CN109455973A - A kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material - Google Patents
A kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material Download PDFInfo
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- CN109455973A CN109455973A CN201811569432.9A CN201811569432A CN109455973A CN 109455973 A CN109455973 A CN 109455973A CN 201811569432 A CN201811569432 A CN 201811569432A CN 109455973 A CN109455973 A CN 109455973A
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- parts
- thixotropic agent
- printing
- paper mill
- mill sludge
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- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
Abstract
The present invention discloses a kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, is made of paper mill sludge ash, polyvinyl alcohol, diatomite, metakaolin, Sodium Polyacrylate.Thixotropic agent of the present invention can will extend to 30 ~ 60 min, and the stability contorting for greatly improving the thixotropic property of 3D printing sulphoaluminate cement base material, realizing 3D printing structure the print time.Furthermore, it is possible to effectively adjust the rheological property and condensation hardening rate, the porosity for reducing cement-based material of 3D printing cement-based material, improve the early mechanics characteristics of 3D printing cement-based material.
Description
Technical field
The present invention relates to a kind of 3D printing thixotropic agent, more particularly to one kind to be suitable for 3D printing sulphoaluminate cement base material
The thixotropic agent of material, belongs to building material technical field.
Background technique
3D printing technique is the benefit to digitize, based on intelligent model as a kind of green, efficient emerging technology
It is successively added up with material to manufacture the rapid shaping technique of 3D solid structure.3D printing is to material requirement with higher, example
Higher viscosity and yield stress, good thixotropy, fast hardness, volume stability, high intensity are such as needed, due to 3D printing
Cement-based material leads to 3D printing cement-based material 3D solid there are early strength low the problems such as being difficult to rheological property
Structure and performance are difficult to realize stability contorting, seriously constrain the development of 3D printing cement-based material technology.Sulphate aluminium cement
Introducing can be good at improving the early mechanics characteristics of 3D printing slurry, but since its faster aquation rate of setting can be led
It causes the printable time shorter and poor with the matching of 3D printing structure, above has biggish difficulty in application.
For sulphoaluminate cement base material using the problems of 3D printing technique preparation, generally pass through addition at present
The problems such as form of thixotropic agent is difficult to improving its rheological property during 3D printing, the printable time is shorter, together
When also tool have some improvement cement-based material morning epistasis can effect.Thixotropic agent can form flocculation knot in cement-based material
Structure is formed by flocculent structure and is broken when cement-based material is by shear action, restores mobility, when shear action is stopped
When only, flocculent structure is re-formed in cement-based material, mobility reduces.Therefore, the introducing of thixotropic agent can be such that slurry is beating
Have good mobile performance before print, and relatively stable 3D structure can be obtained after printing.
201810601982 .8 of patent discloses a kind of dedicated thixotropic agent of 3D printing concrete, by inorganic flocculating agent, organic
Macromolecule thixotroping early strength agent, foam stabilizer composition.The thixotropic agent has preferable thixotropy, can improve the early strength of concrete.But
It is this patent is to be not particularly suited for all cement, and its early strength is lower, the printable time can not be regulated and controled.
Patent 201710417844.X discloses a kind of inorganic ink material and its preparation method and application, inorganic ink material
Material is using magnesia, potassium dihydrogen phosphate, mineral admixture as main raw material(s), incorporation adjustable solidification agent, water-reducing agent and thixotroping regulator,
Even mix forms.But this patent is the dedicated thixotropic agent of magnesium phosphate cement, is not suitable for sulphate aluminium cement, and it is for stream
Denaturation energy can not flexible modulation.
Patent 201610347021.X discloses a kind of 3D printing dry-mixed mortar material and its preparation method and application, should
Dry-mixed mortar material by cement, sand, mineral active admixture, powder water-reducing agent, viscosity modifier, self-supporting adhesive aggregation functional agent,
Accelerator and reinforcing fiber composition.The patent changes the rheology characteristic of conventional cement material, and shape is similar to dough, but its speed
Solidifying component is not particularly suited for sulphoaluminate cement base material.
Summary of the invention
The object of the present invention is to provide a kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, the thixotropic agent
Water absorption rate is higher, can be obviously improved the thixotropic property of 3D printing sulphoaluminate cement base material, improves the morning of cement-based material
Phase intensity extends the print time, solves the problems, such as that 3D printing paste structure is difficult to control.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, the thixotropic agent by following parts by weight raw material group
At: 15 ~ 30 parts of paper mill sludge ash, 5 ~ 15 parts of polyvinyl alcohol, 10 ~ 30 parts of diatomite, 10 ~ 40 parts of metakaolin, Sodium Polyacrylate 5
~ 15 parts.
Preferably, when thixotropic agent each raw material select following parts by weight of component when, performance more preferably: paper mill sludge ash 18 parts,
12 parts of polyvinyl alcohol, 15 parts of diatomite, 15 parts of metakaolin, 12 parts of Sodium Polyacrylate.
Further, the sulphoaluminate cement base material be based on sulphate aluminium cement, by be added it is ultra-fine
The material that quartz sand, polycarboxylate water-reducer etc. are prepared.
Further, the paper mill sludge ash is the calcined product of paper industry byproduct paper mill sludge, main component
For hydrated calcium silicate, some contains dead plaster, because calcium sulfate has deferred action, preferential selection contains anhydrous sulphur
The paper mill sludge ash of sour calcium.The water absorption rate of paper mill sludge ash is 10 ~ 30%.
Further, the alcoholysis degree of the polyvinyl alcohol is 87.0 ~ 90.0 mol%, and viscosity is 20 ~ 25 mPas.
Further, the main component of the diatomite be opal, diatomite partial size be 5 ~ 40 μm, water absorption rate be 100 ~
200%；
Further, the main component of the metakaolin is anhydrous aluminium silicate, and the partial size of metakaolin is 3 ~ 70 μm, water absorption rate
It is 50 ~ 130%.
Further, the viscosity of the Sodium Polyacrylate is 400~600 mPas, and molecular weight is 200~3,000,000.
Thixotropic agent of the present invention is using paper mill sludge ash, polyvinyl alcohol, diatomite, metakaolin, Sodium Polyacrylate as raw material, system
It is standby simple, each raw material is uniformly mixed to obtain the final product.Paper mill sludge ash is the calcined product of paper industry byproduct paper mill sludge, master
Ingredient hydrated calcium silicate is wanted, dead plaster is perhaps contained, hydrated calcium silicate can provide centainly for 3D printing cement-based material
Intensity, dead plaster adjustable setting time.Polyvinyl alcohol can be to cement-based material as high-molecular organic material
Thickening and deferred action are played, the printable time is able to extend, especially suitable for improving the thixotropy of 3D printing cement base slurry
And paste structure.Diatomite main component is opal (silica dioxide gel), is molecular sieve structure, has very big water suction
Rate is particularly suitable for application as improving the thixotropic material of 3D printing slurry, and reduces porosity.Metakaolin is as clay object
Matter has layered silicate structure, and main component is anhydrous aluminium silicate, is high-activity mineral, can be improved 3D printing cement base
Slurry intensity improves thixotropic property.Sodium Polyacrylate can reach 200 ~ 3,000,000 as high molecular material, molecular weight, can
Slow setting and thickening power are played to cement simultaneously, can be realized the stability contorting of 3D printing paste structure, extends the print time.
The present invention provides suitable thixotropic agent for 3D printing sulphoaluminate cement base material, which utilizes clay class
The thixotroping of substance and slow setting component (polyvinyl alcohol and Sodium Polyacrylate) coordinated regulation 3D printing aluminate cement substrate slurry body
Property and condensation hardening rate, and 3D printing aluminate cement sill paste structure can be stablized.It can also be effectively reduced simultaneously
The deformation rate of aluminate cement substrate slurry body extends the print time.
Verified, the aluminate cement substrate slurry body printable time can be extended to 30 ~ 60 by thixotropic agent of the present invention
Min, and greatly improve the thixotropic property of 3D printing sulphoaluminate cement base material, realize 3D printing 3D solid structure
With the stability contorting of performance.Furthermore, it is possible to effectively adjust the rheological property and condensation hardening rate, drop of 3D printing cement-based material
The porosity of low cement-based material improves the early mechanics characteristics of 3D printing cement-based material.
Specific embodiment
The present invention is further detailed below in conjunction with specific embodiments of the present invention, following embodiments are only used for
The bright and explanation present invention, is not intended to limit the present invention.
In following embodiments, paper mill sludge ash used is from the safe paper mill of China, and wherein hydrated calcium silicate content 61%, anhydrous
Calcium sulphate content 39%, water absorption rate 25%.The alcoholysis degree of polyvinyl alcohol is 90.0 mol%, and viscosity is 25 mPas.Diatomite
Partial size is 5 ~ 40 μm, water absorption rate 130%.The partial size of metakaolin is 3 ~ 70 μm, water absorption rate 95%.The viscosity of Sodium Polyacrylate
For 600mPas, molecular weight is 3,000,000.
Embodiment 1
A kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, the composition of raw material is in parts by weight such as
Under: paper mill sludge ash 30 parts, 6 parts of polyvinyl alcohol, 28 parts of diatomite, 30 parts of metakaolin, 6 parts of Sodium Polyacrylate.
Above-mentioned each raw material is uniformly mixed by weight, the present invention is obtained and is suitable for 3D printing sulphoaluminate cement base
The thixotropic agent (abbreviation thixotropic agent, similarly hereinafter) of material.
Embodiment 2
A kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, the composition of raw material in parts by weight: make
18 parts of paper sludge ash, 12 parts of polyvinyl alcohol, 15 parts of diatomite, 15 parts of metakaolin, 12 parts of Sodium Polyacrylate.
Above-mentioned each raw material is uniformly mixed by weight, the present invention is obtained and is suitable for 3D printing sulphoaluminate cement base
The thixotropic agent of material.
Embodiment 3
A kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, the composition of raw material in parts by weight: make
18 parts of paper sludge ash, 11 parts of polyvinyl alcohol, 22 parts of diatomite, 36 parts of metakaolin, 13 parts of Sodium Polyacrylate.
Above-mentioned each raw material is uniformly mixed by weight, the present invention is obtained and is suitable for 3D printing sulphoaluminate cement base
The thixotropic agent of material.
Embodiment 4
A kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, the composition of raw material in parts by weight: make
15 parts of paper sludge ash, 15 parts of polyvinyl alcohol, 10 parts of diatomite, 20 parts of metakaolin, 5 parts of Sodium Polyacrylate.
Above-mentioned each raw material is uniformly mixed by weight, the present invention is obtained and is suitable for 3D printing sulphoaluminate cement base
The thixotropic agent of material.
Embodiment 5
A kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, the composition of raw material in parts by weight: make
20 parts of paper sludge ash, 5 parts of polyvinyl alcohol, 15 parts of diatomite, 40 parts of metakaolin, 15 parts of Sodium Polyacrylate.
Above-mentioned each raw material is uniformly mixed by weight, the present invention is obtained and is suitable for 3D printing sulphoaluminate cement base
The thixotropic agent of material.
Comparative example 1
Thixotropic agent is prepared, raw material and parts by weight dosage are as follows: 18 parts of silicon ash, 12 parts of polyvinyl alcohol, 15 parts of diatomite, flyash
15 parts, 12 parts of Sodium Polyacrylate.Each raw material is uniformly mixed to get thixotropic agent.
Comparative example 2
Prepare thixotropic agent, raw material and parts by weight dosage be as follows: 10 parts of paper mill sludge ash, 25 parts of polyvinyl alcohol, 5 parts of diatomite,
45 parts of metakaolin, 9 parts of Sodium Polyacrylate.Each raw material is uniformly mixed to get thixotropic agent.
Comparative example 3
Thixotropic agent is prepared, raw material and parts by weight dosage be as follows: 18 parts of steel-making slag powder, 12 parts of polyvinyl alcohol, 15 parts of bentonite, higher
Ridge soil 15 parts, 12 parts of triethanolamine, 10 parts of methyl cellulose ether, 5 parts of cellulose.Each raw material is uniformly mixed to get thixotropic agent.
Performance test:
In order to verify the performance indexes of thixotropic agent proposed by the present invention, the present invention is in embodiment 1-5 and comparative example 1-3
The thixotropic agent of preparation is tested.
It prepares 3D printing sulphoaluminate cement base material slurry: sulphate aluminium cement, superfine quartz sand, thixotropic agent is placed in
30 min are mixed in V-type batch mixer, mixing speed is 30 rpm, then by said mixture, polycarboxylate water-reducer and water net
5 min are stirred in slurry blender, mixing speed is 285 rpm, obtains 3D printing sulphoaluminate cement base material slurry.
3D printing prepares sulphoaluminate cement base material: above-mentioned gained 3D printing sulphoaluminate cement base material slurry is put
It sets and is printed in 3D printer according to preset model, 3 mm of nozzle diameter, print speed is 10 mm.By the examination after printing
Sample, which is placed in constant-temp. and-moisture maintenance, conserves 24 h.
The mechanical property of print performance and gained sulphoaluminate cement base material to the slurry of above-mentioned configuration is tested,
The results are shown in Table 1.
In table 1, rheology testing method is (plastic viscosity, yield stress, thixotropic loop area): by the 3D of above-mentioned preparation
Printing sulphoaluminate cement base material slurry, which is placed in rotational rheometer (Britain Malvern kinexus lab+), to be surveyed
Examination, shear rate are 0 ~ 200 s-1, shear time is 4 min.Continuous print time test method are as follows: by the 3D of above-mentioned preparation
Printing sulphoaluminate cement base material slurry is placed in 3D printer batch can, using 3D printer in constant air pump pressure (0.3
Mpa the time continuously squeezed out under).Ultimate deformation test method are as follows: the final size of sample and moulded dimension after 3D printing
Ratio.Pressure-proof and snap-resistent strength test method are as follows: using the U.S. MTS universal testing machine test maintenance 1d printing after sample it is strong
Degree.
Thixotropic agent of the invention can by the plastic viscosity of 3D printing sulphoaluminate cement base material control 2.57 Pa s ~
Within the scope of 3.42 Pa s, by yield stress control within the scope of 588-654 Pa, deformation rate is reduced to 2.02-4.11% range
It is interior, the continuous print time is extended into 30-60 min, early anti pressured intension and flexural strength have obtained significantly being promoted；This pole
The earth improves the thixotropic property of 3D printing sulphoaluminate cement base material, realizes the stability contorting to 3D printing structure, very well
Ground solves 3D printing setting time of cement-based material and is difficult to rheological property and the problems such as early strength is low.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (9)
1. a kind of thixotropic agent suitable for 3D printing sulphoaluminate cement base material, it is characterized in that: by the raw material of following parts by weight
Composition: 15 ~ 30 parts of paper mill sludge ash, 5 ~ 15 parts of polyvinyl alcohol, 10 ~ 30 parts of diatomite, 10 ~ 40 parts of metakaolin, polyacrylic acid
5 ~ 15 parts of sodium.
2. thixotropic agent according to claim 1, it is characterized in that: being made of the raw material of following parts by weight: paper mill sludge ash 18
Part, 12 parts of polyvinyl alcohol, 15 parts of diatomite, 15 parts of metakaolin, 12 parts of Sodium Polyacrylate.
3. thixotropic agent according to claim 1, it is characterized in that: the paper mill sludge ash is the calcined product of paper mill sludge.
4. thixotropic agent according to claim 1 or 3, it is characterized in that: the paper mill sludge ash composition includes aquation silicic acid
Calcium, the water absorption rate of paper mill sludge ash are 10 ~ 30%.
5. thixotropic agent according to claim 4, it is characterized in that: the paper mill sludge ash composition further includes anhydrous slufuric acid
Calcium.
6. thixotropic agent according to claim 1, it is characterized in that: the alcoholysis degree of the polyvinyl alcohol is 87.0 ~ 90.0
Mol%, viscosity are 20 ~ 25 mPas.
7. thixotropic agent according to claim 1, it is characterized in that: the ingredient of the diatomite includes opal, diatomite
Partial size is 5 ~ 40 μm, and water absorption rate is 100 ~ 200%.
8. thixotropic agent according to claim 1, it is characterized in that: the ingredient of the metakaolin includes anhydrous aluminium silicate, partially
Kaolinic partial size is 3 ~ 70 μm, and water absorption rate is 50 ~ 130%.
9. thixotropic agent according to claim 1, it is characterized in that: the viscosity of the Sodium Polyacrylate is 400~600 mPa
S, molecular weight are 200~3,000,000.
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| CN109734355A (en) * | 2019-02-27 | 2019-05-10 | 济南大学 | A kind of viscosity modifier suitable for 3D printing plain boiled water cement-based material |
| CN111689747A (en) * | 2020-05-27 | 2020-09-22 | 广东复特新型材料科技有限公司 | 3D printed color decoration mortar |
| CN111975928A (en) * | 2020-08-24 | 2020-11-24 | 上海建工建材科技集团股份有限公司 | Building 3D printing system with consumable adaptability capable of being intelligently regulated and controlled and printing method |
| CN116553871A (en) * | 2023-05-11 | 2023-08-08 | 苏州太湖中法环境技术有限公司 | Nano silicon dioxide modified sludge peat cement material, preparation method and application |
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Cited By (7)
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| CN109734355A (en) * | 2019-02-27 | 2019-05-10 | 济南大学 | A kind of viscosity modifier suitable for 3D printing plain boiled water cement-based material |
| CN109734355B (en) * | 2019-02-27 | 2021-04-20 | 济南大学 | Viscosity modifier suitable for 3D printing white cement-based material |
| CN111689747A (en) * | 2020-05-27 | 2020-09-22 | 广东复特新型材料科技有限公司 | 3D printed color decoration mortar |
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| CN111975928A (en) * | 2020-08-24 | 2020-11-24 | 上海建工建材科技集团股份有限公司 | Building 3D printing system with consumable adaptability capable of being intelligently regulated and controlled and printing method |
| CN116553871A (en) * | 2023-05-11 | 2023-08-08 | 苏州太湖中法环境技术有限公司 | Nano silicon dioxide modified sludge peat cement material, preparation method and application |
| CN116553871B (en) * | 2023-05-11 | 2023-11-10 | 苏州太湖中法环境技术有限公司 | Nano silicon dioxide modified sludge peat cement material, preparation method and application |
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