CN110342898A - A kind of 3D printing compound magnesium oxysulfide cementitious material and the preparation method and application thereof - Google Patents
A kind of 3D printing compound magnesium oxysulfide cementitious material and the preparation method and application thereof Download PDFInfo
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- CN110342898A CN110342898A CN201910640157.3A CN201910640157A CN110342898A CN 110342898 A CN110342898 A CN 110342898A CN 201910640157 A CN201910640157 A CN 201910640157A CN 110342898 A CN110342898 A CN 110342898A
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- cementitious material
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- magnesium oxysulfide
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- 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
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- 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
- B33Y80/00—Products made by additive manufacturing
-
- 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
- C04B28/30—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 magnesium cements or similar cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Producing Shaped Articles From Materials (AREA)
Abstract
The invention belongs to gel rubber material technical fields, and in particular to a kind of compound magnesium oxysulfide cementitious material of 3D printing, and preparation method and application are further disclosed.Compound magnesium oxysulfide cementitious material of the present invention, it is formed using magnesium oxysulfide cementitious material (MOS) and aggregate, the magnesium oxysulfide cementitious material selects magnesium oxysulfide concrete, water-reducing agent, binder, reinforcing agent, retarder, hydrophober and glass fibre composition, and aggregate is then the fine aggregate of talcum powder and dolomite dust composition.Compared with ordinary portland cement 3D printing material, compound magnesium oxysulfide cementitious material of the present invention has good caking property, plasticity, extrudability and continuity, and there are the advantages such as good mechanical property, high-strength light, early strength are high, later strength continues, cohesiveness is good, anti-carbonation is good, resist various soluble salt erosivenesses strong, the performance requirement that can achieve 3D printing product can be used in 3D printing technique applying.
Description
Technical field
The invention belongs to gel rubber material technical fields, and in particular to a kind of compound magnesium oxysulfide cementitious material of 3D printing, and
Preparation method and application are further disclosed.
Background technique
3D printing technique is one kind based on digital model file, can bond material with powdery metal or plastic etc.
Material constructs the technology of object by layer-by-layer printing.Nowadays, 3D printing technique is widely answered in numerous areas
With, such as military field, biologic medical field, field of house buildings.
But the limitation of material used in 3D printing technique but become one of limitation 3D printing technique development it is crucial because
Element.Currently, used 3D printing material is essentially confined to plastics, certain metals or ceramic material, in addition to this, be gelled material
Material is also very popular in the application of 3D printing industry, but in view of the particularity during 3D printing, so that it is to gel rubber material
Performance requirement is clearly distinguishable from conventional gel material, further limits application of the gel rubber material in 3D printing technique, especially
It is that the research in relation to the compound magnesium oxysulfide cementitious material of 3D printing is even more rarely reported.
It is the gel rubber material mainly formed that magnesium oxysulfide cementitious material, which is with magnesium sulfate, magnesia unslacked, and which overcome traditional chlorine oxygen
The many defective works of magnesium cement, become the developing direction of magnesia gel rubber material.Magnesium oxysulfide cementitious material itself has frost resistance
Well, the advantage that anti-carbonation is good, resists various soluble salt erosivenesses strong, it is quick particularly suitable for marine environment and extreme condition
Repairing work etc..But as the used time of 3D printing material, then require it that must also have good plasticity, extrudability, company
The excellent properties such as the features such as continuous property, early strength are high, cohesiveness is good and high-strength light, inorganic fire are non-ignitable, can convenient for material
To ensure its being continuously conveyed property and morphological stability in print procedure, and it can ensure material adhesive property between layers
It is good, it does not collapse, is indeformable, not accumulating, being suitable for the product for printing exquisite exquisiteness；Meanwhile also fineness of materials being required to answer≤325
Mesh, to prevent being blocked in print procedure；And printed material need to have certain operable time, not up to should within the time
The final setting time of material, while material also being allow to keep good extrudability, plasticity and caking property etc..
As it can be seen that traditional magnesium oxysulfide gel rubber material is not particularly suited for 3D printing technique application, and guarantor can be met by developing one kind
Mould the 3D printing that time, the slump, extrusion pressure and high-intensity performance require has actively with compound magnesium oxysulfide cementitious material
Meaning.
Summary of the invention
For this purpose, technical problem to be solved by the present invention lies in providing a kind of 3D printing compound magnesium oxysulfide cementitious material,
To solve the problems, such as that traditional magnesium oxysulfide cementitious material is unsuitable for 3D printing technique application in the prior art, passes through 3D printing technique
Enable magnesium oxysulfide concrete based composites to produce some complicated exquisite and there is very high value-added product, in order to visit
Magnesium oxysulfide concrete based composites can be applied to building trade field by 3D printing technique by rope future；
Second technical problem to be solved by this invention is to provide above-mentioned compound magnesium oxysulfide cementitious material in 3D printing technique
In application.
In order to solve the above technical problems, a kind of compound magnesium oxysulfide cementitious material of 3D printing of the present invention, including such as
The raw material components of lower mass content:
Light calcined magnesia 30-40wt%；
Magnesium sulfate 15-20wt%；
Water 15-20wt%；
Active blend 0.5-1wt%；
Water-reducing agent 0.5-1wt%；
Plasticity-maintaining agent 5-6wt%；
Reinforcing agent 2-3wt%；
Hydrophober 1.5-3wt%；
Dispersing agent 1.5-3wt%；
Defoaming agent 1.5-3wt%；
Fine aggregate 10-20wt%.
Specifically, the fine aggregate includes talcum powder and/or dolomite dust, fineness is 200-325 mesh.
Preferably, the fine aggregate includes the talcum powder and dolomite dust that mass ratio is 6-8:2-4, and more preferable mass ratio
For 7:3.
Specifically, the 3D printing is in compound magnesium oxysulfide cementitious material:
The fineness of the light calcined magnesia is 200-325 mesh；
The magnesium sulfate is epsom salt；
The active blend includes silicon ash, and fineness is 200-325 mesh；
The water-reducing agent includes naphthalene water reducer；
The plasticity-maintaining agent includes carboxymethyl cellulose；
The reinforcing agent includes sodium sulphate；
The hydrophober includes organosilicon hydrophobic powder；
The dispersing agent includes sodium lignin sulfonate；
The defoaming agent includes tributyl phosphate.
The 3D printing method of compound magnesium oxysulfide cementitious material is prepared the invention also discloses a kind of, including is walked as follows
It is rapid:
(1) it takes a selected amount of magnesium sulfate soluble in water, is configured to MgSO4Solution, it is spare；
(2) Xiang Suoshu MgSO4It is mixed that the water-reducing agent, plasticity-maintaining agent, reinforcing agent, hydrophober, dispersing agent and defoaming agent are added in solution
It is even, and the light calcined magnesia is added, active blend and fine aggregate mix, obtain gel slurry to get.
Specifically, further including using vibration and/or centrifugation that gained gel slurry material heap product is close in the step (2)
Real step.
Specifically, further including carrying out vacuumize process to the gel slurry to reduce the step of stomata in the step (2)
Suddenly.
Application the invention also discloses the 3D printing with compound magnesium oxysulfide cementitious material in 3D printing technique field.
Application the invention also discloses the 3D printing with compound magnesium oxysulfide cementitious material in building trade field.
The invention also discloses as the 3D printing with compound magnesium oxysulfide cementitious material through product made from 3D printing technique.
Compound magnesium oxysulfide cementitious material of the present invention is formed using magnesium oxysulfide cementitious material (MOS) and aggregate, described
Magnesium oxysulfide cementitious material selects magnesium oxysulfide concrete, water-reducing agent, binder, reinforcing agent, retarder, hydrophober and glass fibre group
At, and aggregate is then the fine aggregate of talcum powder and dolomite dust composition.Compared with ordinary portland cement 3D printing material, this hair
The bright compound magnesium oxysulfide cementitious material has good caking property, plasticity, extrudability and continuity, and has mechanical property
Energy is good, high-strength light, early strength is high, later strength continues, cohesiveness is good, anti-carbonation is good, resists various solvable salt corrosion energy
The advantages such as power is strong, can achieve the performance requirement of 3D printing product, suitable for print complicated, fine and smooth, exquisiteness product, facilitate
Improve value-added content of product；And compound magnesium oxysulfide cementitious material bright in color of the present invention, whiteness are fine, have printed product
Have performance attractive in appearance, can be used in 3D printing technique applying so that magnesium oxysulfide cementitious material be applied in 3D printing technique with
Development plays good exploration in building trade field with magnesium oxysulfide cementitious material for 3D printing.
Specific embodiment
In the following each embodiments of the present invention:
The light calcined magnesia be by low-grade magnesite after conventional 185 DEG C of calcinings gained, wherein content of magnesia 70-
80%, dioxide-containing silica 7-9%, calcium oxide content 2-3%；Wherein, active oxidation content of magnesium is in 62-65%, fineness
200-325 mesh, screen over-size are no more than 10%；
The magnesium sulfate be epsom salt, component content 96-99%, Fe :≤0.02%, chloride≤0.2%, boric acid≤
0.2%, water-insoluble≤0.02%；
The active blend is silicon ash, and fineness is 200-325 mesh；
The fine aggregate is the mixture of talcum powder and dolomite dust, and fineness is 200-325 mesh.
Embodiment 1
3D printing described in the present embodiment is with compound magnesium oxysulfide cementitious material, the component including following mass percent: light-burned oxidation
Magnesium 30wt%, epsom salt 20wt%, water 20wt%, silicon ash 1wt%, naphthalene water reducer 1wt%, carboxymethyl cellulose 6wt%, sulfuric acid
Sodium 3wt%, organosilicon hydrophobic powder 3wt%, sodium lignin sulfonate 3wt%, tributyl phosphate 3wt%；Fine aggregate (talcum powder: dolomite
Powder=7:3) 10wt%.
The preparation method of compound magnesium oxysulfide cementitious material of 3D printing described in the present embodiment, includes the following steps:
(1) a selected amount of epsom salt is soluble in water, it is configured to MgSO4Solution is stood for 24 hours, spare；
(2) by the MgSO4Solution, the naphthalene water reducer, carboxymethyl cellulose, sodium sulphate, organosilicon hydrophobic powder, lignin
Sodium sulfonate and tributyl phosphate are added agitating device and stir 2 minutes, and light calcined magnesia is then added and silicon ash continues 4 points of stirring
Clock is eventually adding talcum powder and dolomite dust and stirs 3 minutes, the gel slurry stirred evenly to get.
Gained gel slurry is injected into the material barrel of 3D printer, material accumulation is made using vibration and centrifugation
It is more closely knit；And the stomata in material is reduced, in order to which the material printed has and can connect
Continuous property, is packed to obtain the final product.
Embodiment 2
3D printing described in the present embodiment is with compound magnesium oxysulfide cementitious material, the component including following mass percent: light-burned oxidation
Magnesium 35wt%, epsom salt 17wt%, water 17wt%, silicon ash 1wt%, naphthalene water reducer 1wt%, carboxymethyl cellulose 5.5wt%, sulphur
Sour sodium 2.5wt%, organosilicon hydrophobic powder 2wt%, sodium lignin sulfonate 2wt%, tributyl phosphate 2wt%；Fine aggregate (talcum powder: white
Marble dust=7:3) 15wt%.
With compound magnesium oxysulfide cementitious material, the preparation method is the same as that of Example 1 for 3D printing described in the present embodiment.
Embodiment 3
3D printing described in the present embodiment is with compound magnesium oxysulfide cementitious material, the component including following mass percent: light-burned oxidation
Magnesium 40wt%, epsom salt 15wt%, water 15wt%, silicon ash 0.5wt%, naphthalene water reducer 0.5wt%, carboxymethyl cellulose
5.5wt%, sodium sulphate 2.5wt%, organosilicon hydrophobic powder 2wt%, sodium lignin sulfonate 2wt%, tributyl phosphate 2wt%；Fine aggregate
(talcum powder: dolomite dust=7:3) 15wt%.
With compound magnesium oxysulfide cementitious material, the preparation method is the same as that of Example 1 for 3D printing described in the present embodiment.
Embodiment 4
3D printing described in the present embodiment is with compound magnesium oxysulfide cementitious material, the component including following mass percent: light-burned oxidation
Magnesium 37wt%, epsom salt 15wt%, water 15wt%, silicon ash 0.7wt%, naphthalene water reducer 0.8wt%, carboxymethyl cellulose 5wt%,
Sodium sulphate 2wt%, organosilicon hydrophobic powder 1.5wt%, sodium lignin sulfonate 1.5wt%, tributyl phosphate 1.5wt%；Fine aggregate (talcum
Powder: dolomite dust=6:4) 20wt%.
With compound magnesium oxysulfide cementitious material, the preparation method is the same as that of Example 1 for 3D printing described in the present embodiment.
Embodiment 5
3D printing described in the present embodiment is with compound magnesium oxysulfide cementitious material, the component including following mass percent: light-burned oxidation
Magnesium 34wt%, epsom salt 17wt%, water 18wt%, silicon ash 0.8wt%, naphthalene water reducer 0.7wt%, carboxymethyl cellulose
5.5wt%, sodium sulphate 2.5wt%, organosilicon hydrophobic powder 2wt%, sodium lignin sulfonate 2.5wt%, tributyl phosphate 2wt%；Fine aggregate
(talcum powder: dolomite dust=8:2) 15wt%.
With compound magnesium oxysulfide cementitious material, the preparation method is the same as that of Example 1 for 3D printing described in the present embodiment.
Correlated performance test is carried out to compound magnesium oxysulfide cementitious material obtained in above-described embodiment 1-5, test result is shown in
Shown in the following table 1.
The performance test results of table 1 3D printing magnesium oxysulfide cementitious material
By upper table data it is found that the operable time of compound magnesium oxysulfide cementitious material of the present invention is up to 175min, and protect modeling
Time and slump performance are preferable, the magnesium oxysulfide cementitious material have early strength is high, plastic deformation is small, squeeze out continuity,
The advantages that without accumulation, print surface exquisiteness without cracking, it is completely suitable for 3D printing technique application, and have and build applied to 3D printing
Build the potentiality of industry field.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of compound magnesium oxysulfide cementitious material of 3D printing, which is characterized in that the raw material components including following mass content:
Light calcined magnesia 30-40wt%；
Magnesium sulfate 15-20wt%；
Water 15-20wt%；
Active blend 0.5-1wt%；
Water-reducing agent 0.5-1wt%；
Plasticity-maintaining agent 5-6wt%；
Reinforcing agent 2-3wt%；
Hydrophober 1.5-3wt%；
Dispersing agent 1.5-3wt%；
Defoaming agent 1.5-3wt%；
Fine aggregate 10-20wt%.
2. the compound magnesium oxysulfide cementitious material of 3D printing according to claim 1, which is characterized in that the fine aggregate includes sliding
Mountain flour and/or dolomite dust, fineness are 200-325 mesh.
3. the compound magnesium oxysulfide cementitious material of 3D printing according to claim 2, which is characterized in that the fine aggregate includes matter
Amount is than the talcum powder and dolomite dust for 6-8:2-4.
4. any one of -3 compound magnesium oxysulfide cementitious material of the 3D printing according to claim 1, it is characterised in that:
The fineness of the light calcined magnesia is 200-325 mesh；
The magnesium sulfate is epsom salt；
The active blend includes silicon ash, and fineness is 200-325 mesh；
The water-reducing agent includes naphthalene water reducer；
The plasticity-maintaining agent includes carboxymethyl cellulose；
The reinforcing agent includes sodium sulphate；
The hydrophober includes organosilicon hydrophobic powder；
The dispersing agent includes sodium lignin sulfonate；
The defoaming agent includes tributyl phosphate.
5. a kind of prepare any one of claim 1-4 3D printing method of compound magnesium oxysulfide cementitious material, feature exists
In including the following steps:
(1) it takes a selected amount of magnesium sulfate soluble in water, is configured to MgSO4Solution, it is spare；
(2) Xiang Suoshu MgSO4It is mixed that the water-reducing agent, plasticity-maintaining agent, reinforcing agent, hydrophober, dispersing agent and defoaming agent are added in solution
It is even, and the light calcined magnesia is added, active blend and fine aggregate mix, obtain gel slurry to get.
6. according to claim 5 prepare the 3D printing method of compound magnesium oxysulfide cementitious material, which is characterized in that
In the step (2), include the steps that using vibration and/or centrifugation that gained gel slurry material heap product is closely knit.
7. according to claim 6 prepare the 3D printing method of compound magnesium oxysulfide cementitious material, which is characterized in that
In the step (2), further include the steps that carrying out the gel slurry vacuumize process to reduce stomata.
8. any one of the claim 1-4 3D printing is with compound magnesium oxysulfide cementitious material answering in 3D printing technique field
With.
9. application of any one of the claim 1-4 3D printing with compound magnesium oxysulfide cementitious material in building trade field.
10. as any one of the claim 1-4 3D printing with compound magnesium oxysulfide cementitious material through product made from 3D printing technique.
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| CN110576610A (en) * | 2019-10-28 | 2019-12-17 | 辽宁科技大学 | 3D printer shaping cavity |
| CN113233866A (en) * | 2021-05-26 | 2021-08-10 | 深圳大学 | 3D printing magnesium oxysulfate cement concrete product and maintenance method thereof |
| CN113501703A (en) * | 2021-05-26 | 2021-10-15 | 深圳大学 | 3D printing magnesium phosphate cement concrete product and maintenance method thereof |
| WO2023070140A1 (en) | 2021-10-27 | 2023-05-04 | Breitenberger Georg | Method for producing an additively manufactured and coated casting mould for the production of components in a cold casting process or lamination process |
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| CN110342898B (en) | 2022-04-12 |
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