CN115180978A - Composite slurry for anti-crack coating on back surface of large-plate ceramic tile and coating process - Google Patents
Composite slurry for anti-crack coating on back surface of large-plate ceramic tile and coating process Download PDFInfo
- Publication number
- CN115180978A CN115180978A CN202210738682.0A CN202210738682A CN115180978A CN 115180978 A CN115180978 A CN 115180978A CN 202210738682 A CN202210738682 A CN 202210738682A CN 115180978 A CN115180978 A CN 115180978A
- Authority
- CN
- China
- Prior art keywords
- ceramic tile
- coating
- crack
- plate ceramic
- back surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 108
- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 239000002002 slurry Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229920002678 cellulose Polymers 0.000 claims abstract description 40
- 239000001913 cellulose Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000007581 slurry coating method Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 238000009736 wetting Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000004568 cement Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000006004 Quartz sand Substances 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 22
- 239000012784 inorganic fiber Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 229920001046 Nanocellulose Polymers 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- 239000011398 Portland cement Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 5
- 235000020679 tap water Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 235000013379 molasses Nutrition 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- 235000019794 sodium silicate Nutrition 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 238000005336 cracking Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 239000003469 silicate cement Substances 0.000 description 5
- 229920003043 Cellulose fiber Polymers 0.000 description 4
- 229920001213 Polysorbate 20 Polymers 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 241001374849 Liparis atlanticus Species 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical group [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- -1 wooden boards Substances 0.000 description 1
Images
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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
- B28B11/245—Curing concrete articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B19/00—Machines or methods for applying the material to surfaces to form a permanent layer thereon
- B28B19/0092—Machines or methods for applying the material to surfaces to form a permanent layer thereon to webs, sheets or the like, e.g. of paper, cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28C5/00—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions
- B28C5/40—Mixing specially adapted for preparing mixtures containing fibres
- B28C5/402—Methods
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
- C04B41/5079—Portland cements
-
- 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 discloses an organic-inorganic composite slurry containing nano-cellulose for an anti-cracking coating on the back surface of a large-plate ceramic tile and a coating process of the organic-inorganic composite slurry on the large-plate ceramic tile. The coating process of the composite slurry on the large-plate ceramic tile comprises the following steps: (1) wetting and carrying out hydrophilic modification on the surface of the back of the large-plate ceramic tile; (2) preparing a precursor solution; (3) preparing mixed dry powder; (4) preparing slurry; (5) slurry coating; (6) drying and cooling; and (7) stacking finished products. The anti-crack coating containing the nano-cellulose is prepared by coating immediately after the production of the large-board ceramic tile, and the coating adopts a mechanical coating mode, and meanwhile, the coating has short curing, hardening and drying time, thereby fully meeting the requirements of continuity, rapidness and automation of the production of the large-board ceramic tile. The crack-resistant coating on the back surface of the large-plate ceramic tile containing the nano-cellulose also has the characteristics of thin thickness, high strength, good impact resistance effect and the like, and the performance of the crack-resistant coating is far superior to that of a sample without the crack-resistant coating compared with the large-plate ceramic tile.
Description
Technical Field
The invention belongs to the field of large-board ceramic tile material manufacturing and composite processing, and relates to organic-inorganic composite slurry for an anti-crack coating on the back surface of a large-board ceramic tile and a coating process of the organic-inorganic composite slurry on the large-board ceramic tile, in particular to organic-inorganic composite slurry containing nano-cellulose for the anti-crack coating on the back surface of the large-board ceramic tile and a coating process of the organic-inorganic composite slurry on the large-board ceramic tile.
Background
The large-plate ceramic tile is a plate-shaped ceramic product with the upper surface area not less than 1.62 square meters, which is prepared from various inorganic non-metallic materials such as clay, feldspar, quartz and the like through the production processes of molding, decoration, high-temperature calcination at 1200 ℃ and the like, has the specifications of 1800 multiplied by 900 mm, 2400 multiplied by 1200mm, 3200 multiplied by 1600mm, 3600 multiplied by 1600mm and the like, is a brand new material for non-transparent decorative veneers after natural stone, wooden boards, metal boards, plastic boards and traditional ceramic tiles, has the properties of low water absorption, large specification, thin thickness, energy conservation, environmental protection, light weight, high strength and a plurality of green building materials, and is the most important variety for the development of the current ceramic tiles.
The large-plate ceramic tile is generally thin, only 8-12 mm in thickness and only 2-6 mm in ultrathin type. Due to the characteristics of large size, thin thickness and large brittleness of the large-plate ceramic tile, the large-plate ceramic tile is easy to generate the conditions of corner fracture, breakage, damage and the like due to impact and collision of foreign objects or impact with the ground and surrounding hard objects in the processes of packaging, carrying, transporting and installing, so the operation difficulty of production enterprises and construction enterprises is obviously increased, and the cost of the large-plate ceramic tile is also improved. At present, the mode of manually pasting the glass fiber gridding cloth on the back of the large-plate ceramic tile is generally adopted in the industry to solve the problem, namely, after the large-plate ceramic tile is produced, the modes of manually paving and brushing glue are adopted, the organic adhesive and the glass fiber gridding cloth are brushed on the back of the large-plate ceramic tile, and a product with certain impact resistance is obtained through drying, but the problems of low labor efficiency, high price of the organic adhesive, environment pollution caused by Volatile Organic Compounds (VOC) and the like exist, and the development of a novel impact-resistant coating material which can be integrally prepared with the large-plate ceramic tile is urgently needed.
The nano-cellulose is a filamentous fiber which is obtained by separating plant fibers through high-pressure shearing force and has the diameter of dozens of to hundreds of nanometers and the length of a few micrometers to hundreds of micrometers. The nano-cellulose is used as a basic component unit of the cellulose fiber, not only has the characteristics of cellulose, but also has many characteristics of nano-materials, such as huge specific surface area, higher elastic modulus, adsorption capacity, high reaction activity and the like, and has great difference with common cellulose in structure and performance. The method is widely applied to scenes of papermaking, medicine carrying, filtering, thickening and the like, but the application of the nano-cellulose in the anti-crack coating on the back surface of the ceramic tile with the large board is not reported at present.
Disclosure of Invention
In view of the above problems, the invention aims to provide an organic-inorganic composite slurry which uses nano-cellulose as a key raw material and is used for industrial preparation of an anti-crack coating on the back surface of a large-plate ceramic tile, and the invention also aims to provide a coating process of the organic-inorganic composite slurry on the large-plate ceramic tile.
In order to realize the first aim of the invention, the invention provides an organic-inorganic composite slurry containing nano-cellulose for an anti-cracking coating on the back surface of a large-plate ceramic tile, which comprises the following main raw materials in percentage by mass: 10 to 30 percent of superfine cement, 1 to 5 percent of nano-cellulose, 0.1 to 1 percent of water reducing agent, 0.01 to 0.5 percent of retarder, 10 to 30 percent of quartz sand, 1 to 5 percent of inorganic fiber, 0.1 to 1 percent of surfactant and 27.5 to 77.79 percent of water.
In order to realize the second object of the invention, the invention provides a coating process of organic-inorganic composite slurry containing nano-cellulose on a large-board ceramic tile, which is used for an anti-cracking coating on the back surface of the large-board ceramic tile, and comprises the following steps:
(1) Wetting and hydrophilic modification of the surface of the back of the large-plate ceramic tile: soaking with water or water solution; when an aqueous solution soaking method is adopted, one or more hydrophilic modifiers of commercial surfactant, sodium silicate, sodium metasilicate and sodium polyphosphate are added into water to realize the hydrophilicity of the hydrophobic large-plate ceramic tile and the permeation of water in capillary channels on the back surface of the large-plate ceramic tile;
(2) Preparing a precursor solution: weighing water with required dosage, placing the water in a stirring barrel, sequentially adding a nano-cellulose solution, a retarder and a surfactant, and stirring to obtain a precursor solution;
(3) Preparing mixed dry powder: weighing superfine cement, a water reducing agent, quartz sand and inorganic fiber with required dosage, and placing the materials in a mixer to mix to obtain mixed dry powder;
(4) Preparing slurry: slowly adding the mixed dry powder into the precursor liquid under the stirring state, and stirring to obtain slurry;
(5) Slurry coating: loading the slurry into a charging bucket, and uniformly coating the slurry on the surface of the wet large-plate ceramic tile by a slurry coating machine;
(6) Drying and cooling: drying the ceramic tiles coated with the slurry by a tunnel kiln, and cooling at room temperature;
(7) Finished product stacking: stacking and packaging the cooled and dried large-plate ceramic tiles to form products.
Has the advantages that:
the invention is characterized in that the organic-inorganic composite anti-crack coating is constructed by combining the nano-cellulose and the ultra-fine pure silicate cement. The nano-cellulose is an ultralong, high-toughness and flexible high molecular polymer derived from natural plant fibers, and has the outstanding characteristics that a framework is flexible and good in elasticity, and meanwhile, the diameter of the fibers is in a nano range, so that a high-strength and high-toughness nano structure can be formed by randomly bending, overlapping and winding the fibers on a nano scale; meanwhile, a large number of functional groups such as hydroxyl, glycosidic bonds and the like exist on the surface of the cellulose, and can form molecular scale connection with a cement hydration product and inorganic fiber surface functional groups (silicon hydroxyl) through hydrogen bonds, so that the strength and toughness of the skeleton are enhanced, and the shock resistance of the system is improved.
The invention has the outstanding characteristics that the superfine pure portland cement is adopted as the main cementing material of the slurry, the superfine pure portland cement does not contain mineral admixture such as fly ash, slag and the like, and the particle size is less than 5 micrometers and far less than that of ordinary cement, so that the superfine pure portland cement can be hydrated and hardened in a short time, high strength is formed, and the production conditions of rapid hardening of the crack-resistant coating on the back surface of the large-plate ceramic tile, timely stacking and warehousing are met. The hydration product of the superfine silicate cement is in nano-scale, is a hydrated calcium silicate inorganic material, can be mutually interwoven and wound with the nano-cellulose on the micro-scale, and enhances the resistance of the coating to external impact.
The invention is characterized in that the adopted nano-cellulose raw material is aqueous solution, and high consistency can be obtained at very small concentration of 1-5 percent due to high dispersity and nano-scale of the nano-cellulose raw material. The method is used for preparing the large-plate ceramic tile anti-cracking coating, in the drying process of the large-plate ceramic tile anti-cracking coating, the moisture in the nano-cellulose is gradually removed at high temperature, the remained nano-cellulose fiber framework is firmly fixed with cement hydration products, inorganic fibers and the like, high strength and high toughness are generated, and the reinforcing and toughening effects of the nano-cellulose fiber framework are far superior to those of the traditional cellulose and other organic polymer materials.
The invention has the outstanding characteristics that the preparation of the crack-resistant coating containing the nano-cellulose and the superfine cement is to coat the coating immediately after the production of the large-plate ceramic tile, the coating adopts a mechanical coating mode, and the curing, hardening and drying time of the coating is less than 1 hour, thereby fully meeting the requirements of the continuous, rapid and automatic production of the large-plate ceramic tile.
The back crack-resistant coating of the large-plate ceramic tile containing the nano-cellulose prepared by the technology has the characteristics of thin thickness, high strength, good impact resistance effect and the like, the thickness can be as small as 0.5 mm and as large as 2 mm, the highest impact resistance indexes can reach 100cm (112 g steel balls) and 50cm (450 g steel balls) through ball drop test tests, the performance is far better than that of a large-plate ceramic tile sample without the crack-resistant coating, and after the front surface of the large-plate ceramic tile is damaged through the impact resistance test, the through cracks only appear on the front surface, but the whole large-plate ceramic tile still keeps complete and does not break and scatter; the back coating is free from any damage and kept complete, not only can not hurt personnel, but also is easy to clean, and is greatly convenient for the processes of carrying, loading and unloading, construction and the like.
Drawings
FIG. 1 is a schematic view of the microstructure of a crack resistant coating on the back of a large ceramic tile containing nanocellulose; in the figure, 1-large ceramic tiles placed with their backs facing upwards; 2-a large-board ceramic tile back anti-crack coating containing nano-cellulose; 201-nanocellulose; 202-ultra fine cement hydration product.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The invention provides an organic-inorganic composite slurry containing nano-cellulose for an anti-cracking coating on the back of a large-board ceramic tile, which comprises the following main raw materials in percentage by mass: 10 to 30 percent of superfine cement, 1 to 5 percent of nano-cellulose, 0.1 to 1 percent of water reducing agent, 0.01 to 0.5 percent of retarder, 10 to 30 percent of quartz sand, 1 to 5 percent of inorganic fiber, 0.1 to 1 percent of surfactant and 27.5 to 77.79 percent of water.
In the invention, the superfine cement is superfine pure portland cement with the average grain diameter of less than 5 microns; the nano-cellulose is an aqueous solution of nano-cellulose fibers, and the concentration of the nano-cellulose is in the range of 1-5%; the water reducing agent is a polycarboxylic acid water reducing agent; the retarder is molasses retarder and/or citric acid retarder; the quartz sand is high-purity quartz sand with the mesh number of 100-1000 meshes; the inorganic fiber is glass fiber, basalt fiber or other inorganic fiber with the length of 3-12 mm; the surfactant is anionic surfactant and/or nonionic surfactant; the water is common municipal tap water.
Preferably, the invention selects the superfine pure portland cement with the average particle size of less than 1 micron, aims to realize the rapid setting and hardening of slurry after coating and form strength, and is convenient for the continuous production, stacking and transportation of large-plate ceramic tile products. The particle size of the common cement is generally less than 45 microns, the particles are coarse, and simultaneously, the common cement contains a large amount of mineral admixtures such as slag, fly ash and the like, the hydration is slow, the hardening time is generally 8 hours to 1 day, and the common cement cannot be used for continuous production and rapid drying of the crack-resistant coating on the back surface of the large-plate ceramic tile. The superfine pure portland cement has much smaller particles than common cement, does not contain any mineral admixture, has extremely high hydration speed, can realize gelatinization and solidification within minutes to 1 hour, and can quickly form strength at high temperature, so that the rapid production of the crack-resistant coating on the back surface of the large-plate ceramic tile becomes possible.
The water reducing agent is used for reducing the water consumption of cement and slurry and accelerating the later drying rate. The water reducing agent is a high molecular or amphoteric molecular compound with amphiphilic functional groups, can be adsorbed on the surfaces of cement and filler particles, and reduces the adsorption of the particles to water by virtue of double electric layers and charge action, so that the system can obtain good fluidity on the premise of less water consumption.
The retarder aims at regulating and controlling the gelation time of the superfine cement, so that the requirements of slurry coating construction and subsequent rapid gelation and solidification can be met.
The surfactant in the invention is used for promoting the uniform dispersion of the superfine cement particles and the nano cellulose in the slurry. The surfactant molecules contain both hydrophilic and lipophilic groups, so that the surface tension of the system can be greatly reduced through adsorption, and the efficient and uniform dispersion of the ultrafine nanoparticles and the nanofibers in an aqueous solution is promoted.
The anti-crack coating on the back of the large-plate ceramic tile also contains quartz sand and inorganic fibers, wherein the quartz sand can greatly enhance the hardness and the shock resistance of the coating, and the inorganic fibers can enhance the hardness of the coating and assist in enhancing the micro toughness and the shock resistance.
On the other hand, the invention provides a coating process of organic-inorganic composite slurry containing nano-cellulose on a large-board ceramic tile, which is used for an anti-cracking coating on the back surface of the large-board ceramic tile, and the coating process comprises the following steps:
(1) Wetting and hydrophilic modification of the surface of the back of the large-plate ceramic tile: soaking the back of the large-plate ceramic tile upwards in a water tank by adopting a water or aqueous solution soaking method, maintaining for 1-5 minutes, and then taking out to ensure that the back of the large-plate ceramic tile maintains the state of soaking the slurry; when the aqueous solution soaking method is adopted, hydrophilic modifiers such as commercial surfactants, sodium silicate, sodium metasilicate, sodium polyphosphate and the like are added into the water;
(2) Preparing a precursor solution: weighing water with required dosage, placing the water in a stirring barrel, sequentially adding the nano-cellulose solution, the retarder and the surfactant, and stirring for 5-10 minutes to obtain a precursor solution;
(3) Preparing mixed dry powder: weighing the superfine cement, the water reducing agent, the quartz sand and the inorganic fiber with required dosage, and placing the materials in a mixer for mixing for 5-10 minutes to obtain mixed dry powder;
(4) Preparing slurry: slowly adding the mixed dry powder into the precursor liquid under stirring, and continuously stirring for 5-20 minutes after adding to obtain slurry;
(5) Slurry coating: loading the slurry into a material barrel, and uniformly coating the slurry on the surface of the wet large-plate ceramic tile by a slurry coating machine (such as a bell jar slurry spraying device, a slurry spraying device or a slurry scraping device);
(6) Drying and cooling: the ceramic tile coated with slurry is dried by a tunnel kiln, and the drying system is as follows: 80-15 minutes, 120-15 minutes, 150-15 minutes, and cooling for 15 minutes at room temperature;
(7) Finished product stacking: stacking and packaging the cooled and dried large-plate ceramic tiles to form products.
In the invention, a ceramic tile impact resistance tester is adopted to test the impact resistance of the obtained large-plate ceramic tile back crack-resistant coating, the falling balls are respectively 112 g and 450 g of steel balls with mass, the large-plate ceramic tile is cut into a size of 300 multiplied by 300mm for testing, the maximum crack-resistant index of the large-plate ceramic tile back crack-resistant coating prepared according to the invention can reach 100cm (112 g of steel balls) and 50cm (450 g of steel balls), the large-plate ceramic tile is not broken and scattered after being broken, the surface layer is removed from microcracks, the back coating is still intact, so the large-plate ceramic tile back crack-resistant coating can not cause damage to the surrounding environment, personnel and the like, and the cleaning is convenient. Table 1 shows the results of the impact resistance test of the crack-resistant coating on the back surface of the ceramic tile made by the present invention.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also merely one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) Selecting materials: superfine pure silicate cement with average grain size less than 2 microns is prepared with sea snail 525 cement and through self-grinding; 2 percent of nano-cellulose, wherein the water reducing agent is selected from polycarboxylic acid water reducing agent, the retarder is selected from molasses retarder, the quartz sand is selected from high-purity quartz sand with the mesh number of 400, the inorganic fiber is selected from glass fiber with the length of 3 mm, the surfactant is selected from sodium dodecyl sulfate, and the water is common municipal tap water;
(2) The raw material ratio is as follows: 20% of superfine cement, 25% of nano-cellulose, 0.2% of water reducing agent, 0.02% of retarder, 15% of quartz sand, 3% of inorganic fiber and 36.78% of water;
(3) Wetting the surface of the back of the large-plate ceramic tile: upwards soaking the back of the large-plate ceramic tile in a water tank, maintaining for 3 minutes, and taking out;
(4) Preparing a precursor solution: weighing water with required dosage, placing the water in a stirring barrel, sequentially adding the nano-cellulose solution, the retarder and the sodium dodecyl sulfate, and stirring for 5 minutes to obtain a precursor solution;
(5) Preparing mixed dry powder: weighing the superfine cement, the water reducing agent, the quartz sand and the inorganic fiber with required dosage, and placing the materials in a mixer for mixing for 5 minutes to obtain mixed dry powder;
(6) Preparing slurry: slowly adding the mixed dry powder into the precursor liquid under the stirring state, and continuing stirring for 15 minutes after adding the mixed dry powder to obtain slurry;
(7) Slurry coating: loading the slurry into a charging bucket, and uniformly coating the slurry on the surface of the wet large-plate ceramic tile by a slurry coating machine (such as bell jar slurry spraying equipment, slurry spraying equipment or slurry blade coating equipment);
(8) Drying and cooling: the slurry-coated large-plate ceramic tile is dried by a tunnel kiln, and the system is as follows: 80-15 minutes, 120-15 minutes, 150-15 minutes, and cooling for 15 minutes at room temperature;
(9) Finished product stacking: stacking and packaging the cooled and dried large-plate ceramic tiles to form products.
The anti-cracking coating on the back of the large-plate ceramic tile prepared according to the embodiment 1 is earthy yellow, uniform and compact in appearance, and the anti-cracking indexes of the large-plate ceramic tile are 112 g of steel ball-88cm and 450 g of steel ball-40 cm through an impact resistance test.
Example 2
(1) Selecting materials: superfine pure silicate cement with average grain size smaller than 1 micron is prepared with sea snail 525 cement and through self grinding; the water reducer is selected from polycarboxylic acid water reducers, the retarder is selected from citric acid, the quartz sand is selected from high-purity quartz sand with the mesh number of 800 meshes, the inorganic fiber is selected from glass fiber with the length of 6 millimeters, the surfactant is selected from TWEEN-20 nonionic surfactant, and the water is common municipal tap water;
(2) The raw material ratio is as follows: 15% of superfine cement, 22% of nano-cellulose, 0.15% of water reducing agent, 0.01% of retarder, 30% of quartz sand, 2% of inorganic fiber, 1.5% of TWEEN-20 and 29.34% of water;
(3) Wetting and hydrophilic modification of the surface of the back of the large-plate ceramic tile: and (3) upwards soaking the back of the large-plate ceramic tile in a water-sodium polyphosphate mixed solution, maintaining for 3 minutes, and taking out.
The other preparation process was the same as in example 1. Tests show that the crack resistance indexes of the crack resistance coating on the back surface of the large-plate ceramic tile prepared in example 2 are 112 g steel ball-91cm and 450 g steel ball-43 cm.
Example 3
(1) Selecting materials: superfine pure silicate cement with average grain size smaller than 1 micron is prepared with sea snail 525 cement and through self grinding; 5% of nano cellulose solution, wherein the water reducing agent is selected from polycarboxylic acid water reducing agent, the retarder is selected from sodium citrate, the quartz sand is selected from pure white high-purity quartz sand with the mesh number of 600 meshes, the inorganic fiber is selected from aluminum silicate fiber with the length of 12 mm, the surfactant is selected from TWEEN20 nonionic surfactant, and the water is common municipal tap water;
(2) The raw material ratio is as follows: 25% of superfine cement, 30% of nano-cellulose, 0.25% of water reducing agent, 0.02% of retarder, 20% of quartz sand, 5% of inorganic fiber, 0.8% of TWEEN-20 and 18.93% of water;
(3) Wetting and hydrophilic modification of the surface of the back of the large-plate ceramic tile: the back of the large-plate ceramic tile is upwards soaked in the water-sodium dodecyl benzene sulfonate mixed solution, and the large-plate ceramic tile is taken out after being maintained for 5 minutes.
The other preparation process was the same as in example 1. Tests show that the crack resistance index of the crack resistance coating on the back surface of the large-plate ceramic tile prepared in the embodiment 3 is 112 g steel ball-100cm and 450 g steel ball-50 cm.
Table 1 shows the impact resistance of the crack-resistant coating on the back surface of the large-plate ceramic tile prepared by the invention:
| steel ball with ball weight of 112 g | Steel ball with weight of 450 g | |
| Non-coating brick | 52cm | 27cm |
| Example 1 | 88cm | 40cm |
| Example 2 | 91cm | 43cm |
| Example 3 | 100cm | 50cm |
Claims (9)
1. The organic-inorganic composite slurry containing the nano-cellulose for the anti-crack coating on the back surface of the large-plate ceramic tile is characterized by comprising the following main raw materials in percentage by mass: 10 to 30 percent of superfine cement, 1 to 5 percent of nano-cellulose, 0.1 to 1 percent of water reducing agent, 0.01 to 0.5 percent of retarder, 10 to 30 percent of quartz sand, 1 to 5 percent of inorganic fiber, 0.1 to 1 percent of surfactant and 27.5 to 77.79 percent of water.
2. The organic-inorganic composite slurry containing nano-cellulose for the crack-resistant coating on the back surface of the large-board ceramic tile as claimed in claim 1, wherein the ultra-fine cement is ultra-fine pure portland cement with an average particle size of less than 5 μm; the water reducing agent is a polycarboxylic acid water reducing agent; the retarder is molasses retarder and/or citric acid retarder; the quartz sand is high-purity quartz sand with the mesh number of 100-1000 meshes; the inorganic fiber is glass fiber with the length of 3-12 mm, basalt fiber or other inorganic fibers; the surfactant is an anionic surfactant and/or a nonionic surfactant; the water is common municipal tap water.
3. The process for coating the organic-inorganic composite slurry containing the nanocellulose on the large-plate ceramic tile for the crack-resistant coating on the back surface of the large-plate ceramic tile according to claim 1, which is characterized by comprising the following steps: (1) wetting and hydrophilic modification of the surface of the back of the large-plate ceramic tile; (2) preparing a precursor solution; (3) preparing mixed dry powder; (4) preparing slurry; (5) slurry coating; (6) drying and cooling; and (7) stacking finished products.
4. The process for coating the organic-inorganic composite slurry containing the nanocellulose on the large-plate ceramic tile for the crack-resistant coating on the back surface of the large-plate ceramic tile according to claim 3, wherein the wetting and hydrophilic modification of the back surface of the large-plate ceramic tile adopts an aqueous solution soaking method, and comprises the following steps: soaking the back side of the large-plate ceramic tile upwards in a water tank, maintaining for 1-5 minutes, and taking out; the water solution is prepared by adding one or more of commercial surfactant, sodium silicate, sodium metasilicate and sodium polyphosphate into water.
5. The process for coating the organic-inorganic composite slurry containing the nanocellulose on the large-board ceramic tile for the crack-resistant coating on the back surface of the large-board ceramic tile according to claim 3, wherein the preparation of the precursor solution comprises the following steps: weighing water with required dosage, placing the water in a stirring barrel, sequentially adding the nano-cellulose solution, the retarder and the surfactant, and uniformly stirring.
6. The process for coating the organic-inorganic composite slurry containing the nanocellulose on the large-board ceramic tile for the crack-resistant coating on the back surface of the large-board ceramic tile according to claim 3, wherein the preparation of the mixed dry powder comprises the following steps: weighing the superfine cement, the water reducing agent, the quartz sand and the inorganic fiber with required dosage, and placing the materials in a mixer to mix evenly.
7. The process for coating the organic-inorganic composite slurry containing the nanocellulose on the large-board ceramic tile for the crack-resistant coating on the back surface of the large-board ceramic tile according to claim 3, wherein the preparation of the slurry comprises the following steps: and slowly adding the mixed dry powder into the precursor liquid under the stirring state, and continuously stirring uniformly after adding.
8. The process for coating the organic-inorganic composite slurry containing the nanocellulose on the large-board ceramic tile for the crack-resistant coating on the back surface of the large-board ceramic tile according to claim 3, wherein the slurry coating comprises the following steps: and (3) loading the slurry into a charging bucket, and uniformly coating the slurry on the surface of the wet large-plate ceramic tile by using a slurry coating machine.
9. The coating process of the nanocellulose-containing organic-inorganic composite slurry for the large-board ceramic tile back crack-resistant coating on the large-board ceramic tile, which is prepared according to any one of claims 3 to 8, is characterized in that the crack-resistant index of the coating for the large-board ceramic tile back crack-resistant coating is 88 to 100cm (112 g of steel balls) and 40 to 50cm (450 g of steel balls) through an impact resistance test; after the impact resistance test, the large-plate ceramic tile is not broken and scattered, and the anti-crack coating on the back surface is kept complete.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210738682.0A CN115180978A (en) | 2022-06-28 | 2022-06-28 | Composite slurry for anti-crack coating on back surface of large-plate ceramic tile and coating process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210738682.0A CN115180978A (en) | 2022-06-28 | 2022-06-28 | Composite slurry for anti-crack coating on back surface of large-plate ceramic tile and coating process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115180978A true CN115180978A (en) | 2022-10-14 |
Family
ID=83515464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210738682.0A Pending CN115180978A (en) | 2022-06-28 | 2022-06-28 | Composite slurry for anti-crack coating on back surface of large-plate ceramic tile and coating process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115180978A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116477923A (en) * | 2023-03-22 | 2023-07-25 | 雅安沃克林环保科技有限公司 | Method for preparing ceramic connecting plate by utilizing ceramic membrane waste and ceramic connecting plate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613347A (en) * | 2013-12-10 | 2014-03-05 | 广东龙马化学有限公司 | Waterproof ceramic tile adhesive material |
| CN108585667A (en) * | 2018-02-26 | 2018-09-28 | 上海牛元工贸有限公司 | High-adhesion energy ceramic tile adhesive and preparation method thereof |
| US20190062211A1 (en) * | 2017-08-25 | 2019-02-28 | The Governors Of The University Of Alberta | Cementitious inorganic material containing cellulosic nanofibers |
| CN109626892A (en) * | 2019-01-28 | 2019-04-16 | 武汉市市政建设集团有限公司 | A kind of pellet class curing agent and the high-strength low-shrinkage anti-crack road surface base material using its preparation |
| CN111472510A (en) * | 2020-03-18 | 2020-07-31 | 浙江解放装饰工程有限公司 | Construction process for preventing large-plate ceramic tile from cracking and before installation |
| CN112723841A (en) * | 2021-02-08 | 2021-04-30 | 北京金隅砂浆有限公司 | Anti-crack plastering mortar |
| CN113416048A (en) * | 2021-07-12 | 2021-09-21 | 广东浮斐尼创意科技有限公司 | Bi-component micro cement coating and preparation process thereof |
-
2022
- 2022-06-28 CN CN202210738682.0A patent/CN115180978A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613347A (en) * | 2013-12-10 | 2014-03-05 | 广东龙马化学有限公司 | Waterproof ceramic tile adhesive material |
| US20190062211A1 (en) * | 2017-08-25 | 2019-02-28 | The Governors Of The University Of Alberta | Cementitious inorganic material containing cellulosic nanofibers |
| CN108585667A (en) * | 2018-02-26 | 2018-09-28 | 上海牛元工贸有限公司 | High-adhesion energy ceramic tile adhesive and preparation method thereof |
| CN109626892A (en) * | 2019-01-28 | 2019-04-16 | 武汉市市政建设集团有限公司 | A kind of pellet class curing agent and the high-strength low-shrinkage anti-crack road surface base material using its preparation |
| CN111472510A (en) * | 2020-03-18 | 2020-07-31 | 浙江解放装饰工程有限公司 | Construction process for preventing large-plate ceramic tile from cracking and before installation |
| CN112723841A (en) * | 2021-02-08 | 2021-04-30 | 北京金隅砂浆有限公司 | Anti-crack plastering mortar |
| CN113416048A (en) * | 2021-07-12 | 2021-09-21 | 广东浮斐尼创意科技有限公司 | Bi-component micro cement coating and preparation process thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116477923A (en) * | 2023-03-22 | 2023-07-25 | 雅安沃克林环保科技有限公司 | Method for preparing ceramic connecting plate by utilizing ceramic membrane waste and ceramic connecting plate |
| CN116477923B (en) * | 2023-03-22 | 2024-04-05 | 雅安沃克林环保科技有限公司 | Method for preparing ceramic connecting plate by utilizing ceramic membrane waste and ceramic connecting plate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Iucolano et al. | Fibre-reinforced lime-based mortars: A possible resource for ancient masonry restoration | |
| CN109336556B (en) | A kind of enhancing of architectural pottery prestressing force coating paste and preparation method thereof and architectural pottery product | |
| CN103664094B (en) | A kind of lightweight aggregate concrete and preparation method thereof | |
| CN102674730B (en) | Surface treating agent of recycled aggregate and preparation method thereof | |
| CN103435305A (en) | Basalt fiber concrete and preparation method thereof | |
| TW201504196A (en) | Rapid curing of thin composite material sections | |
| CN105174890A (en) | Composite light partition board and manufacturing method thereof | |
| CN109437759A (en) | A kind of high-early-strength type composite repair mortar | |
| CN113968697B (en) | Dry powder interface treating agent for aerated concrete and preparation method thereof | |
| CN103255888A (en) | Full-body dry hanging plate and manufacturing method thereof | |
| CN105585111A (en) | Basalt fiber composite as well as preparation method and application thereof | |
| CN103240927A (en) | Reinforced cement machine-made board with three-dimensional cavity fiber structure and production method of board | |
| US20210340019A1 (en) | Artificial nacre material with layered structure and preparation method thereof | |
| CN109665763A (en) | A kind of high-early-strength type composite repair mortar | |
| CN100457413C (en) | Concrete mortar interface processing method | |
| CN104478386A (en) | Mix-enhanced binding gypsum and preparation method thereof | |
| CN111432994A (en) | Self-reinforced cementitious composite compositions for building-scale three-dimensional (3D) printing | |
| CN115180978A (en) | Composite slurry for anti-crack coating on back surface of large-plate ceramic tile and coating process | |
| CN110845973B (en) | Flexible reinforcing material of ceramic tile glue and preparation method and application thereof | |
| CN113135712B (en) | High-strength concrete and production process thereof | |
| CN108383446B (en) | A kind of Ultrastrength cement base repair materials that metal-organic framework materials are modified | |
| Zaki et al. | Characteristics of paper-cement composite | |
| CN108083725B (en) | Polymer modified cement-based composite board and preparation method thereof | |
| CN113636808A (en) | Self-cleaning cement-based composite material and production method thereof | |
| CN113213880A (en) | Transparent geopolymer material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221014 |