CN116354688B - 3D printing porous gypsum material for purifying formaldehyde and preparation method thereof - Google Patents
3D printing porous gypsum material for purifying formaldehyde and preparation method thereof Download PDFInfo
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- CN116354688B CN116354688B CN202310058824.3A CN202310058824A CN116354688B CN 116354688 B CN116354688 B CN 116354688B CN 202310058824 A CN202310058824 A CN 202310058824A CN 116354688 B CN116354688 B CN 116354688B
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000010440 gypsum Substances 0.000 title claims abstract description 129
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 129
- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000010146 3D printing Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 7
- 239000006260 foam Substances 0.000 claims abstract description 6
- 229910021487 silica fume Inorganic materials 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000007639 printing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000004088 foaming agent Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 238000005187 foaming Methods 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000011164 primary particle Substances 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 6
- 239000000701 coagulant Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008719 thickening Effects 0.000 claims description 5
- 239000013008 thixotropic agent Substances 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 2
- 235000021120 animal protein Nutrition 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims description 2
- 235000018102 proteins Nutrition 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000004566 building material Substances 0.000 abstract description 9
- 238000005034 decoration Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 150000001720 carbohydrates Chemical class 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002893 slag Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- -1 phosphogypsum dihydrate Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000009740 moulding (composite fabrication) Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 241000220479 Acacia Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
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
- C04B28/14—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 calcium sulfate cements
- C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
-
- 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
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
-
- 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
- B28C5/003—Methods for mixing
- B28C5/006—Methods for mixing involving mechanical aspects
-
- 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
- B28C5/08—Apparatus or methods for producing mixtures of cement with other substances, e.g. slurries, mortars, porous or fibrous compositions using driven mechanical means affecting the mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
-
- 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
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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
- C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
-
- 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
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
-
- 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
- C04B2111/40—Porous or lightweight materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The application discloses a formaldehyde-purifying 3D printing porous gypsum material and a preparation method thereof; the formaldehyde factor is strongly adsorbed by the porous material, and is self-decomposed into nontoxic and harmless inert carbohydrate by the formaldehyde catalytic decomposition agent. The 3D printing gypsum-based material prepared by the application uses the silica fume as a foam stabilizer to stabilize foam, and the mechanical property and the cracking resistance of paste are improved by cooperatively using the composite fiber, so that the stability of the foam in a three-dimensional space structure is improved. The gypsum product printed by 3D has excellent formaldehyde adsorption capacity, so that free formaldehyde volatilized into the air from the decoration building material is effectively reduced, and the problem of long formaldehyde purification period of the newly-installed house is solved.
Description
Technical Field
The invention relates to the field of functional gypsum building materials, in particular to a formaldehyde-purifying 3D printing porous gypsum material and a preparation method thereof.
Background
The 3D printing is a technology which is based on a digital modeling file, uses printing materials such as metal materials, gypsum materials, durable nylon materials and the like, controls layer-by-layer printing through a computer three-dimensional model and finally changes a blueprint into a real object. 3D printing has a plurality of different technologies, and the different technologies are characterized in that materials are used, and components are built and built in different layers, so that the method has wide application prospect, and particularly has great advantages in the aspects of individuation and diversification of buildings, convenience and individuation of building decoration and integration of functions.
Nowadays, with the enhancement of environmental protection consciousness and safety consciousness of people, the requirements on functional gypsum are growing increasingly. The formaldehyde source is glue products, and in the decoration process, a large amount of glue is needed to be used for enabling paint to adhere to components such as walls, furniture wardrobe and cabinets, and a large amount of formaldehyde gas can be emitted from the components after decoration, so that the long-term inhalation can seriously harm the health of people. Since the formaldehyde emission period is 3-5 years and exists at every corner of the house, there is a need for a gypsum board that can absorb formaldehyde factor for a long period of time and can be covered in all directions. The existing formaldehyde-removing gypsum has single shape, only depends on physical adsorption materials, so that the gypsum adsorption effect is unstable, if the formaldehyde concentration in the air is too high, the gypsum board is easy to adsorb and saturate, the effect is not thorough, secondary release can be caused, and the effect is difficult to guarantee. Therefore, the 3D printing technology is applied at present, the labor and the construction cost are reduced, the formaldehyde-removing gypsum board is covered in an all-round way during decoration, the mode is not limited to gypsum boards, formaldehyde can be adsorbed together by manufacturing gypsum artware and the like, and the formaldehyde-removing efficiency is improved.
CN114605135A discloses a 3D printing gypsum-based material for building printing and a preparation method thereof, the gypsum-based material comprises the following components: gypsum: 60-85 percent of admixture: 15-40% of water reducer: 0.2-0.5%, retarder: 0.1-0.4%, regulator: 1.8-3%, complexing agent: 1-2.2 percent of composite fiber: 0.6-1.2%, water: 25-40%; the 3D printing gypsum for building printing provided by the invention lacks functionality, can not meet the requirements of people on different functionalities of gypsum, and has the advantages of single manufacturing usage and wide audience.
CN109956728a discloses a gypsum board for removing formaldehyde and a preparation method thereof, which is characterized in that a formaldehyde adsorption material is prepared by a specific method, and polypeptide, high molecular amines, acacia powder and phosphate are added. The gypsum-based material component contains: 100 parts of gypsum powder, 0-1 part of reinforcing agent, 0-2.5 parts of water reducer, 0.02-1 part of modified starch and 0.05-1 part of foaming agent. The formaldehyde-removing gypsum board provided by the invention has long adsorption and decomposition maintaining time and obvious effect, but is complex to operate, has higher requirements on materials and technology, and is not beneficial to large-scale production.
Disclosure of Invention
The invention aims at solving the problems that the existing 3D printing gypsum material has low functional directivity, complex operation process, high technical requirement, difficult mass production, poor strength of gypsum printing products, difficult molding and low accuracy, thereby providing a preparation method for the functional building material 3D printing formaldehyde-removing gypsum material, which not only expands the application of the gypsum building material, diversifies and facilitates the mass production of the gypsum building material.
In order to achieve the above object, the present invention provides the following technical solutions:
In a first aspect, the invention provides a formaldehyde-purifying 3D printing porous gypsum material, characterized in that: the gypsum material comprises the following raw materials in parts by mass: 60-85 parts of gypsum, 10-25 parts of admixture, 0-0.4 part of water reducer, 0.1-0.5 part of retarder, 0.5-0.8 part of foaming agent, 0.5-1.0 part of composite fiber, 5-8 parts of diatomite, 1-5 parts of active carbon, 5-8 parts of nano TiO 2, 0.2-0.6 part of thickening thixotropic agent, 4-8 parts of regulator and 0.1-0.4 part of coagulant.
As a preferable scheme, the gypsum is high-strength gypsum powder, and is prepared from desulfurized gypsum or phosphogypsum by a pressurized hydrothermal method or an atmospheric salt solution method; the high-strength gypsum powder has the flexural strength of more than 5MPa for 2 hours and the dry compressive strength of more than 30MPa.
Further, the admixture comprises silica fume and quicklime, wherein the mass ratio of the silica fume to the quicklime is (15-20): 5-8.
Further, the water reducing agent is a polycarboxylate water reducing agent, and the water reducing rate is 25% -35%; the retarder is a protein retarder; the foaming agent is prepared by compounding an animal protein foaming agent and a surfactant.
Further, the composite fiber is obtained by mixing lignin fiber and basalt fiber according to the mass ratio of 1:1-1:2; the diatomite consists of remains of diatom and mainly comprises SiO 2; the micropore diameter of the surface of the active carbon is between 20 and 50 nm; the particle size of the nano TiO 2 is 10-50nm.
Further, the thickening thixotropic agent is fumed silica, amorphous SiO 2: the primary particle size (since fumed silica is first hydrolyzed and condensed into individual silica particles during production, and then gradually grown into spherical particles of 7-40nm, which are called "primary particles" of silica [ PRIMARY PARTICLE ]; primary particle size generally refers to the arithmetic average of the primary particle sizes in individual silica or aggregates) is between 7-40 nm; aggregate particle size ("primary particles" continue to move forward in the reaction furnace along with the flame direction, the particles collide with each other, at this time, because the temperature in the reaction furnace is higher, the particles are still close to a molten state, the particles are fused together after collision to form particles with a three-dimensional dendritic structure fused together by a plurality of spherical particles, namely, an aggregate of silicon dioxide [ AGGREGATE PARTICLE [, the particles in the aggregate are fused together, thus being of a stable structure and almost impossible to separate), the particle size is about 200-500nm, the specific surface area is 100-400m2/g, the purity is high, and the SiO 2 content is not less than 99.8%; the coagulant adopts saturated sulfate; the regulator is a mixture of alumina, talcum powder and polycarboxylic acid dispersing agent.
In a second aspect, the invention provides a preparation method of a formaldehyde-purifying 3D printing porous gypsum material, which is characterized by comprising the following steps: the method comprises the following steps:
S1: placing 60-85 parts of phosphogypsum, 50-70 parts of water, 10-25 parts of admixture, 0.1-0.5 part of retarder, 0-0.4 part of water reducer, 4-8 parts of regulator and 0.5-1.0 part of wood composite fiber into a container, continuously stirring for 3-4min by using an electric stirrer, and uniformly mixing to prepare gypsum slurry;
S2: a high-speed stirrer is adopted, and a high-speed blade of the stirrer is utilized to stir the foaming agent to obtain foam; the rotating speed of the stirrer is required to be more than 1000r/min, and the stirring time is required to be more than 2 min;
S3: preparing formaldehyde adsorbent, wherein the material is 5-8 parts of diatomite, 1-5 parts of activated carbon and 5-8 parts of nano TiO 2; purifying diatomite by a roasting method, wherein the content of SiO 2 after purification is up to 90%, and then preparing a composite material from TiO 2, purified diatomite and nano-scale activated carbon by a sol-gel method by taking butyl titanate as a raw material; uniformly coating nano TiO 2 factors and active carbon factors on the surfaces of the micro diatomite particles to finally prepare formaldehyde adsorption gel;
S4: pouring the prepared foaming solution and formaldehyde adsorbent into gypsum slurry, and adopting a high-speed stirrer to fully fuse the three solutions, wherein the stirring time is controlled to be 1-3min, and the foaming is uniform, fine and stable; then adding aluminum oxide and talcum powder to increase the fluidity of the slurry, and obtaining the 3D printing gypsum-based slurry with the required fluidity of more than 280mm and the viscosity of less than 0.3 Pa.s; preparing a gypsum-based 3D printing material with formaldehyde purifying function;
s5: pouring the prepared gypsum-based 3D printing material with formaldehyde purifying function into a 3D printing device, arranging a spraying device around a printer nozzle, pouring saturated sulfate solution into the device, spraying the saturated sulfate solution on the surface of gypsum during printing, and rapidly hardening gypsum on the surface layer of the gypsum, so that the time for rapidly solidifying the gypsum by high-flow-state slurry is less than 2min, and finally preparing the gypsum-based 3D printing product with formaldehyde purifying function.
Compared with the prior art, the invention has the following advantages:
The technical key point of the invention is that the formaldehyde-purifying porous gypsum is prepared by adding functional components and applying a 3D printing technology. The formaldehyde can be adsorbed for a long time by utilizing solid waste and the porous structure of gypsum, so that the problem of long formaldehyde purification period is solved; can ensure the mechanical property of gypsum while absorbing formaldehyde. The method has the specific advantages that:
1. the 3D printing formaldehyde-removing gypsum building material disclosed by the invention is capable of improving the fluidity, plasticity and rheological property of a 3D printing gypsum-based material through various regulators, thickening thixotropic agents and coagulants. The slurry is extruded and printed through the nozzle of the 3D printer with proper fluidity, the operation time is proper, and meanwhile, the coagulant can be sprayed to harden the slurry rapidly while extruding, so that the precision of gypsum products is ensured, the volume stability of gypsum materials is improved, and the 3D printing quality is effectively improved.
2. The 3D printing formaldehyde-removing gypsum building material combines a 3D printing technology with the functional material, not only can meet the requirements of the market on gypsum functional types, but also can realize large-scale comprehensive utilization of industrial byproduct phosphogypsum, solve the problem of stacking byproduct gypsum, and effectively reduce manpower and material resources.
3. The 3D printing formaldehyde-removing gypsum building material fully utilizes the porous characteristic of gypsum, the formaldehyde catalytic decomposer and the porous phosphogypsum are synergistic, the foaming agent is used for increasing the porosity of the gypsum and reducing the apparent density to ensure that the apparent density is lower than 800kg/m < 3 >, the heat conductivity is lower than 0.12W/(m.K), and the fiber and the silica fume are added to stabilize the foam porous structure and improve the mechanical property. The porous material is favorable for the formaldehyde adsorption material to fully play the adsorption role, and the free formaldehyde in the air is adsorbed and decomposed into nontoxic and harmless inert carbohydrate through the catalytic decomposer, so that the purpose of purifying the formaldehyde is achieved.
The invention has the core advantages that: by utilizing the porous structure of the gypsum, the pore diameter is increased by adding the foaming agent, so that the pore distribution is more uniform, the adsorption capacity is enhanced, and the adsorption effect is improved. Pertinently, compared with the prior art, the invention has the following beneficial effects:
1) The solid waste is utilized, so that the environment is protected;
2) The formaldehyde release period is generally 3-15 years, and the gypsum product has long formaldehyde removal duration and is not easy to lose efficacy.
3) The formaldehyde decomposer is prepared by compounding TiO 2 and diatomite, the degradation performance of the composite material is best, and the diatomite is a good carrier material of nano titanium dioxide.
Detailed Description
In order to further describe the technical scheme of the present invention, the present invention will be described in further detail with reference to examples.
The embodiment of the invention provides a preparation method of a formaldehyde-removing functional building material manufactured by a 3D printing technology. Phosphogypsum used in the embodiment of the invention is an industrial byproduct which is obtained by a wet method for preparing phosphoric acid and takes calcium sulfate dihydrate as a main component, the purity is 60% -90%, the pH is about 1.9-5.3, and the particle size is 5-50 mu m.
Example 1
Step S1: 60 parts of phosphogypsum dihydrate, 60 parts of water, 40 parts of slag, 5 parts of carbide slag, 0.2 part of retarder, 0.1 part of water reducing agent, 6 parts of regulator and 0.5 part of wood composite fiber are taken, and stirred for 4min at a rotating speed of 145r/min, so that gypsum slurry is obtained.
Step S2: 0.5 part of foaming agent is taken and stirred for 4min at the rotating speed of 1000r/min to prepare foaming solution.
Step S3: 5 parts of diatomite is taken and roasted and purified. 1 part of active carbon and 5 parts of nano TiO2. TiO2, purified diatomite and nano-scale activated carbon are prepared into a composite material on the premise of taking butyl titanate as a raw material by a sol-gel method.
Step S4: adding the prepared foaming solution and formaldehyde catalytic decomposer into gypsum slurry, stirring by a high-speed stirrer at 900r/min for 4min, and adding aluminum oxide and talcum powder during stirring to increase the fluidity of the slurry.
Step S5: pouring the prepared gypsum-based material into a printing pump machine, printing and forming, and spraying 0.2 part of saturated sulfate by a spraying device to quickly shape; the gypsum-based material obtained in this example was designated as P1.
Example 2
Step S1: 70 parts of phosphogypsum dihydrate, 60 parts of water, 30 parts of slag, 5 parts of carbide slag, 0.3 part of retarder, 0.2 part of water reducing agent, 6 parts of regulator and 0.7 part of wood composite fiber are taken, and stirred for 3min at a rotating speed of 155r/min, so that gypsum slurry is obtained.
Step S2: 0.6 part of foaming agent is taken and stirred for 3min at the rotating speed of 1200r/min to prepare foaming solution.
Step S3: 6 parts of diatomite is taken and roasted and purified. 3 parts of active carbon and 6 parts of nano TiO2. TiO2, purified diatomite and nano-scale activated carbon are prepared into a composite material on the premise of taking butyl titanate as a raw material by a sol-gel method.
Step S4: adding the prepared foaming solution and formaldehyde catalytic decomposer into gypsum slurry, stirring by a high-speed stirrer at a rotating speed of 1000r/min for 3min, and adding aluminum oxide and talcum powder in the stirring process to increase the fluidity of the slurry.
Step S5: pouring the prepared gypsum-based material into a printing pump machine, printing and forming, and spraying 0.3 part of saturated sulfate by a spraying device to quickly shape; the gypsum-based material obtained in this example was designated as P2.
Example 3
Step S1: 80 parts of phosphogypsum dihydrate, 60 parts of water, 20 parts of slag, 5 parts of carbide slag, 0.4 part of retarder, 0.3 part of water reducing agent, 6 parts of regulator and 0.8 part of wood composite fiber are taken, and stirred for 2min at a rotating speed of 170r/min, so that gypsum slurry is obtained.
Step S2: 0.7 part of foaming agent is taken and stirred for 2min at the rotating speed of 1500r/min to prepare foaming solution.
Step S3: 7 parts of diatomite is taken and roasted and purified. 4 parts of active carbon and 7 parts of nano TiO2. TiO2, purified diatomite and nano-scale activated carbon are prepared into a composite material on the premise of taking butyl titanate as a raw material by a sol-gel method.
Step S4: adding the prepared foaming solution and formaldehyde catalytic decomposer into gypsum slurry, stirring by a high-speed stirrer at a rotating speed of 1200r/min for 2min, and adding aluminum oxide and talcum powder in the stirring process to increase the fluidity of the slurry.
Step S5: pouring the prepared gypsum-based material into a printing pump machine, printing and forming, and spraying 0.4 part of saturated sulfate by a spraying device to quickly shape; the gypsum-based material obtained in this example was designated as P3.
Example 4
Step S1: 90 parts of phosphogypsum dihydrate, 60 parts of water, 10 parts of slag, 5 parts of carbide slag, 0.5 part of retarder, 0.4 part of water reducing agent, 8 parts of regulator and 1.0 part of wood composite fiber are taken, and stirred for 1min at a rotating speed of 200r/min, so that gypsum slurry is obtained.
Step S2: 0.8 part of foaming agent is taken and stirred for 1min at the rotation speed of 1800r/min to prepare foaming solution.
Step S3: 8 parts of diatomite is taken and roasted and purified. 5 parts of active carbon and 8 parts of nano TiO2. TiO2, purified diatomite and nano-scale activated carbon are prepared into a composite material on the premise of taking butyl titanate as a raw material by a sol-gel method.
Step S4: adding the prepared foaming solution and formaldehyde catalytic decomposer into gypsum slurry, stirring by a high-speed stirrer at a rotating speed of 1500r/min for 1min, and adding aluminum oxide and talcum powder in the stirring process to increase the fluidity of the slurry.
Step S5: pouring the prepared gypsum-based material into a printing pump machine, printing and forming, and spraying 0.5 part of saturated sulfate by a spraying device to quickly shape the gypsum-based material; the gypsum-based material obtained in this example was designated as P4.
Comparative example 1
This comparative example is used to demonstrate the rapid setting and ease of printing, porous light weight, high adsorptivity, and high formaldehyde-purifying performance of the 3D printing formaldehyde-removing gypsum-based material provided by the present invention, as compared to example 4.
The raw material components and amounts used in this comparative example were the same as those of example 4, except that in this comparative example, the foaming solution and the formaldehyde decomposer were not prepared and the gypsum-based material was prepared by directly mixing the gypsum slurry with other raw materials except for the raw materials used for preparing the gypsum slurry, as follows:
Step one: 90 parts of phosphogypsum dihydrate, 60 parts of water, 10 parts of slag, 5 parts of carbide slag, 0.5 part of retarder, 0.4 part of water reducer and 6 parts of regulator are taken and stirred for 1min at a rotating speed of 200r/min, so that gypsum slurry is obtained. Alumina and talc were added during stirring to increase the fluidity of the slurry.
Step two: pouring the prepared gypsum-based material into a printing pump machine, printing and forming, and spraying 0.5 part of saturated sulfate by a spraying device to quickly shape the gypsum-based material; the gypsum-based material obtained in this comparative example was designated as EP1.
Comparative example 2
This comparative example is used to demonstrate the rapid setting and ease of printing, porous light weight, high adsorptivity, and high formaldehyde-purifying performance of the 3D printing formaldehyde-removing gypsum-based material provided by the present invention, as compared to example 4. The raw material components and amounts used in this comparative example were the same as in example 4 except that in this comparative example, the regulator and the accelerator were not prepared, but the gypsum slurry was directly mixed with the other raw materials except for the raw materials used for preparing the gypsum slurry to prepare a gypsum-based material, as follows:
step one: 90 parts of phosphogypsum dihydrate, 60 parts of water, 10 parts of slag, 8 parts of carbide slag, 0.5 part of retarder, 0.4 part of water reducer and 8 parts of regulator are taken and stirred for 1min at a rotating speed of 200r/min, so that gypsum slurry is obtained.
Step two: 8 parts of diatomite is taken and roasted and purified. 5 parts of active carbon and 8 parts of nano TiO2. TiO2, purified diatomite and nano-scale activated carbon are prepared into a composite material on the premise of taking butyl titanate as a raw material by a sol-gel method.
Step three: adding the prepared formaldehyde catalytic decomposer into gypsum slurry, stirring by a high-speed stirrer, wherein the rotating speed is 1500r/min, and the time is controlled to be 1min.
Step four: pouring the prepared gypsum-based material into a printing pump, and printing and molding; the gypsum-based material obtained in this comparative example was designated as EP2.
Next, the fluidity, initial setting and final setting tests, extrusion continuity judgment, porosity, flexural strength, compressive strength tests were carried out on the gypsum-based materials P1 to P4 for 3D printing and EP1 to EP2 obtained in examples 1 to 4 and comparative examples 1 to 2, respectively.
The prepared gypsum-based material is detected according to a GB/T2419-2005 cement mortar fluidity detection method;
the initial setting and final setting test adopts national standard GB/T23456-2009; printing nozzle gypsum extrusion refers to gypsum extrusion type 3D printing forming process specification, and judges the continuity of the gypsum extrusion type 3D printing forming process specification; flexural strength and compressive strength are tested by GB/T17671-1999 "cement mortar Strength test method"; the results of the above test are shown in table 1 below:
TABLE 1
| Project | Slurry P1 | Slurry P2 | Slurry P3 | Slurry P4 | Slurry EP1 | Slurry EP2 |
| Fluidity/mm | 200 | 198 | 194 | 189 | 192 | 193 |
| Initial setting time/min | 9 | 12 | 13 | 15 | 15 | 14 |
| Final setting time/min | 32 | 39 | 42 | 46 | 45 | 43 |
| Apparent density/kg/m 3 | 788 | 735 | 710 | 658 | 1216 | 1208 |
| Flexural Strength/MPa | 1.6 | 1.5 | 1.5 | 1.4 | 2.4 | 2.3 |
| Compressive Strength/MPa | 3.8 | 3.4 | 3.1 | 2.7 | 8.8 | 8.4 |
| Extrusion continuity determination | Preferably, it is | Preferably, it is | Excellent quality | Excellent quality | In general | Fracture occurs |
| 24H formaldehyde purification rate/% | 87.6％ | 88.9％ | 90.4％ | 92.1％ | 65.6％ | 62.8％ |
In table 1: "fluidity" and "extrusion continuity judgment" reflect the printability of the 3D printing material; the "initial setting time" and "final setting time" reflect the setting speed of the 3D printed material; "apparent density" reflects the pore distribution of gypsum; the "flexural strength" and "compressive strength" reflect the mechanical properties of gypsum; the "24h formaldehyde purification rate" reflects the absorption and decomposition effects of gypsum on formaldehyde.
As can be seen from the data in Table 1, the 3D printing pastes P1 to P4 obtained in examples 1 to 4 using the gypsum product for 3D printing provided by the present invention were superior in effect to the 3D printing pastes EP1 to EP2 obtained in comparative examples 1 to 2, regardless of setting time, mechanical properties and printability; wherein, the comparative example 2 is formed too fast, which causes the condition that the continuity of printing extrusion is broken, and printing cannot be realized; comparative example 1, although print-formable, has much less effect than examples 1-4, particularly in setting time, printability, and formaldehyde adsorption capacity.
Therefore, as apparent from the above table 1, the material prepared by the preparation method of the gypsum-based material for 3D printing provided by the present invention, when used for 3D printing, can enable 3D printing to have the properties of fast early setting speed, high strength, excellent thixotropic property and printability, and small apparent density, and can strongly adsorb formaldehyde.
Claims (7)
1. The utility model provides a purify formaldehyde 3D and print porous gypsum material which characterized in that: the gypsum material comprises the following raw materials in parts by mass: 60-85 parts of gypsum, 10-25 parts of admixture, 0-0.4 part of water reducer, 0.1-0.5 part of retarder, 0.5-0.8 part of foaming agent, 0.5-1.0 part of composite fiber, 0.2-0.6 part of thickening thixotropic agent, 4-8 parts of regulator and 0.1-0.4 part of coagulant; the components further comprise a formaldehyde adsorbent;
the formaldehyde adsorbent is prepared by the following steps: the material used is 5-8 parts of diatomite, 1-5 parts of activated carbon and 5-8 parts of nano TiO 2; purifying diatomite by a roasting method, wherein the content of SiO 2 after purification is up to 90%, and then preparing a composite material from TiO 2, purified diatomite and nano-scale activated carbon by a sol-gel method by taking butyl titanate as a raw material; uniformly coating nano TiO 2 factors and active carbon factors on the surfaces of the micro diatomite particles to finally prepare formaldehyde adsorption gel;
the coagulant adopts saturated sulfate;
the regulator is a mixture of alumina, talcum powder and polycarboxylic acid dispersing agent.
2. The formaldehyde-purifying 3D printing porous gypsum material of claim 1, wherein: the gypsum is high-strength gypsum powder, and is prepared from desulfurized gypsum or phosphogypsum by a pressurized hydrothermal method or an atmospheric salt solution method; the high-strength gypsum powder has the flexural strength of more than 5 MPa after 2 hours and the dry compressive strength of more than 30 MPa.
3. The formaldehyde-purifying 3D printing porous gypsum material of claim 2, wherein: the admixture comprises silica fume and quicklime, wherein the mass ratio of the silica fume to the quicklime is (15-20) and (5-8).
4. The formaldehyde-purifying 3D printing porous gypsum material of claim 3, wherein:
the water reducing agent is a polycarboxylate water reducing agent, and the water reducing rate is 25% -35%;
the retarder is a protein retarder;
the foaming agent is prepared by compounding an animal protein foaming agent and a surfactant.
5. The formaldehyde-purifying 3D printing porous gypsum material of claim 4, wherein:
the composite fiber is obtained by mixing lignin fiber and basalt fiber according to the mass ratio of 1:1-1:2;
the diatomite consists of remains of diatom and mainly comprises SiO 2;
The micropore diameter of the surface of the active carbon is between 20 and 50 nm;
the particle size of the nano TiO 2 is 10-50 nm.
6. The formaldehyde-purifying 3D printing porous gypsum material of claim 5, wherein:
The thickening thixotropic agent is fumed silica and is amorphous SiO 2: the primary particle size is between 7 and 40 nm; the aggregate particle size is 200-500 nm, the specific surface area is 100-400 m2/g, the purity is high, and the SiO 2 content is not less than 99.8%.
7. A method of preparing the purified formaldehyde 3D printed porous gypsum material of any one of claims 1 to 6, characterized by: the method comprises the following steps:
S1: placing 60-85 parts of phosphogypsum, 50-70 parts of water, 10-25 parts of admixture, 0.1-0.5 part of retarder, 0-0.4 part of water reducer, 4-8 parts of regulator and 0.5-1.0 part of wood composite fiber into a container, continuously stirring 3-4 min parts of the mixture by using an electric stirrer, and uniformly mixing the mixture to prepare gypsum slurry;
S2: a high-speed stirrer is adopted, and a high-speed blade of the stirrer is utilized to stir the foaming agent to obtain foam; the rotation speed of the stirrer is required to be more than 1000 r/min, and the stirring time is required to be more than 2 min;
S3: preparing formaldehyde adsorbent, wherein the material is 5-8 parts of diatomite, 1-5 parts of activated carbon and 5-8 parts of nano TiO 2; purifying diatomite by a roasting method, wherein the content of SiO 2 after purification is up to 90%, and then preparing a composite material from TiO 2, purified diatomite and nano-scale activated carbon by a sol-gel method by taking butyl titanate as a raw material; uniformly coating nano TiO 2 factors and active carbon factors on the surfaces of the micro diatomite particles to finally prepare formaldehyde adsorption gel;
S4: pouring the prepared foaming solution and formaldehyde adsorbent into gypsum slurry, and adopting a high-speed stirrer to fully fuse the three solutions, wherein the stirring time is controlled to be 1-3 min, and the foaming is uniform, fine and stable; then adding aluminum oxide and talcum powder to increase the fluidity of the slurry, and obtaining the 3D printing gypsum-based slurry with the required fluidity of more than 280 mm and the viscosity of less than 0.3 Pa s; preparing a gypsum-based 3D printing material with formaldehyde purifying function;
S5: pouring the prepared gypsum-based 3D printing material with formaldehyde purifying function into a 3D printing device, arranging a spraying device around a printer nozzle, pouring saturated sulfate solution into the device, spraying the saturated sulfate solution on the surface of gypsum during printing, and rapidly hardening gypsum on the surface layer of the gypsum, so that the time for rapidly solidifying the gypsum by high-flow-state slurry is less than 2 min, and finally preparing the gypsum-based 3D printing product with formaldehyde purifying function.
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