CN109455973B - Thixotropic agent suitable for 3D printing of sulphoaluminate cement-based material - Google Patents
Thixotropic agent suitable for 3D printing of sulphoaluminate cement-based material Download PDFInfo
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- CN109455973B CN109455973B CN201811569432.9A CN201811569432A CN109455973B CN 109455973 B CN109455973 B CN 109455973B CN 201811569432 A CN201811569432 A CN 201811569432A CN 109455973 B CN109455973 B CN 109455973B
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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
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Abstract
The invention discloses a thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material, which consists of papermaking sludge ash, polyvinyl alcohol, diatomite, metakaolin and sodium polyacrylate. The thixotropic agent can prolong the printing time to 30-60 min, greatly improves the thixotropic property of 3D printing sulphoaluminate cement-based materials, and realizes the stable control of a 3D printing structure. In addition, the rheological property and the setting and hardening rate of the 3D printing cement-based material can be effectively adjusted, the porosity of the cement-based material is reduced, and the early mechanical property of the 3D printing cement-based material is improved.
Description
Technical Field
The invention relates to a thixotropic agent for 3D printing, in particular to a thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material, and belongs to the technical field of building materials.
Background
The 3D printing technology is a green and efficient emerging technology, and is a rapid forming technology for manufacturing a three-dimensional solid structure by accumulating materials layer by layer on the basis of a digital and intelligent model. The 3D printing has higher requirements on materials, such as higher viscosity and yield stress, good thixotropy, fast hardness, volume stability, high strength and the like, and the 3D printing of the cement-based material has the problems of low early strength, difficult regulation and control of rheological property and the like, so that the three-dimensional solid structure and performance of the 3D printing cement-based material are difficult to realize stable control, and the development of the 3D printing cement-based material technology is severely restricted. The introduction of the sulphoaluminate cement can well improve the early mechanical property of 3D printing slurry, but the rapid hydration and setting rate of the sulphoaluminate cement can result in short printing time and poor matching with a 3D printing structure, thereby having great difficulty in application.
Aiming at the problems of the preparation of the sulphoaluminate cement-based material by adopting a 3D printing technology, the problems that the rheological property of the sulphoaluminate cement-based material is difficult to regulate and control, the printing time is short and the like in the 3D printing process are generally improved by adding a thixotropic agent, and meanwhile, the sulphoaluminate cement-based material also has a certain effect of improving the early strength property of the cement-based material. The thixotropic agent can form a flocculation structure in the cement-based material, when the cement-based material is subjected to shearing action, the formed flocculation structure is broken, the fluidity is recovered, and when the shearing action is stopped, the flocculation structure is formed again in the cement-based material, and the fluidity is reduced. Therefore, the thixotropic agent is introduced to enable the paste to have good flowing property before printing, and a stable 3D structure can be obtained after printing.
Patent 201810601982.8 discloses a thixotropic agent special for 3D printed concrete, which is composed of an inorganic flocculant, an organic polymer thixotropic early strength agent and a foam stabilizer. The thixotropic agent has better thixotropy and can improve the early strength of concrete. However, this patent is not applicable to all cements and its early strength is low and is not controllable for the printable time.
Patent 201710417844.X discloses an inorganic ink material and a preparation method and application thereof, wherein the inorganic ink material is prepared by taking magnesium oxide, monopotassium phosphate and mineral admixture as main raw materials, adding a coagulation regulator, a water reducing agent and a thixotropic regulator, and uniformly mixing. However, the thixotropic agent is a special thixotropic agent for magnesium phosphate cement, is not suitable for sulphoaluminate cement, and cannot flexibly regulate and control rheological properties.
Patent 201610347021.X discloses a dry-mixed mortar material for 3D printing and a preparation method and application thereof, wherein the dry-mixed mortar material comprises cement, sand, a mineral active admixture, a powder water reducing agent, a viscosity regulator, a self-supporting cohesive function agent, an accelerator and reinforcing fibers. This patent changes the rheological characteristics of conventional cement materials in a shape similar to a dough, but its quick setting component is not suitable for sulphoaluminate cement-based materials.
Disclosure of Invention
The invention aims to provide a thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material, which has high water absorption rate, can obviously improve the thixotropic performance of the 3D printing sulphoaluminate cement-based material, improves the early strength of the cement-based material, prolongs the printing time, and solves the problem that the 3D printing slurry structure is difficult to control.
In order to achieve the purpose, the invention adopts the following technical scheme:
a thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material is composed of the following raw materials in parts by weight: 15-30 parts of papermaking sludge ash, 5-15 parts of polyvinyl alcohol, 10-30 parts of diatomite, 10-40 parts of metakaolin and 5-15 parts of sodium polyacrylate.
Preferably, the performance is better when the following components in parts by weight are selected for each raw material of the thixotropic agent: 18 parts of papermaking sludge ash, 12 parts of polyvinyl alcohol, 15 parts of diatomite, 15 parts of metakaolin and 12 parts of sodium polyacrylate.
Furthermore, the sulphoaluminate cement-based material is prepared by adding superfine quartz sand, a polycarboxylic acid water reducing agent and the like on the basis of sulphoaluminate cement.
Furthermore, the papermaking sludge ash is a calcined product of the papermaking sludge which is a byproduct of the papermaking industry, the main component of the papermaking sludge ash is hydrated calcium silicate, and some papermaking sludge ash contains anhydrous calcium sulfate, and because the calcium sulfate has a retarding effect, the papermaking sludge ash containing the anhydrous calcium sulfate is preferably selected. The water absorption rate of the papermaking sludge ash is 10-30%.
Furthermore, the alcoholysis degree of the polyvinyl alcohol is 87.0-90.0 mol%, and the viscosity of the polyvinyl alcohol is 20-25 mPa & s.
Further, the main component of the diatomite is opal, the particle size of the diatomite is 5-40 mu m, and the water absorption rate is 100-200%;
furthermore, the main component of the metakaolin is anhydrous aluminum silicate, the particle size of the metakaolin is 3-70 mu m, and the water absorption rate is 50-130%.
Furthermore, the viscosity of the sodium polyacrylate is 400-600 mPa & s, and the molecular weight of the sodium polyacrylate is 200-300 ten thousand.
The thixotropic agent takes papermaking sludge ash, polyvinyl alcohol, diatomite, metakaolin and sodium polyacrylate as raw materials, is simple to prepare, and is obtained by uniformly mixing the raw materials. The papermaking sludge ash is a calcined product of papermaking sludge which is a byproduct of the papermaking industry, the main component of the papermaking sludge ash is hydrated calcium silicate, and anhydrous calcium sulfate may be contained, the hydrated calcium silicate can provide certain strength for 3D printing of a cement-based material, and the anhydrous calcium sulfate can adjust the setting time. The polyvinyl alcohol as an organic polymer material can play a role in thickening and retarding coagulation of cement-based materials, can prolong the printable time, and is particularly suitable for improving the thixotropy and the paste structure of 3D printing cement-based paste. The diatomite mainly comprises opal (silica gel) and has a molecular sieve structure, so that the diatomite has a high water absorption rate, is particularly suitable for being used as a thixotropic material for improving 3D printing slurry, and reduces the porosity. Metakaolin, as a clay substance, has a layered silicate structure, the main component of the metakaolin is anhydrous aluminum silicate, and the metakaolin is a high-activity mineral, so that the strength of the 3D printing cement-based paste can be improved, and the thixotropic property can be improved. Sodium polyacrylate is as macromolecular material, and its molecular weight can reach 200~300 ten thousand, can play slow setting and thickening effect to cement simultaneously, can realize the stable control of 3D printing slurry structure, prolongs the printing time.
The invention provides a proper thixotropic agent for 3D printing sulphoaluminate cement-based materials, the thixotropic agent utilizes clay substances and retarding components (polyvinyl alcohol and sodium polyacrylate) to cooperatively regulate and control the thixotropy and the setting and hardening rate of 3D printing aluminate cement-based material slurry, and can stabilize the 3D printing aluminate cement-based material slurry structure. Meanwhile, the deformation rate of the aluminate cement-based material slurry can be effectively reduced, and the printing time is prolonged.
The thixotropic agent disclosed by the invention is verified to be capable of prolonging the printable time of the aluminate cement-based material slurry to 30-60 min, greatly improving the thixotropic performance of 3D printing sulphoaluminate cement-based materials and realizing the stable control of the structure and performance of a 3D printing three-dimensional entity. In addition, the rheological property and the setting and hardening rate of the 3D printing cement-based material can be effectively adjusted, the porosity of the cement-based material is reduced, and the early mechanical property of the 3D printing cement-based material is improved.
Detailed Description
The present invention will be further described with reference to specific examples, which are provided for illustration and explanation, and are not intended to limit the present invention.
In the following examples, the paper sludge ash used was from a Huatai paper mill, in which the content of calcium silicate hydrate was 61%, the content of anhydrous calcium sulfate was 39%, and the water absorption rate was 25%. The polyvinyl alcohol had an alcoholysis degree of 90.0 mol% and a viscosity of 25 mPas. The particle size of the diatomite is 5-40 mu m, and the water absorption rate is 130%. The particle size of the metakaolin is 3-70 mu m, and the water absorption rate is 95%. The viscosity of the sodium polyacrylate is 600 mPas, and the molecular weight is 300 ten thousand.
Example 1
A thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material comprises the following raw materials in parts by weight: 30 parts of papermaking sludge ash, 6 parts of polyvinyl alcohol, 28 parts of diatomite, 30 parts of metakaolin and 6 parts of sodium polyacrylate.
The raw materials are uniformly mixed according to the parts by weight, and the thixotropic agent (the thixotropic agent for short, the same below) suitable for 3D printing of the sulphoaluminate cement-based material is prepared.
Example 2
A thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material comprises the following raw materials in parts by weight: 18 parts of papermaking sludge ash, 12 parts of polyvinyl alcohol, 15 parts of diatomite, 15 parts of metakaolin and 12 parts of sodium polyacrylate.
The thixotropic agent for 3D printing of the sulphoaluminate cement-based material is prepared by uniformly mixing the raw materials in parts by weight.
Example 3
A thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material comprises the following raw materials in parts by weight: 18 parts of papermaking sludge ash, 11 parts of polyvinyl alcohol, 22 parts of diatomite, 36 parts of metakaolin and 13 parts of sodium polyacrylate.
The thixotropic agent for 3D printing of the sulphoaluminate cement-based material is prepared by uniformly mixing the raw materials in parts by weight.
Example 4
A thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material comprises the following raw materials in parts by weight: 15 parts of papermaking sludge ash, 15 parts of polyvinyl alcohol, 10 parts of diatomite, 20 parts of metakaolin and 5 parts of sodium polyacrylate.
The thixotropic agent for 3D printing of the sulphoaluminate cement-based material is prepared by uniformly mixing the raw materials in parts by weight.
Example 5
A thixotropic agent suitable for 3D printing of a sulphoaluminate cement-based material comprises the following raw materials in parts by weight: 20 parts of papermaking sludge ash, 5 parts of polyvinyl alcohol, 15 parts of diatomite, 40 parts of metakaolin and 15 parts of sodium polyacrylate.
The thixotropic agent for 3D printing of the sulphoaluminate cement-based material is prepared by uniformly mixing the raw materials in parts by weight.
Comparative example 1
Preparing a thixotropic agent, wherein the raw materials and the weight parts of the thixotropic agent are as follows: 18 parts of silica fume, 12 parts of polyvinyl alcohol, 15 parts of diatomite, 15 parts of fly ash and 12 parts of sodium polyacrylate. The thixotropic agent is obtained by uniformly mixing the raw materials.
Comparative example 2
Preparing a thixotropic agent, wherein the raw materials and the weight parts of the thixotropic agent are as follows: 10 parts of papermaking sludge ash, 25 parts of polyvinyl alcohol, 5 parts of diatomite, 45 parts of metakaolin and 9 parts of sodium polyacrylate. The thixotropic agent is obtained by uniformly mixing the raw materials.
Comparative example 3
Preparing a thixotropic agent, wherein the raw materials and the weight parts of the thixotropic agent are as follows: 18 parts of steel slag powder, 12 parts of polyvinyl alcohol, 15 parts of bentonite, 15 parts of metakaolin, 12 parts of triethanolamine, 10 parts of methyl cellulose ether and 5 parts of cellulose. The thixotropic agent is obtained by uniformly mixing the raw materials.
And (3) performance testing:
in order to verify the various performance criteria of the thixotropic agents proposed by the present invention, the thixotropic agents prepared in examples 1-5 and comparative examples 1-3 were tested.
Preparing 3D printing sulphoaluminate cement-based material slurry: and (2) putting the sulphoaluminate cement, the superfine quartz sand and the thixotropic agent into a V-shaped mixer, mixing for 30 min at the stirring speed of 30 rpm, and then stirring the mixture, the polycarboxylic acid water reducing agent and water in a paste mixer for 5 min at the stirring speed of 285 rpm to obtain the 3D printing sulphoaluminate cement-based material slurry.
Preparing a sulphoaluminate cement-based material by 3D printing: and (3) placing the obtained 3D printing sulphoaluminate cement-based material slurry in a 3D printer for printing according to a preset model, wherein the diameter of a nozzle is 3 mm, and the printing speed is 10 mm. And placing the printed sample in a constant temperature and humidity curing box for curing for 24 hours.
The printing performance of the slurry prepared above and the mechanical properties of the resulting sulphoaluminate cement-based material were tested, with the results shown in table 1.
In table 1, the rheological property test methods are (plastic viscosity, yield stress, thixotropic ring area): the prepared 3D printing sulphoaluminate cement-based material slurry is placed in a rotational rheometer (British Markovian kinexus lab +) for testing, and the shear rate is 0-200 s-1The shearing time was 4 min. The continuous printing time testing method comprises the following steps: and (3) placing the prepared 3D printing sulphoaluminate cement-based material slurry into a 3D printer charging bucket, and continuously extruding for a time under the constant air pump pressure (0.3 Mpa) by using a 3D printer. The method for testing the ultimate deformation rate comprises the following steps: ratio of final dimensions of the sample to model dimensions after 3D printing. The method for testing the compressive and flexural strength comprises the following steps: the strength of the cured 1d printed samples was tested using a U.S. MTS Universal tester.
The thixotropic agent can control the plastic viscosity of a 3D printing sulphoaluminate cement-based material within the range of 2.57 Pa.s-3.42 Pa.s, control the yield stress within the range of 588-654 Pa, reduce the deformation rate to within the range of 2.02-4.11 percent, prolong the continuous printing time to 30-60 min, and greatly improve the early compressive strength and the rupture strength; the thixotropic property of the 3D printing sulphoaluminate cement-based material is greatly improved, the stable control of the 3D printing structure is realized, and the problems that the setting time and the rheological property of the 3D printing sulphoaluminate cement-based material are difficult to regulate and control, the early strength is low and the like are well solved.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (3)
1. A thixotropic agent suitable for 3D printing of sulphoaluminate cement-based materials is characterized in that: the composition is characterized by comprising the following raw materials in parts by weight: 15-30 parts of papermaking sludge ash, 5-15 parts of polyvinyl alcohol, 10-30 parts of diatomite, 10-40 parts of metakaolin and 5-15 parts of sodium polyacrylate; the papermaking sludge ash comprises calcium silicate hydrate, the water absorption rate of the papermaking sludge ash is 10-30%, the alcoholysis degree of the polyvinyl alcohol is 87.0-90.0 mol%, and the viscosity is 20-25 mPa & s;
the diatomite comprises opal, the particle size of the diatomite is 5-40 mu m, and the water absorption rate is 100-200%;
the metakaolin comprises anhydrous aluminum silicate, the particle size of the metakaolin is 3-70 mu m, and the water absorption rate is 50-130%;
the viscosity of the sodium polyacrylate is 400-600 mPa & s, and the molecular weight of the sodium polyacrylate is 200-300 ten thousand.
2. The thixotropic agent of claim 1, wherein: the composition is characterized by comprising the following raw materials in parts by weight: 18 parts of papermaking sludge ash, 12 parts of polyvinyl alcohol, 15 parts of diatomite, 15 parts of metakaolin and 12 parts of sodium polyacrylate.
3. The thixotropic agent of claim 1, wherein: the papermaking sludge ash also comprises anhydrous calcium sulfate.
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| CN109734355B (en) * | 2019-02-27 | 2021-04-20 | 济南大学 | Viscosity modifier suitable for 3D printing white cement-based material |
| CN111689747B (en) * | 2020-05-27 | 2022-03-11 | 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 |
| 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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| CN105294141A (en) * | 2014-07-29 | 2016-02-03 | 金承黎 | Nano porous concrete taking thixotropic colloid as template agent and preparation method |
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