[Al2O3]+0.28×[Fe2O3]) / (100%-α)=12.14%; In the formula, α is the loss on ignition of the raw meal.

[0048] S2. Place the raw material in a rotary kiln and calcine it at 1250℃. Grind it to obtain high free calcium belite sulfoaluminate clinker.

[0049] Furthermore, the present invention also provides a method for preparing the above-mentioned high-strength, water-resistant, and frost-resistant putty, comprising the following steps: After mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty, water is added and mixed, and the water-to-material ratio is controlled at 0.36 to obtain high-strength water-resistant and frost-resistant putty.

[0050] After curing the high-strength, water-resistant, and frost-resistant putty of this embodiment for 28 days, an electron microscope scanning test was performed. The test results are as follows: Figure 1 As shown.

[0051] Example 2 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 42.48% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.0% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG46 gypsum retarder, and 0.05% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV.

[0052] The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 1.

[0053] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0054] After curing the high-strength, water-resistant, and frost-resistant putty of this embodiment for 28 days, an electron microscope scanning test was performed. The test results are as follows: Figure 2 As shown.

[0055] Example 3 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 32.5% S75 grade granulated blast furnace slag powder, 30.5% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.1% sodium citrate, and 0.03% Casucol S301; The filler consists of 30% 120-180 mesh dolomite powder and 0.5% talc powder; The water-retaining agent is HPMC 2W.

[0056] The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 1.

[0057] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0058] Example 4 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 31.8% S95 grade granulated blast furnace slag powder, 31% filler, 0.2% ELOTEX® SEAL80 waterproofing agent, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.1% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 30% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV.

[0059] The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 1.

[0060] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0061] Example 5 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 31.9% S95 grade granulated blast furnace slag powder, 31% filler, 0.1% ELOTEX® SEAL80 waterproofing agent, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.1% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 30% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV.

[0062] The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 1.

[0063] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0064] Example 6 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% fluorogypsum-based dihydrate gypsum, 42.28% S95 grade granulated blast furnace slag powder, 20.8% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, and 0.05% Casucol S301; The filler consists of 20% 100-200 mesh quartz powder and 0.8% talc powder; The water-retaining agent has a concentration of 40,000 PFV.

[0065] The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 1.

[0066] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.33, thereby obtaining high-strength water-resistant and frost-resistant putty.

[0067] Example 7 This embodiment provides a high-strength, water-resistant, and freeze-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% dried desulfurized gypsum, 41.96% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.12% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV.

[0068] The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 1.

[0069] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.37, to obtain high-strength water-resistant and frost-resistant putty.

[0070] Example 8 This embodiment provides a high-strength, water-resistant, and freeze-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% dried phosphogypsum, 42.06% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.02% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV.

[0071] The high-free-calcium belite sulfoaluminate clinker comprises the following mineral components by weight percentage: anhydrous calcium sulfoaluminate 25.31%, free calcium sulfate 12.26%, free calcium oxide 14.82%, belite 33.87%, tetracalcium aluminoferrite 6.08%, and mixed mineral components 7.66%. The high-free-calcium belite sulfoaluminate clinker also comprises the following oxides by weight percentage: SiO2 11.80%, Al2O3 14.00%, CaO 55.00%, SO3 10.50%, Fe2O3 2.00%, and mixed oxides 6.70%.

[0072] The preparation method of the above-mentioned high free calcium berite sulfoaluminate clinker includes the following steps: S1. Take limestone, bauxite and gypsum in a mass ratio of 60.0:21.3:18.7, mix them and grind them. After passing through a 0.08mm square hole sieve, 12% residue is obtained to obtain raw material. The chemical components in the raw material satisfy the following: ([CaO]-1.87×[SiO2]-1.05×[Fe2O3]-0.7×[TiO2]-0.55×[Al2O3]-0.7×[SO3]) / (100%-α)=14.82%; (1.7×[SO3]-0.45×[Al2O3]+0.28×[Fe2O3]) / (100%-α)=12.26%; In the formula, α is the loss on ignition of the raw meal.

[0073] S2. Place the raw material in a rotary kiln and calcine it at 1200℃. Grind it to obtain high free calcium belite sulfoaluminate clinker.

[0074] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0075] Example 9 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% anhydrite, 42.1% S95 grade granulated blast furnace slag powder, 21% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV.

[0076] The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 8.

[0077] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.32, to obtain high-strength water-resistant and frost-resistant putty.

[0078] Example 10 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% α-high-strength gypsum, 41.04% S95 grade granulated blast furnace slag powder, 22% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.06% sodium gluconate, and 0.03% Casucol S301; The filler consists of 20% 120-180 mesh dolomite powder and 2% talc powder; The water-retaining agent is HPMC 2W; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 8.

[0079] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0080] Example 11 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 41.84% S95 grade granulated blast furnace slag powder, 21% filler, 0.2% SM water-reducing agent, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 8.

[0081] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0082] Example 12 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 37.01% S95 grade granulated blast furnace slag powder, 21.5% filler, 0.03% polycarboxylate superplasticizer, 2% 7400P waterproof adhesive powder, 0.35% water-retaining agent, 0.08% sodium gluconate, 0.03% ELOSET542 starch ether, and 4% S313 iron oxide yellow; The filler consists of 20% 100-200 mesh quartz powder and 1.5% talc powder; The water-retaining agent is HPMC 2W; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 8.

[0083] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0084] Example 13 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4.0% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 41.49% S95 grade granulated blast furnace slag powder, 21% filler, 0.4% SM water-reducing agent, 1.5% 7400P waterproof adhesive powder, 0.5% water-retaining agent, 0.08% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 8.

[0085] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.35, to obtain high-strength water-resistant and frost-resistant putty.

[0086] Example 14 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 8.5% high-free-calcium belite sulfoaluminate clinker, 21% desulfurized gypsum-based building gypsum, 47.52% S95 grade granulated blast furnace slag powder, 21% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 8.

[0087] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0088] Example 15 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 8.5% high-free-calcium belite sulfoaluminate clinker, 21% desulfurized gypsum-based building gypsum, 37.5% S95 grade granulated blast furnace slag powder, 31% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.1% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 30% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The high-free-calcium belite sulfoaluminate clinker comprises the following mineral components by weight percentage: 29.27% ​​belite, 32.08% anhydrous calcium sulfoaluminate, 16.92% free calcium oxide, 9.57% free calcium sulfate, 6.08% iron phase, and 6.08% mixed mineral components. The high-free-calcium belite sulfoaluminate clinker comprises, by weight percentage, oxides: 10.20% SiO2, 17.40% Al2O3, 55.20% CaO, 9.80% SO3, 2.00% Fe2O3, and 5.40% mixed oxides. Its preparation method is as follows: S1. Take limestone, bauxite and gypsum in a mass ratio of 61.9:20.6:17.5, mix them and grind them. After passing through a 0.08mm square hole sieve, 14% residue is obtained to obtain raw material. The chemical components in the raw material satisfy the following: ([CaO]-1.87×[SiO2]-1.05×[Fe2O3]-0.7×[TiO2]-0.55×[Al2O3]-0.7×[SO3]) / (100%-α)=16.92%; (1.7×[SO3]-0.45×[Al2O3]+0.28×[Fe2O3]) / (100%-α)=9.57%; In the formula, α is the loss on ignition of the raw meal.

[0089] S2. Place the raw material in a rotary kiln and calcine it at 1300℃. Grind it to obtain high free calcium belite sulfoaluminate clinker.

[0090] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0091] Example 16 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 8.5% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 27.48% S95 grade granulated blast furnace slag powder, 31% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.12% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 30% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 15.

[0092] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.37, to obtain high-strength water-resistant and frost-resistant putty.

[0093] Example 17 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 34.04% S95 grade granulated blast furnace slag powder, 21% filler, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG46 gypsum retarder, 0.03% ELOSET542 starch ether, and 6% S313 iron oxide yellow; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 15.

[0094] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0095] Example 18 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 43% desulfurized gypsum-based building gypsum, 27.96% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.12% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 15.

[0096] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.37, to obtain high-strength water-resistant and frost-resistant putty.

[0097] Example 19 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 43% desulfurized gypsum-based building gypsum, 1% amorphous calcium aluminate, 26.96% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.12% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 15.

[0098] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.37, to obtain high-strength water-resistant and frost-resistant putty.

[0099] Example 20 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 43% α-high-strength gypsum, 28.0% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 15.

[0100] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0101] Example 21 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 43% phosphogypsum-based building materials, 24.6% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 3.0% 328 redispersible latex powder, 0.2% water-retaining agent, 0.16% AG36 gypsum retarder, and 2% S313 iron oxide yellow; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 15.

[0102] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.37, to obtain high-strength water-resistant and frost-resistant putty.

[0103] Example 22 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 43% phosphogypsum-based building gypsum, 28.06% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.02% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The high-free-calcium belite sulfoaluminate clinker comprises the following mineral components by weight percentage: 6.55% free calcium sulfate, 19.71% free calcium oxide, 31.92% anhydrous calcium sulfoaluminate, 32.14% belite, 4.56% tetracalcium aluminoferrite and 5.12% mixed mineral components. The high-free-calcium belite sulfoaluminate clinker comprises, by weight percentage, oxides: 11.20% SiO2, 17.0% Al2O3, 58.0% CaO, 8.0% SO3, 1.50% Fe2O3, and 4.30% mixed oxides. Its preparation method is as follows: S1. Take limestone, bauxite and gypsum in a mass ratio of 66.4:19.3:14.3, mix them and grind them. After passing through a 0.08mm square hole sieve, 13% residue is obtained to obtain raw material. The chemical components in the raw material satisfy the following: ([CaO]-1.87×[SiO2]-1.05×[Fe2O3]-0.7×[TiO2]-0.55×[Al2O3]-0.7×[SO3]) / (100%-α)=19.71%; (1.7×[SO3]-0.45×[Al2O3]+0.28×[Fe2O3]) / (100%-α)=6.55%; In the formula, α is the loss on ignition of the raw meal.

[0104] S2. Place the raw material in a rotary kiln and calcine it at 1250℃. Grind it to obtain high free calcium belite sulfoaluminate clinker.

[0105] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.33, thereby obtaining high-strength water-resistant and frost-resistant putty.

[0106] Example 23 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 43% dried desulfurized gypsum, 0.5% amorphous calcium aluminate, 27.32% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.1% sodium citrate, 0.16% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 22.

[0107] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.38, to obtain high-strength water-resistant and frost-resistant putty.

[0108] Example 24 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 43% dried phosphogypsum, 26.02% S95 grade granulated blast furnace slag powder, 23% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.06% sodium citrate, and 0.03% Casucol S301; The filler consists of 20% 120-180 mesh dolomite powder and 3% talc powder; The water-retaining agent is HPMC 2W; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 22.

[0109] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.37, to obtain high-strength water-resistant and frost-resistant putty.

[0110] Example 25 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4% high-free-calcium belite sulfoaluminate clinker, 31% desulfurized gypsum-based building gypsum, 42.02% S95 grade granulated blast furnace slag powder, 21% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 22.

[0111] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0112] Example 26 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 6% high-free-calcium belite sulfoaluminate clinker, 21% desulfurized gypsum-based building gypsum, 50.02% S95 grade granulated blast furnace slag powder, 21% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 22.

[0113] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0114] Example 27 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4% high-free-calcium belite sulfoaluminate clinker, 21% desulfurized gypsum-based building gypsum, 52.02% S95 grade granulated blast furnace slag powder, 21% filler, 0.02% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.08% AG46 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 22.

[0115] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain high-strength water-resistant and frost-resistant putty.

[0116] Example 28 This embodiment provides a high-strength, water-resistant, and frost-resistant putty, comprising the following components by weight percentage: 4% high-free-calcium belite sulfoaluminate clinker, 27% desulfurized gypsum-based building gypsum, 45.96% S95 grade granulated blast furnace slag powder, 21% filler, 0.04% polycarboxylate superplasticizer, 1.5% 328 redispersible latex powder, 0.35% water-retaining agent, 0.12% AG36 gypsum retarder, and 0.03% ELOSET542 starch ether; The filler consists of 20% 100-200 mesh quartz powder and 1% talc powder; The water-retaining agent has a concentration of 40,000 PFV; The components and preparation method of the high free calcium belite sulfoaluminate clinker are the same as those in Example 22.

[0117] In addition, the present invention also provides a method for preparing the above-mentioned high-strength water-resistant and frost-resistant putty, comprising the following steps: mixing the raw material components of the above-mentioned high-strength water-resistant and frost-resistant putty and adding water to mix, controlling the water-to-material ratio to be 0.37, to obtain high-strength water-resistant and frost-resistant putty.

[0118] Comparative Example 1 This comparative example provides a gypsum-based putty composed of the following components by weight percentage: 31% desulfurized gypsum-based building gypsum, 66.58% dolomite powder (120-180 mesh), 0.1% ELOTEX® SEAL80 waterproofing agent, 1.8% 328 redispersible latex powder, 0.32% 40000 PFV, 0.02% ELOSET542 starch ether, and 0.2% AG36 gypsum retarder.

[0119] The preparation method of gypsum-based putty includes the following steps: mixing the components of the above-mentioned gypsum-based putty and adding water, with a water-to-material ratio of 0.34, to obtain gypsum-based putty.

[0120] Comparative Example 2 This comparative example provides a cement-based putty composed of the following components by weight percentage: 30% white silicate cement P·W32.5, 13% 100-200 mesh quartz powder, 56.12% 120-180 mesh dolomite powder, 0.1% ELOTEX® SEAL80 waterproofing agent, 0.5% 328 redispersible latex powder, 0.15% 40000 PFV, 0.03% ELOSET542 starch ether, and 0.1% sodium gluconate.

[0121] The preparation method of cement-based putty includes the following steps: mixing the components of the above-mentioned cement-based putty and adding water to mix, controlling the water-to-material ratio to be 0.28, to obtain cement-based putty.

[0122] Comparative Example 3 This comparative example provides a gypsum-based putty composed of the following components by weight percentage: 43% desulfurized gypsum-based building gypsum, 18% 100-200 mesh quartz powder, 36.45% 120-180 mesh dolomite powder, 0.1% ELOTEX® SEAL80 waterproofing agent, 2.0% 328 redispersible latex powder, 0.2% 40000 PFV, 0.02% ELOSET542 starch ether, and 0.23% AG46 gypsum retarder.

[0123] The preparation method of the above-mentioned gypsum-based putty includes the following steps: mixing the components of the above-mentioned gypsum-based putty and adding water to mix, controlling the water-to-material ratio to be 0.36, to obtain gypsum-based putty.

[0124] After curing the gypsum-based putty in this comparative example for 28 days, an electron microscope scan test was performed. The test results are as follows: Figure 3 As shown.

[0125] Example of effect The putty provided in Examples 1-28 and Comparative Examples 1-3 was subjected to performance tests, and the test results are shown in Tables 1-3.

[0126] The test methods, specifications, and product standards adopted are as follows: Bulk density and water retention rate tests are performed according to national standard GB / T28627-2023 "Plastering Gypsum"; dry compressive strength tests are performed according to national standard GB / T 17669.3-1999 "Determination of Mechanical Properties of Building Gypsum"; wet compressive strength tests are performed according to GB / T 17671-2021 "Test Method for Strength of Cement Mortar (ISO Method)"; shrinkage rate tests are performed according to industry standard JGJ / T70-2009 "Standard for Basic Performance Test Methods of Building Mortar"; bond strength (standard state, 5 freeze-thaw cycles, 10 freeze-thaw cycles, 7 days of standard state curing followed by 7 days of water curing, 28 days of standard state curing), as well as workability, drying time, initial drying crack resistance, sandability, water absorption, alkali resistance, water resistance, putty film flexibility, and dynamic crack resistance are performed according to JG / T157-2009 "Putty for Building Exterior Walls". The bond strength measured after 7 days of standard curing followed by 7 days of water immersion curing is recorded as the water immersion bond strength.

[0127] Table 1 Performance test results of mortars in the examples and comparative examples 1

[0128] Table 2 Performance test results of mortars in the examples and comparative examples 2

[0129] Table 3 Performance test results of mortars in the examples and comparative examples 3

[0130] As can be seen from the table, the 28-day dry compressive strength of the high-strength, water-resistant, and frost-resistant putty in Examples 1-28 of this invention is as high as 11.8 MPa to 28.3 MPa, and the 28-day wet compressive strength is as high as 13.9 MPa to 31.3 MPa. The ratio of the 28-day wet compressive strength to the dry compressive strength is over 100%. The 28-day dry compressive strength and wet compressive strength of the cement-based putty in Comparative Example 2 are only 11.6 MPa and 11.8 MPa, respectively, which is much lower than that of the examples of this invention. The raw materials and proportions of the gypsum-based putty mortar in Comparative Example 1 are similar to those in Example 5. The gypsum content and waterproofing agent content are the same in Comparative Example 1 and Example 5. The water-to-material ratio of Comparative Example 1 is lower than that of Example 5, and the amount of redispersible latex powder in Comparative Example 1 is higher than that in Example 5. Example 5 of this invention significantly improves the strength and water resistance of the mortar by adding an appropriate amount of high-free-calcium belite sulfoaluminate clinker and granulated blast furnace slag powder. The 28-day dry compressive strength of Comparative Example 1 was 10.1 MPa, while that of Example 5 was 24.3 MPa; the 28-day wet compressive strength of Comparative Example 1 was 2.2 MPa (the strength decreased several times after wet curing), while that of Example 5 was 25.8 MPa; the ratio of the 28-day wet compressive strength to the dry compressive strength of Comparative Example 1 was 22%, while that of Example 5 was as high as 106%. The gypsum content of Comparative Example 3 is the same as that of Example 18. The amount of 328 redispersible latex powder in Comparative Example 3 is higher than that in Example 18. Comparative Example 3 also contains 0.1% more water-repellent agent and has a lower water-to-material ratio of 0.01. By using clinker with optimized mineral composition, the mechanical properties of the mortar are significantly improved. The 28-day dry compressive strength of Comparative Example 3 is 13.5 MPa, while that of Example 18 is 22.1 MPa; the 28-day wet compressive strength of Comparative Example 3 is 2.8 MPa, while that of Example 18 is 23.8 MPa; the ratio of the 28-day wet compressive strength to the dry compressive strength of Comparative Example 3 is 21%, while that of Example 18 is as high as 108%. These data and comparisons demonstrate that the high-strength, water-resistant, and frost-resistant putty of this invention has high strength and excellent water resistance. The compressive strength after 28 days of standard underwater curing is greater than that after 28 days of standard dry air curing.

[0131] The 28-day shrinkage rate of the high-strength, water-resistant, and frost-resistant putty in Examples 1-28 of this invention is only 0.063%~0.098%, while the 28-day shrinkage rate of the cement-based putty in Comparative Example 2 is as high as 0.21%, more than three times that of the former. The above data and comparisons demonstrate that the high-strength, water-resistant, and frost-resistant putty of this invention has superior crack resistance compared to cement-based putty.

[0132] The bonding strength of the high-strength water-resistant and frost-resistant putty in Examples 1-28 of this invention, after 14 days in the standard state, is 1.17 MPa to 2.05 MPa; the bonding strength of the putty in Comparative Examples 1-3, after 14 days in the standard state, is 0.68 MPa, 0.88 MPa, and 0.82 MPa, respectively. The bonding strength of the high-strength water-resistant and frost-resistant putty in Examples 1-28 of this invention, after 28 days in the standard state, is 1.51 MPa to 2.52 MPa; the bonding strength of the putty in Comparative Examples 1-3, after 28 days in the standard state, is only 0.46 MPa, 0.59 MPa, and 0.56 MPa, respectively. These data and comparisons demonstrate that the high-strength water-resistant and frost-resistant putty of this invention has a bonding strength to the substrate that is 3 to 5 times that of the comparative examples.

[0133] The bonding strength of the high-strength, water-resistant, and frost-resistant putty in Examples 1-28 of this invention, under water immersion conditions, ranges from 1.43 MPa to 2.77 MPa. In contrast, the mortars in Comparative Examples 1 and 3 showed no strength after water immersion treatment, with the specimens exhibiting powdering and failure. The bonding strength of Comparative Example 2 after water immersion treatment was 0.7 MPa. These data and comparisons demonstrate that the bonding strength between the high-strength, water-resistant, and frost-resistant putty of this invention and the substrate after water immersion treatment is 2 to 4 times that of the comparative examples.

[0134] The bonding strength test specimens of the high-strength water-resistant and frost-resistant putty in Examples 1-28 of this invention showed a bonding strength of 0.87 MPa to 2.22 MPa after 5 freeze-thaw cycles. The bonding strength of the high-strength water-resistant and frost-resistant putty test specimens in Examples 1-28 showed a bonding strength of 0.78 MPa to 2.31 MPa after 10 freeze-thaw cycles. The cement putty of Comparative Example 2 showed a bonding strength of 0.64 MPa after 5 freeze-thaw cycles and 0.36 MPa after 10 freeze-thaw cycles. The bonding strength between the high-strength water-resistant and frost-resistant putty of this invention and the substrate after 10 freeze-thaw cycles was 2 to 6 times that of the comparative examples. The frost resistance of Comparative Examples 1-3 was inferior to that of the examples. The gypsum-based putty of Comparative Examples 1 and 3 completely pulverized and lost strength after 5 freeze-thaw cycles, further verifying the poor frost resistance of traditional gypsum-based mortar.

[0135] The high-strength water-resistant and frost-resistant putty in Examples 1 to 28 of this invention meets the requirements of JG / T157-2009 "Putty for Building Exterior Walls" standard in terms of workability, drying time, initial drying crack resistance, sandability, water absorption, water resistance, alkali resistance, putty film flexibility, dynamic crack resistance, and other technical indicators.

[0136] In summary, the high-strength, water-resistant, and frost-resistant putty provided by this invention outperforms cement-based and gypsum-based putty in all aspects. It can be widely used for interior and exterior walls of buildings, especially suitable for cold, rainy, or high-performance regions, and is also more cost-effective, showing great promise. This high-strength, water-resistant, and frost-resistant putty expands the application fields of industrial by-product gypsum, provides new technical ideas for the recycling of industrial by-product gypsum, and promotes the harmless, large-scale, and resource-based utilization of industrial by-product gypsum.

[0137] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A high-strength, water-resistant, and frost-resistant putty, characterized in that, It comprises the following components by weight percentage: 4%~8.5% high free calcium belite sulfoaluminate clinker, 24.6%~52.1% granulated blast furnace slag powder, 21%~43% gypsum, 21%~31% filler, 1.0%~3.0% latex powder and 0.2%~0.5% water-retaining agent; The high-free-calcium belite sulfoaluminate clinker comprises the following mineral components by weight percentage: 25.31%~33.27% anhydrous calcium sulfoaluminate, 14.82%~19.71% free calcium oxide, 6.55%~12.26% free calcium sulfate, 27.27%~33.87% belite, and 3.04%~6.08% iron phase.

2. The high-strength, water-resistant, and frost-resistant putty as described in claim 1, characterized in that, The high-free-calcium berit sulfoaluminate clinker comprises the following oxides by weight percentage: 55%~58% CaO, 14%~18% Al2O3, 9.5%~11.8% SiO2, 8%~11% SO3 and 1%~2% Fe2O3.

3. The high-strength, water-resistant, and frost-resistant putty as described in claim 1, characterized in that, The filler includes at least one of talc powder, quartz powder, or dolomite powder.

4. The high-strength, water-resistant, and frost-resistant putty as described in claim 1, characterized in that, The high-strength, water-resistant, and frost-resistant putty also includes the following components by weight percentage: 0~1% amorphous calcium aluminate, 0~0.4% water-reducing agent, 0~0.05% starch ether, 0~0.26% retarder, 0~0.2% waterproofing agent, and 0~6% pigment.

5. The high-strength, water-resistant, and frost-resistant putty as described in claim 4, characterized in that, The amorphous content of the amorphous calcium aluminate is ≥99.0%, and the specific surface area is ≥500 m². 2 / kg.

6. The high-strength, water-resistant, and frost-resistant putty as described in claim 4, characterized in that, The water-retaining agent includes at least one of hydroxyethyl methylcellulose, methylcellulose, carboxymethylcellulose, hydroxyethyl methylcellulose, or hydroxypropyl methylcellulose.

7. The high-strength, water-resistant, and frost-resistant putty as described in any one of claims 1 to 6, characterized in that, The high-strength, water-resistant, and frost-resistant putty exhibits a compressive strength of 15.4 MPa to 31.3 MPa after 28 days of standard underwater curing; and / or The compressive strength after 28 days of dry-air standard curing is 11.8 MPa to 28.3 MPa; and / or The high-strength water-resistant putty has a bonding strength of 0.78MPa~2.31MPa after 10 freeze-thaw cycles.

8. The method for preparing high-strength, water-resistant, and frost-resistant putty according to any one of claims 1 to 7, characterized in that, The preparation method includes the following steps: taking each component of the high-strength water-resistant and frost-resistant putty according to the design ratio, adding water and mixing, controlling the water-to-material ratio to be 0.32~0.38, to obtain the high-strength water-resistant and frost-resistant putty.

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