CN117003530A - Water-based material for beautifying and protecting bare concrete and application thereof - Google Patents

Water-based material for beautifying and protecting bare concrete and application thereof Download PDF

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Publication number
CN117003530A
CN117003530A CN202310635256.9A CN202310635256A CN117003530A CN 117003530 A CN117003530 A CN 117003530A CN 202310635256 A CN202310635256 A CN 202310635256A CN 117003530 A CN117003530 A CN 117003530A
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CN
China
Prior art keywords
parts
emulsion
powder
water
aqueous material
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Pending
Application number
CN202310635256.9A
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Chinese (zh)
Inventor
李霞
李彦波
袁静
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Beijing Beautiful Times Technology Development Co ltd
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Beijing Beautiful Times Technology Development Co ltd
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Priority to CN202310635256.9A priority Critical patent/CN117003530A/en
Publication of CN117003530A publication Critical patent/CN117003530A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C04B2111/00508—Cement paints
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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

Abstract

The invention relates to an aqueous material for beautification and protection of bare concrete and application thereof. The water-based material for the beautification and protection of the bare concrete comprises powder and emulsion, wherein the powder comprises cement, sand powder, mineral powder, a dispersion suspending agent, titanium pigment and fly ash; the emulsion comprises high molecular polymerization emulsion, a defoaming agent, a water reducing agent and water. The water-based material provided by the invention remarkably improves the bonding force of the beautified protective material and the interface of bare concrete, has the bonding strength of more than 2.5Mpa after 28 days, and has good anti-permeability, freeze thawing resistance and other durability: the secondary impervious pressure can reach more than 0.6Mpa, and the freezing and thawing process is carried out 150 times without cracking and falling off; the pore structure and the compactness of the beautifying material are improved, the strength and the quality of the beautifying material are improved, the appearance of the beautifying material is more attractive and firm, and the erosion of moisture and harmful substances is effectively prevented.

Description

Water-based material for beautifying and protecting bare concrete and application thereof
Technical Field
The invention relates to an aqueous material for beautifying and protecting bare concrete and application thereof, belonging to the technical field of concrete material additives.
Background
The bare concrete is affected by factors such as raw materials, surface microcracks and the like, and the effect is not very good after most casting and forming: the appearance quality of the bare concrete is poor due to the influence of factors such as the production place, color and luster, gradation difference and construction, and the like, so that the defects such as chromatic aberration, holes and the like are generated; after casting, the surface and the inside of the bare concrete are subjected to water loss to generate a plurality of microcracks, so that channels are provided for external rainwater, carbon dioxide, acidic substances and other degradation factors, and the concrete is subjected to carbonization, freeze thawing and other diseases, so that the durability is poor.
Aiming at the above situation, as the bare concrete beautifying and protecting materials are widely used in the market at present, most of organic materials mainly comprising acrylic resin, organic silicon resin and fluorocarbon polymer are inflammable, odorous and toxic, and the construction process has pollution to the environment. After the material is used, a layer of nonporous and airtight coating film is formed on the surface of the concrete, so that the outward diffusion of harmful water vapor in the concrete is inhibited, and when the expansion force of the water vapor accumulated at the interface is greater than the binding force, the coating film is easy to bulge and crack; meanwhile, the comprehensive mechanical properties of the coating are not matched with those of concrete (modulus, poisson ratio, aging performance and the like), so that the phenomena of aging, skinning, falling and the like of the coating can occur after the coating is used for 1-3 years, the concrete body is damaged, and the beautifying and protecting effects of the coating cannot be maintained for a long time. Therefore, the water-based inorganic material has the advantages of no smell and toxicity, environmental friendliness to construction and personnel, comprehensive mechanical properties the same as those of the concrete body, capability of forming a one-way breathable beautifying protective layer and good durability, and has very important significance.
The active component of the nano modified silicate permeable crystallization material can permeate into the concrete, and can be used with calcium ions to generate C-S-H crystals in a reverse direction, so that pores or capillary pores in the concrete are filled, and the compactness of the surface layer of the concrete and the overall comprehensive durability are improved, but the material has no beautifying and protecting effects on the surface of the concrete and needs to be matched with a fresh water concrete beautifying and protecting material.
Disclosure of Invention
First, the technical problem to be solved
In order to solve the problems in the prior art, the invention provides a water-based inorganic concrete beautifying and protecting material and a use method thereof, which solve the problems that the existing fair-faced concrete beautifying and protecting material is easy to crack, age, peel, fall off and the like and cannot maintain the fair-faced concrete beautifying and protecting for a long time.
(II) technical scheme
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
the water-based material for the beautification and protection of the bare concrete comprises the following components in parts by weight:
powder material: 40-55 parts of cement, 5-15 parts of sand powder, 5-15 parts of mineral powder, 1-3 parts of dispersing suspending agent, 3-5 parts of titanium dioxide and 5-15 parts of fly ash;
emulsion: 45-55 parts of high molecular polymer emulsion, 1-5 parts of defoamer, 0.5-1.5 parts of water reducer and 30-40 parts of water.
The water-based material as described above, preferably, the cement is one, two or more of silicate, aluminate or aluminoferrite, sulfate cement and white cement.
Further preferably, the cement is 40 parts Portland cement, 13 parts aluminoferrite cement and 2 parts white cement.
The above aqueous material, preferably, the dispersion suspending agent is powder, and is one or more of polyalkylene oxide chain copolymer, lignosulfonate and naphthalene sulfonate formaldehyde condensate sulfonate compound.
The above aqueous material preferably has a size of 100 to 120 mesh.
The aqueous material as described above, preferably the ore fines are grade S95.
The specific surface area of the fly ash is preferably more than or equal to 500m 2 /kg。
The aqueous material as described above, preferably, the high molecular polymer emulsion is one, two or more of styrene-acrylic emulsion, vinyl acetate copolymer emulsion, silicone-acrylic emulsion or acrylic emulsion.
The above aqueous material, preferably, the defoaming agent is one or more of emulsified organic silicon, polysiloxane and aqueous organic silicon defoaming agent;
the water-based material is preferably one or more of modified polymer sulfonic acid, high polymer viscosity modifier and sulfonated melamine water reducer.
The aqueous material as described above is preferably prepared or used by directly mixing the powder and the emulsion at the time of preparation, and when in use, the powder is poured into a container, then the emulsion is poured into the container according to the recommended proportion, and then the mixture is stirred for 1-2 minutes by using an electric stirrer (550 rpm), and the mixture is used for the same day.
The aqueous material is preferably used by uniformly mixing the powder and the emulsion in a weight ratio of 1.2:1-2:1, and the dosage of the aqueous material is 100-120 g per square meter, and most preferably 120g per square meter.
Use of an aqueous material for the aesthetic protection of bare concrete, said aqueous material being used for the durable protection and beautification of new or old concrete building surfaces, preferably in an amount of 100g to 120g, most preferably 120g, of said aqueous material for painting or spraying on new or old concrete building surfaces.
(III) beneficial effects
The beneficial effects of the invention are as follows:
the aqueous material for the beautification protection of bare concrete is modified by adding the high molecular polymer emulsion, so that the cohesion and the tensile strength of the material are improved, and meanwhile, the adhesive force between the beautification protection material and the concrete interface is remarkably improved because the aqueous inorganic beautification protection material is the same as a concrete matrix, and the adhesive strength after 28 days is more than 2.5Mpa.
The water-based material for the beautification protection of bare concrete has good impermeability, freeze thawing resistance and other durability: the secondary impervious pressure can reach more than 0.6Mpa, and the secondary impervious pressure is frozen and thawed 150 times without cracking and falling.
The water-based material for the beautification protection of the bare concrete is added with the defoaming agent and the water reducing agent, so that bubbles generated when the beautification materials are mixed can be eliminated, the pore structure and the compactness of the beautification materials are improved, the strength and the quality of the beautification materials are improved, the appearance of the beautification materials is more attractive and firm, and the erosion of moisture and harmful substances is effectively prevented.
The aqueous material for the beautification protection of the bare concrete adopts the high molecular polymer emulsion as the adhesive, inorganic powder materials with different particle diameters are mixed and bonded together, capillary holes are reserved among the particles, and water used for adjusting the viscosity in the emulsion component can generate hydration heat reaction with the inorganic powder materials to a certain extent, and new capillary holes are generated among the particles; the coating can form a protective layer with capillary holes and unidirectional ventilation on bare concrete, the aperture is about 105-5010 nm, so that the water vapor (the grain diameter is about 0.4 nm) in the concrete can not be prevented from diffusing outwards, meanwhile, the infiltration of water drops (the grain diameter is 0.1-7 mm) can be prevented, the unidirectional breathing performance is realized, the original color and state of the concrete can be reproduced, and the durability of the concrete is improved.
The water-based material for beautification provided by the invention can penetrate into the concrete through the capillary holes, so that the performance of the permeable protective material is maintained.
Detailed Description
The inside of the concrete mainly has gel pores, capillary pores, coarse pores and more microcracks or defects, wherein the pore diameter of the gel pores is generally less than 10nm, the pore diameter of the capillary pores is generally 100-1000 nm, and the pore diameter of the macropores is more than 1000nm. It is considered that the medium pores of 10 to 50nm and the large pores of 50 to 10000nm affect the strength and permeability of concrete.
The beautified and protected water-based material provided by the invention is the same as the main material of the concrete matrix, but the molding process is different, the inorganic powder provided by the invention and the water in the emulsion and the water for adjusting the viscosity are subjected to hydration heat reaction, meanwhile, the emulsion is used as an adhesive, and the pores and large pores can be filled, so that the inorganic powder with different particle diameters and the concrete matrix generated by the reaction are bonded together, and therefore, the material provided by the invention has a plurality of capillary pores. The prior traditional film forming material forms a compact and nonporous protective layer on the surface of concrete, external water drops can not permeate the protective layer, and water vapor in the concrete can not diffuse to the outside, when the diffusion force of the water vapor on the interface exceeds the bonding force of the interface, the aging phenomena such as bulge, cracking and the like are easy to occur, the water-based material for beautifying and protecting can form a protective layer with capillary holes and unidirectional ventilation, the aperture of the protective layer is about 10-50 nm, the water vapor (the grain diameter is about 0.4 nm) in the concrete can not be prevented from diffusing outwards, meanwhile, the water drops (the grain diameter is 0.1-7 mm) can be prevented from penetrating, the water-based material has unidirectional breathing property, the original color and state of the concrete can be reproduced, and the durability of the concrete can be improved, namely, the water-based material for beautifying and protecting provided by the invention has unidirectional ventilation property, namely, the water vapor in the concrete can diffuse to the outside through the water drops, and can not permeate the outside.
The material is modified by the high molecular polymer emulsion, so that the cohesive force and the tensile strength of the material are improved, the stability of colloid is improved, the adhesive force and the ageing resistance are improved, and one or more of styrene-acrylic emulsion, vinyl acetate copolymer emulsion, silicone-acrylic emulsion or acrylic emulsion are preferred, however, the research shows that the weather resistance of the styrene-acrylic emulsion is general and is widely used for inner walls; the silicone-acrylic emulsion is weather-resistant, water-resistant and stain-resistant, but has higher price; the acrylic emulsion is weather-resistant in the invention, has moderate price and is used for more outer walls; the vinyl acetate copolymer emulsion has good film forming effect, high tensile strength and small elongation at break. It is preferable to use an acrylic emulsion or a vinyl acetate copolymer as the main component. The material of the invention is added with the defoaming agent and the water reducing agent, which can eliminate bubbles generated when the beautifying materials are mixed, improve the pore structure and the compactness of the beautifying materials, improve the strength and the quality of the beautifying materials, ensure that the appearance of the beautifying materials is more attractive and stronger, effectively prevent the erosion of moisture and harmful substances, and is preferably one or more of emulsified organic silicon, polysiloxane and water-based organic silicon, and the water reducing agent is one or more of modified polymer sulfonic acid, high polymer viscosity modifier and sulfonated melamine.
The present invention will be described in detail below with reference to specific embodiments for better explaining the present invention.
Example 1
The embodiment provides a bare concrete beautifying and protecting material, which comprises powder and high polymer emulsion. The powder comprises the following components in parts by weight: 40 parts of silicate cement, 13 parts of aluminoferrite cement, 2 parts of white cement, 13 parts of S95-level slag powder, 10 parts of sand powder (with the grain size of 100-120 meshes), 4 parts of titanium dioxide and 15 parts of fly ash (with the specific surface area more than or equal to 500 m) 2 /kg) 3 parts of lignin sulfonate sodium salt dispersing agent. The components of the polymer emulsion are as follows (according to parts by weight): 50 parts of vinyl acetate copolymer emulsion (non-volatile component (45+/-1)%, viscosity is 800-1000 mPa.s), 3.5 parts of polysiloxane defoamer B-296 (milky white liquid or transparent liquid, pH is 6.5-7.8), 1.5 parts of modified polymer sulfonic acid water reducer (model FDN-I) and 100 parts of water.
The using method comprises the following steps: the powder and the polymer emulsion are stirred uniformly according to the weight ratio of 1.8:1 without caking, the specific operation is that firstly, the powder is poured into a container, then the emulsion is poured into the container according to the recommended ratio, then the mixture is stirred for 2 minutes at 550 r/min by using an electric stirrer, and the mixture is coated by using a roller brush, wherein the material consumption is 120g per square meter.
After the powder and the emulsion are mixed, the emulsion is dispersed in cement mortar in the form of particles by an electric mixer, an organic-inorganic interpenetrating polymer network structure is formed along with the generation of cement paste hydration products, when the mixing amount of the emulsion reaches a certain proportion, a continuous net film structure can be formed, the pore diameter is about 10-50 nm, the material has unidirectional respiration which does not influence the outward diffusion of water vapor in the concrete, and meanwhile, the mixture of the powder and the emulsion can infiltrate into microcracks or pores of 1-2 mm on the surface of the concrete to form an interweaved structure. Therefore, the material of the invention has better bonding strength, toughness and shock resistance than cement-based materials. It should be noted that: the powder and the emulsion provided by the invention are required to be packaged separately and mixed before use, and the powder and the emulsion react after being mixed, and are required to be used within 24 hours after being mixed, and can be coagulated into blocks for a long time to be unusable.
Example 2
The embodiment provides a bare concrete beautifying and protecting material, which comprises powder and high polymer emulsion. The powder comprises the following components in parts by weight:
40 parts of silicate cement, 15 parts of aluminoferrite cement, 13 parts of S95-level slag powder, 10 parts of sand powder (with the particle size of 100-120 meshes), 4 parts of titanium dioxide and 15 parts of fly ash (with the specific surface area more than or equal to 500 m) 2 3 parts of lignin sulfonate dispersant.
The components of the polymer emulsion are as follows (according to parts by weight): 53 parts of acrylic emulsion (solid content (57+/-1)%, viscosity 300-750 mPa.s), 3.5 parts of aqueous organosilicon defoamer B-313 (milky white liquid, pH 6.5-7.8), 1.5 parts of sulfonated melamine water reducer (model SM) and water to 100 parts.
The using method comprises the following steps: the powder and the polymer emulsion are stirred uniformly according to the weight ratio of 1.25:1 without caking, the specific operation is that firstly, the powder is poured into a container, then the emulsion is poured into the container according to the recommended ratio, then the mixture is stirred for 2 minutes at 550 r/min by using an electric stirrer, and the mixture is coated by using a roller brush, wherein the material consumption is 120g per square meter.
Example 3
The embodiment provides a bare concrete beautifying and protecting material, which comprises powder and high polymer emulsion. The powder comprises the following components in parts by weight:
40 parts of silicate cement, 15 parts of aluminoferrite cement, 13 parts of S95-level slag powder, 10 parts of sand powder (with the particle size of 100-120 meshes), 4 parts of titanium dioxide and 15 parts of fly ash (with the specific surface area more than or equal to 500 m) 2 3 parts of lignin sulfonate dispersant.
The components of the polymer emulsion are as follows (according to parts by weight): 51 parts of styrene-acrylic emulsion (solid content (56+/-1)%, viscosity of 900-1200 mPa.s), 3.5 parts of polysiloxane defoamer B-313 (milky white liquid, pH of 6.5-7.8), 1.5 parts of sulfonated melamine water reducer (model SM) and water to 100 parts.
The using method comprises the following steps: the powder and the polymer emulsion are stirred uniformly according to the weight ratio of 1.5:1 without caking, the specific operation is that firstly, the powder is poured into a container, then the emulsion is poured into the container according to the recommended ratio, then the mixture is stirred for 2 minutes at 550 r/min by using an electric stirrer, and the mixture is coated by using a roller brush, wherein the material consumption is 120g per square meter.
Comparative example 1
Based on the embodiment 1, the addition amount of the titanium dioxide is changed to 2 parts, the addition amount of the white cement is changed to 4 parts, and other parameters are kept unchanged.
Comparative example 2
Based on the embodiment 1, the addition amount of the titanium dioxide is changed to 0 part, the addition amount of the white cement is changed to 6 parts, and other parameters are kept unchanged.
Comparative example 3
The traditional acrylic resin coating is used for beautifying and protecting the fresh water concrete, and the material consumption is 120g per square meter.
Comparative example 4
The amount of material was changed to 220g per square meter based on comparative example 1.
Comparative examples 5 to 7
Based on examples 1 to 3, the material usage was changed to 220g per square meter.
The products obtained according to the proportion are constructed according to the specified material consumption, the main performance indexes are detected according to GBT 50081-2019 'test method Standard for physical and mechanical properties of concrete' and GBT 50082-2009 'test method Standard for long-term Performance and durability of common concrete', and the specific results are shown in the following tables 3 and 4.
Table 3 performance index of each example and comparative example
Table 4 Performance index of each comparative example
As can be seen from the performance indexes tested in examples 1-3, the effect of beautifying and protecting by adopting the vinyl acetate copolymer emulsion is best; as can be seen by comparing the performance indexes tested in comparative examples 1-2, the appearance color of the product added with 4 parts of titanium dioxide and 2 parts of white cement is closest to the original color of the bare concrete, and the product reaches the optimal performance index and ageing resistance, and the original color of the bare concrete cannot be maintained when the product is lower than 2 parts of titanium dioxide or higher than 4 parts of white cement; the performance indexes tested in the example 1 and the comparative example 3 show that the performance of the material is superior to that of the traditional material, and the material has excellent bonding performance, ageing resistance and unidirectional respiration; the performance indexes tested by comparing comparative examples 5 to 7 show that the use amount of the beautifying protective material is optimal to 120g per square meter.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any person skilled in the art may make modifications or alterations to the above disclosed technical content to equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (10)

1. The water-based material for the beautification and protection of the bare concrete is characterized by comprising the following components in parts by weight:
powder material: 40-55 parts of cement, 5-15 parts of sand powder, 5-15 parts of mineral powder, 1-3 parts of dispersing suspending agent, 3-5 parts of titanium dioxide and 5-15 parts of fly ash;
emulsion: 45-55 parts of high molecular polymer emulsion, 1-5 parts of defoamer, 0.5-1.5 parts of water reducer and 30-40 parts of water.
2. The aqueous material of claim 1, wherein the cement is one, two or more of silicate, aluminate, aluminoferrite or sulfate cements.
3. The aqueous material of claim 1, wherein the cement is 40 parts Portland cement, 13 parts aluminoferrite cement, and 2 parts white cement.
4. The aqueous material of claim 1, wherein the dispersion suspending agent is one, two or more of a copolymer of polyalkylene oxide chains, a lignosulfonate, a sulfonate compound in naphthalene sulfonate formaldehyde condensate.
5. The aqueous material of claim 1, wherein the sand powder has a size of 100 mesh to 120 mesh; the mineral powder is of grade S95, theThe specific surface area of the fly ash is more than or equal to 500m 2 /kg。
6. The aqueous material of claim 1, wherein the high molecular polymer emulsion is one, two or more of styrene-acrylic emulsion, vinyl acetate copolymer emulsion, silicone-acrylic emulsion or acrylic emulsion.
7. The aqueous material of claim 1, wherein the defoamer is one or more of an emulsified silicone, a polysiloxane, and an aqueous silicone defoamer.
8. The aqueous material of claim 1, wherein the water reducer is one or more of modified polymer sulfonic acids, high polymer viscosity modifiers, and sulfonated melamine water reducers.
9. The aqueous material according to claim 1, wherein the powder and the emulsion are mixed uniformly in a weight ratio of 1.2:1-2:1, and the amount of the powder to the emulsion is 100 g-120 g per square meter.
10. Use of an aqueous material for the beautification protection of bare concrete buildings according to any of claims 1 to 9, in the durable protection and beautification of new or old concrete building surfaces, characterized in that said application is carried out in an amount of 100g to 120g of said aqueous material for the painting or spraying of new or old concrete building surfaces.
CN202310635256.9A 2023-05-31 2023-05-31 Water-based material for beautifying and protecting bare concrete and application thereof Pending CN117003530A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310635256.9A CN117003530A (en) 2023-05-31 2023-05-31 Water-based material for beautifying and protecting bare concrete and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310635256.9A CN117003530A (en) 2023-05-31 2023-05-31 Water-based material for beautifying and protecting bare concrete and application thereof

Publications (1)

Publication Number Publication Date
CN117003530A true CN117003530A (en) 2023-11-07

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Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
CN (1) CN117003530A (en)

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