CN109399995B - Viscosity modifier suitable for 3D printing of sulphoaluminate cement-based material - Google Patents
Viscosity modifier suitable for 3D printing of sulphoaluminate cement-based material Download PDFInfo
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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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- 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
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Abstract
The invention relates to a viscosity modifier suitable for 3D printing of a sulphoaluminate cement-based material, and belongs to the technical field of cement viscosity modifiers. The viscosity modifier comprises the following components in parts by weight: 5-10 parts of polyethylene glycol, 20-40 parts of graphene oxide, 10-20 parts of glycerol, 10-20 parts of a water reducing agent, 5-20 parts of starch and 5-10 parts of quartz powder. The viscosity modifier provided by the invention can control the plastic viscosity of the 3D printing cement-based material within the range of 2.4-3.5 Pa.s, greatly improve the thixotropic property of the 3D printing sulphoaluminate cement-based material and realize the stable control of a 3D printing structure. In addition, the invention can effectively regulate and control the rheological property of the slurry and prolong the setting time so as to regulate the 3D printing time and improve the operability of 3D printing of the cement-based material.
Description
Technical Field
The invention belongs to the technical field of cement viscosity modifiers, and particularly relates to a viscosity modifier suitable for 3D printing of a sulphoaluminate cement-based material.
Background
The 3D printing technology has become a novel and green forming method in the field of building materials, wherein the printing model is designed based on computer software, and the cement material is printed from a 3D printer according to a predetermined model in a layer-by-layer overlapping manner. 3D prints building material can obviously shorten the engineering time, greatly reduced cost, also need not a large amount of workman to build, can improve production efficiency. Furthermore, it is very easy to print complex curved buildings, which are otherwise difficult to construct. However, the development of 3D printing cement-based materials is severely restricted due to the problems that the correlation between the setting time and the rheological property of the 3D printing cement-based materials is difficult to regulate, the early strength is low and the like. For 3D printing of cement-based materials, the printing mode is similar to that of FDM (fused deposition modeling), which requires that the printed slurry does not collapse and deform; therefore, the 3D cement paste requires a large plastic viscosity and yield stress and good thixotropy to keep the printed sample from deforming. However, most of the current 3D printing cement-based materials mainly use a single viscosity modifier to control the rheological properties, such as the commonly used cellulose ethers, but the relationship between the setting and printing time and the rheological properties cannot be comprehensively considered and controlled, and the loss strength cannot be compensated. Therefore, there is a need to develop a new viscosity modifier for 3D printing of sulphoaluminate cement-based materials, which is intended to solve at least some of the above-mentioned problems of the prior art.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials. The viscosity modifier provided by the invention can control the plastic viscosity of the 3D printing cement-based material within the range of 2.4-3.5 Pa.s, greatly improve the thixotropic property of the 3D printing sulphoaluminate cement-based material and realize the stable control of a 3D printing structure. In addition, the invention can effectively regulate and control the rheological property of the slurry and prolong the setting time so as to regulate the 3D printing time and improve the operability of 3D printing of the cement-based material.
One of the objects of the present invention is to provide a viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials.
The invention also aims to provide application of the viscosity modifier suitable for 3D printing of the sulphoaluminate cement-based material.
In order to achieve the above purpose, the invention specifically discloses the following technical scheme:
the invention discloses a viscosity modifier suitable for 3D printing of a sulphoaluminate cement-based material, which comprises the following components in parts by weight: 5-10 parts of polyethylene glycol, 20-40 parts of graphene oxide, 10-20 parts of glycerol, 10-20 parts of a water reducing agent, 5-20 parts of starch and 5-10 parts of quartz powder.
Preferably, the viscosity modifier comprises the following components in parts by weight: 5-8 parts of polyethylene glycol, 22-28 parts of graphene oxide, 11-15 parts of glycerol, 10-14 parts of a water reducing agent, 5-12 parts of starch and 5-7 parts of quartz powder. Tests prove that when the content of each component of the viscosity modifier is controlled within the range, the viscosity of the cement-based material can be further improved.
Preferably, the viscosity modifier comprises the following components in parts by weight: 6-8 parts of polyethylene glycol, 25-35 parts of graphene oxide, 14-18 parts of glycerol, 13-16 parts of a water reducing agent, 10-16 parts of starch and 6-8 parts of quartz powder. Tests prove that when the content of each component of the viscosity modifier is controlled within the range, the viscosity of the cement-based material can be further improved.
The viscosity modifier can control the plastic viscosity of the 3D printing cement-based material within the range of 2.4-3.5 Pa.s, and experiments prove that: when the plastic viscosity is controlled within the range, the deformation rate of the printed slurry is below 5%, so that the printed slurry cannot collapse and deform, the plastic viscosity of the slurry is greater than 3.5 Pa.s, and the slurry cannot be extruded from a charging bucket through a 3D printer, and the viscosity modifier controls the plastic viscosity of the slurry to be 2.4-3.5 Pa.s, so that the slurry well meets the special requirements of 3D printing on the performance of a cement-based material, and obtains excellent technical effects.
Further, the molecular weight of the polyethylene glycol is 1300-1600, and the test proves that: polyethylene glycol as a high polymer material can play a good role in modifying the plastic viscosity of the 3D printing cement paste; in addition, polyethylene glycol as a high polymer material can have good regulation and control effects on thickening and slow setting of the 3D printing sulphoaluminate cement-based material, so that the rheological property and the hydration coagulation property of slurry are improved.
Further, the specific surface area of the graphene oxide is 355m2(ii) in terms of/g. The graphene oxide is of a layered structure, a large number of oxygen-containing groups are arranged between layers and on the surface of the graphene oxide, the graphene oxide has large water content, the yield stress of the 3D printing paste can be regulated and controlled, the thixotropic property of the 3D printing paste can be improved, and meanwhile, the small particle size of the graphene oxide can obviously reduce the porosity and improve the mechanical property. Because the 3D printing slurry is extruded by the air pump after being stirred by the screw, the slurry needs to present better fluidity when the screw is stirred, and the slurry needs to be solidified in a short time after being extruded, so that the 3D printing slurry needs to have better thixotropy.
Further, the glycerin had a water solubility of 550g/L and a viscosity of 200 mPas. The glycerol has a large amount of alcoholic hydroxyl groups, can influence the setting performance of sulphoaluminate cement slurry, and then regulate and control its setting time and continuous printing performance, 3D prints the cement-based material and is different from traditional method, it has special demand to the performance of slurry, the early strength of 3D printing cement slurry can obviously be reduced to overlength setting time, simultaneously under the influence of long-time action of gravity, seriously influence the deformation of slurry, but the printable time can be shortened to the prohibitively short setting time, lead to the slurry can't extrude from the material jar.
Further, the water reducing agent is a naphthalene water reducing agent, the main components of the water reducing agent are naphthalene sulfonic acid formaldehyde condensation compound, triethylene glycol and glycerol, and the water reducing rate is 25-32%. The thickening water reducer can further improve and compensate the thixotropic property of 3D printing sulphoaluminate cement paste, reduce the water consumption and improve the mechanical property of cement.
Further, the starch is amylose, and the main component is glucose. The starch is a glucose molecular polymer and has higher molecular weight, so that the apparent viscosity and the plastic viscosity of the 3D printing slurry can be obviously improved, the deformation rate of the slurry is effectively reduced, and the collapse phenomenon of the 3D printed slurry is avoided, so that the printing failure is caused.
Furthermore, the particle size of the quartz powder is 0.5-20 μm. The quartz powder has high water absorption rate, so that the yield stress of the slurry is improved, the deformation rate is reduced, meanwhile, the porosity of the 3D printing slurry can be obviously reduced, the early mechanical property is improved, and when the particle size of the quartz is controlled within the range, the performance can be further improved.
Compared with the singly-doped viscosity modifier, the components in the viscosity modifier provided by the invention have obvious overall performance improvement effects, such as: (1) the polyethylene glycol and the glycerol are used as liquid additives, although starch is not obviously improved on rheological property, the polyethylene glycol and the glycerol do not occupy excessive proportion of cement in raw materials, so that the strength of a product is not reduced, and the setting time can be prolonged; (2) the thickening water reducer adopted by the invention can obviously make up the condition that other additives do not improve the thixotropy enough, and can also obviously improve the strength of the product. (3) The graphene and the quartz powder can obviously improve the printing property of cement paste, improve the product strength and improve the thixotropy.
Secondly, the preparation method of the viscosity modifier suitable for 3D printing of the sulphoaluminate cement-based material comprises the following steps: the raw material components are uniformly mixed.
Finally, the invention discloses the application of the viscosity modifier suitable for 3D printing of the sulphoaluminate cement-based material in the field of building materials.
Compared with the prior art, the invention has the beneficial effects that:
(1) the viscosity modifier provided by the invention utilizes the thickening component and the retarding component to cooperatively regulate and control the rheological property and the setting and hardening performance of 3D printing slurry, obviously reduces the deformation rate of the 3D printing slurry, and is beneficial to the establishment of a 3D structure. At the same time, the setting time can be prolonged, and the printing performance can be improved.
(2) The viscosity modifier can control the plastic viscosity of a 3D printing cement-based material within the range of 2.4 Pa.s-3.5 Pa.s, control the yield stress within the range of 580-640Pa, reduce the deformation rate to within the range of 3.21-4.21 percent, prolong the initial setting time to 58-71min, prolong the continuous printing time to 31-45min, and greatly improve the compressive strength and the flexural strength; the thixotropic property of the 3D printing sulphoaluminate cement-based material can be greatly improved, and the stable control of the 3D printing structure is realized; the problems that the correlation between the setting time and the rheological property of the 3D printing cement-based material is difficult to regulate and control, the early strength is low and the like are well solved.
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The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
Fig. 1 is a diagram illustrating the effect of 3D printing of cement-based materials according to the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the development of 3D printing cement-based materials is severely restricted due to the problems that the correlation between the setting time and the rheological property of the 3D printing cement-based materials is difficult to regulate, the early strength is low and the like. Therefore, the present invention provides a viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials, and the present invention is further described with reference to the following embodiments.
In the following examples, the molecular weight of the polyethylene glycol is 1300-1600; the specific surface area of the graphene oxide is 355m2(ii) in terms of/g. The water solubility of the glycerol is 550g/L, and the viscosity of the glycerol is 200mPa & s. The water reducing agent is a naphthalene water reducing agent, and the main components of the water reducing agent are a naphthalene sulfonic acid formaldehyde condensation compound, triethylene glycol and glycerol, wherein the proportion of the naphthalene sulfonic acid formaldehyde condensation compound to the triethylene glycol to the glycerol is as follows: 2:1:1, and the water reducing rate is 25-32%. The starch is amylose, and the main component of the starch is glucose.
Example 1
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 6 parts of polyethylene glycol, 22 parts of graphene oxide, 11 parts of glycerol, 12 parts of a water reducing agent, 6 parts of starch and 6 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns.
Example 2
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 8 parts of polyethylene glycol, 31 parts of graphene oxide, 15 parts of glycerol, 14 parts of a water reducing agent, 14 parts of starch and 7 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns.
Example 3
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 9 parts of polyethylene glycol, 37 parts of graphene oxide, 18 parts of glycerol, 18 parts of a water reducing agent, 19 parts of starch and 8 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns.
Example 4
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 5 parts of polyethylene glycol, 20 parts of graphene oxide, 20 parts of glycerol, 15 parts of a water reducing agent, 10 parts of starch and 5 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns.
Example 5
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 10 parts of polyethylene glycol, 28 parts of graphene oxide, 10 parts of glycerol, 10 parts of a water reducing agent, 5 parts of starch and 7 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns.
Example 6
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 7 parts of polyethylene glycol, 40 parts of graphene oxide, 14 parts of glycerol, 20 parts of a water reducing agent, 20 parts of starch and 6 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns.
Example 7
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 6 parts of polyethylene glycol, 35 parts of graphene oxide, 16 parts of glycerol, 10 parts of a water reducing agent, 12 parts of starch and 10 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns.
Test example 1
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 22 parts of graphene oxide, 11 parts of glycerol, 12 parts of a water reducing agent, 6 parts of starch and 6 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 mu m. Through tests, the results are shown in tables 1 and 2, and it can be seen that compared with example 1 in which polyethylene glycol is added, the cement paste viscosity modifier of test example 1 has a certain reduction in plastic viscosity and initial setting time, which is mainly that polyethylene glycol as a polymer material can perform a good modification effect on the plastic viscosity of 3D printing cement paste; the thickening and retarding of the cement-based material are well regulated, so that the rheological and hydration coagulation performances of the slurry are improved, and in addition, when the polyethylene glycol and the glycerol are simultaneously used as liquid additives, the setting time can be prolonged.
Test example 2
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 8 parts of polyethylene glycol, 15 parts of glycerol, 14 parts of a water reducing agent, 14 parts of starch and 7 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 mu m. Through tests, the results are shown in tables 1 and 2, and it can be seen that when no graphene is added, the cement paste of the test example 2 has lower thixotropy, initial strength and other properties compared with the cement paste of the example 2, mainly because the graphene oxide adopted by the invention can regulate and control the yield stress of the 3D printing paste and improve the thixotropy, and meanwhile, the smaller particle size of the graphene oxide can obviously reduce the porosity and improve the mechanical properties; and when the graphene oxide and the quartz powder are added simultaneously, the printing performance of the cement paste can be obviously improved, the product strength is improved, and the thixotropy is improved.
Test example 3
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 9 parts of polyethylene glycol, 37 parts of graphene oxide, 18 parts of a water reducing agent, 19 parts of starch and 8 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns. Test example 3 is mainly to verify the influence of glycerol on the performance of the viscosity modifier of the invention, and the results are shown in tables 1 and 2, as the comparison of test example 3, the initial setting time and the continuous printing time of example 3 are both greatly improved, and after analysis, the reason that glycerol has a large amount of alcoholic hydroxyl groups can influence the setting performance of the sulphoaluminate cement slurry, and further the setting time and the continuous printing performance of the sulphoaluminate cement slurry can be regulated and controlled is mainly found.
Test example 4
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 5 parts of polyethylene glycol, 20 parts of graphene oxide, 20 parts of glycerol, 10 parts of starch and 5 parts of quartz powder, wherein the particle size of the quartz powder is 0.5-20 microns. The performance test results of the viscosity modifier obtained in test example 4 are shown in table 2, and it can be seen that, compared with the comparative test (example 4), the thixotropic property and the mechanical property are greatly reduced, mainly because the thickening type water reducing agent mainly comprising naphthalenesulfonic acid-formaldehyde condensate, triethylene glycol and glycerol is adopted in the invention, the water reducing agent can further improve and compensate the thixotropic property of 3D printing sulphoaluminate cement slurry, reduce the water consumption and improve the mechanical property of the cement.
Test example 5
A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials comprises the following components in parts by weight: 10 parts of polyethylene glycol, 28 parts of graphene oxide, 10 parts of glycerol, 10 parts of a water reducing agent and 5 parts of starch. In the initial experiment, the viscosity modifier is not added with quartz powder, and the performance of the viscosity modifier is shown in table 2 after testing, so that the obtained yield stress, deformation rate, printing performance, thixotropy and the like are all not ideal, particularly the deformation rate cannot meet the requirement of being controlled below 5 percent, and the printed slurry has deformation to a certain degree and has a local collapse phenomenon from the test result; after the quartz powder is added, the yield stress of the slurry is obviously improved by utilizing the advantage of high water absorption rate, the deformation rate is reduced, meanwhile, the porosity of the 3D printing slurry can be obviously reduced by the ultrafine quartz, the early mechanical property (shown in table 1, embodiment 5) is improved, and the printing property, the strength and the thixotropy of the cement slurry can be further improved when the graphene and the quartz powder are added simultaneously.
And (3) performance testing:
in order to verify the various performance criteria of the viscosity modifiers proposed by the present invention, the viscosity modifiers prepared in test examples 1-5 and examples 1-7 were tested by the present invention. The test method adopted by the invention comprises the following steps: compressive and flexural strength was measured using a U.S. MTS Universal tester. Rheological properties (plastic viscosity, yield stress, thixotropic ring area) were measured using a marvensitexus lab + rotational rheometer in the uk.
The results of examples 1-7 are shown in Table 1, after testing.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Plastic viscosity/pas | 2.42 | 3.44 | 2.61 | 2.57 | 3.39 | 2.47 | 2.52 |
| Yield stress/Pa | 588 | 601 | 641 | 633 | 629 | 596 | 617 |
| Percent deformation rate/%) | 4.21 | 3.88 | 3.21 | 4.16 | 3.37 | 4.08 | 3.74 |
| Thixotropic Ring area/Pa/s | 5864 | 5731 | 5942 | 6018 | 5807 | 5729 | 5901 |
| Initial setting time/min | 58 | 69 | 71 | 63 | 67 | 73 | 64 |
| Continuous printing time/min | 31 | 41 | 45 | 39 | 42 | 34 | 36 |
| Compressive strength/MPa (3d) | 38.5 | 40.2 | 41.7 | 39.4 | 43.8 | 40.6 | 44.1 |
| Flexural strength/MPa (3d) | 3.9 | 4.3 | 4.5 | 3.8 | 4.4 | 4.1 | 4.8 |
The results of tests conducted in test examples 1 to 5 are shown in Table 2.
| Test examples | Test example 1 | Test example 2 | Test example 3 | Test example 4 | Test example 5 |
| Plastic viscosity/pas | 1.13 | 3.18 | 3.05 | 2.94 | 2.83 |
| Yield stress/Pa | 561 | 584 | 626 | 605 | 328 |
| Percent deformation rate/%) | 5.18 | 3.09 | 3.98 | 5.05 | 8.46 |
| Thixotropic Ring area/Pa/s | 5919 | 2327 | 5766 | 2196 | 2213 |
| Initial setting time/min | 35 | 67 | 39 | 57 | 64 |
| Continuous printing time/min | 23 | 43 | 29 | 41 | 19 |
| Compressive strength/MPa (3d) | 36.4 | 22.6 | 38.1 | 19.5 | 18.2 |
| Flexural strength/MPa (3d) | 4.1 | 2.7 | 4.4 | 2.1 | 2.6 |
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (6)
1. A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials is characterized in that: the viscosity modifier comprises the following components in parts by weight: 5-10 parts of polyethylene glycol, 20-40 parts of graphene oxide, 10-20 parts of glycerol, 10-20 parts of a water reducing agent, 5-20 parts of starch and 5-10 parts of quartz powder;
the molecular weight of the polyethylene glycol is 1300-1600, and the specific surface area of the graphene oxide is 355m2The water solubility of the glycerol is 550g/L, the viscosity of the glycerol is 200 mPa.s, the water reducing agent is a naphthalene water reducing agent, the main components of the water reducing agent are a naphthalene sulfonic acid formaldehyde condensation compound, triethylene glycol and glycerol, and the particle size of the quartz powder is 0.5-20 microns.
2. A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials according to claim 1 wherein: the viscosity modifier comprises the following components in parts by weight: 5-8 parts of polyethylene glycol, 22-28 parts of graphene oxide, 11-15 parts of glycerol, 10-14 parts of a water reducing agent, 5-12 parts of starch and 5-7 parts of quartz powder.
3. A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials according to claim 1 wherein: the viscosity modifier comprises the following components in parts by weight: 6-8 parts of polyethylene glycol, 25-35 parts of graphene oxide, 14-18 parts of glycerol, 13-16 parts of a water reducing agent, 10-16 parts of starch and 6-8 parts of quartz powder.
4. A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials according to claim 1 wherein: the water reducing rate of the water reducing agent is 32%.
5. A viscosity modifier suitable for 3D printing of sulphoaluminate cement-based materials according to claim 1 wherein: the starch is amylose, and the main component of the starch is glucose.
6. Use of a viscosity modifier suitable for 3D printing of a sulphoaluminate cement-based material according to any one of claims 1 to 5 in the field of building materials.
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| CN110078411B (en) * | 2019-05-06 | 2022-03-25 | 济南大学 | Coloring agent suitable for 3D printing white cement-based material and use method and application thereof |
| CN111517740B (en) * | 2020-05-09 | 2022-05-27 | 深圳大学 | Cement-based composite material for 3D printing and preparation method thereof |
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