CN110372296A - A kind of Self-curing cement base 3D printing material and preparation method thereof - Google Patents
A kind of Self-curing cement base 3D printing material and preparation method thereof Download PDFInfo
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- CN110372296A CN110372296A CN201910654729.3A CN201910654729A CN110372296A CN 110372296 A CN110372296 A CN 110372296A CN 201910654729 A CN201910654729 A CN 201910654729A CN 110372296 A CN110372296 A CN 110372296A
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Classifications
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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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- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/04—Portland 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
Abstract
The present invention provides a kind of Self-curing cement base 3D printing material, belongs to building material technical field.In terms of mass fraction, comprising: 600~800 parts of cement, 250~300 parts of microballon, 50~80 parts of mineral powder, 1000~1200 parts of fine aggregate, 250~300 parts of water, 12~20 parts of polycarboxylate water-reducer, 9~12 parts of workability regulator, 0.20~0.50 part of sodium gluconate, 4~18 parts of accelerator, 0.005~0.006 part of defoaming agent, 18~36 parts of thixotropic agent, 0.5~1 part of water-absorbing resin, 3~6 parts of sodium methyl silicate, 4~10 parts of fiber, 0.04~0.05 part of thickener.The present invention also provides the preparation methods of the 3D printing material.Self-curing cement base 3D printing material of the present invention is more soft, caking property is excellent, good flowing properties, transporting resistance is small, mechanical property is good, setting time is controllable, thixotropic property is obvious, differential settlement is small, discharging rear stability is high, it spontaneous can conserve, the discharging spray nozzle for being 5~60mm suitable for diameter, can large-scale popularization application.
Description
Technical field
The invention belongs to building material technical field, specially a kind of Self-curing cement base 3D printing material and its preparation side
Method.
Background technique
With society it is increasingly developed, the upsurge of 3D printing sweeps over, and 3D printing is in metal, plastics, rubber object
Matter has carried out successful application, and 3D printing building is also emerging rapidly.Building 3D printing is usually in Computerized three-dimensional software
Control under, based on profile technique according to preset route by concrete delamination spray squeeze accumulation molding.3D printing building with
The advantages that traditional architecture is compared, and is formed with no mold, and construction efficiency is high, and construction-time is short, and basic No Assets waste, meets and works as
The building demand of preceding environmentally protective novel building style and economizing type, is one of the development trend of future architecture industry.
But for metal and plastic or other material, cement-based material has condition of molding complicated, and control difficulty is big, mechanics
The disadvantages such as property development is slow and tensile strength is low do not have good operability, so that cement-based material 3D printing is in reality
It is limited in the application of border.Filling mold forming is poured different from conventional concrete, this requires cement base printed material to have fairly good glue
Poly- property, extrudability, stability and reasonable setting time.
Extrudability can guarantee printed material squeeze out print procedure in have good mobility, do not occur plugging,
Phenomena such as fracture；Preferable cohesiveness can guarantee that type-script Coating combination is secured, promote globality；Good stability can
So that type-script keeps good overall stability, it can continue to stack, will not collapse easily；And suitable setting time can
During type-script height increase, strong support is provided for the self weight of subsequent printed material, is to guarantee that print procedure is high
Effect property and continuity essential condition.Further, since print component is almost one-pass molding, and large specific surface area, and it is straight
It connects and is exposed in air, moisture loss is serious, phenomena such as be easy to causeing shrinkage cracking, jeopardizes safety and the durability of type-script
Energy.
Summary of the invention
The purpose of the present invention is to provide a kind of Self-curing cement base 3D printing material and preparation method thereof, autotrophys of the present invention
Protect that cement base 3D printing material is more soft, caking property is excellent, good flowing properties, transporting resistance is small, mechanical property is good, condensation when
Between it is controllable, thixotropic property is obvious, differential settlement is small, discharging rear stability is high, spontaneous can conserve, being suitable for diameter is 5~60mm
Discharging spray nozzle, can large-scale popularization application.
The object of the invention is achieved through the following technical solutions:
A kind of Self-curing cement base 3D printing material, in terms of mass fraction, comprising: 600~800 parts of cement, microballon 250~
300 parts, 50~80 parts of mineral powder, 1000~1200 parts of fine aggregate, 250~300 parts of water, 12~20 parts of polycarboxylate water-reducer, and
Easy 9~12 parts of regulator of property, 0.20~0.50 part of sodium gluconate, 4~18 parts of accelerator, 0.005~0.006 part of defoaming agent,
18~36 parts of thixotropic agent, 0.5~1 part of water-absorbing resin, 3~6 parts of sodium methyl silicate, 4~10 parts of fiber, thickener 0.04~0.05
Part.
Further, the cement is portland cement or ordinary portland cement, preferably 42.5 normal silicate of P.O
Cement, performance meet " common portland cement " GB 175-2007 requirement；The microballon is that superfined flyash alumino-silicate is fine
Microballon, performance meet " flyash for cement and concrete " GB/T 1596-2017 requirement；The mineral powder be 600~
The limestone micropowder of 800 mesh.
Further, the fiber is the composite fibre of inorfil flexible, organic fiber or both；The fiber it is straight
Diameter is not more than 0.5mm, and the length range of single fiber is 5~25mm.
Further, the inorfil is basalt fibre, glass fibre, asbestos fibre, boron fibre, ceramic fibre, carbon
One or more of fiber, the organic fiber are polyethylene fibre, polypropylene fibre, polyacrylonitrile fibre, polyvinyl alcohol
The one or more of fiber, polyester fiber, cellulose fibre, lignin fibre.
Further, the fine aggregate is the Machine-made Sand of natural sand or particle shape almost spherical, the fineness modulus of the fine aggregate
It is 1.0~1.4, nominal maximum aggregate size is not more than 0.60mm, and 0.15~0.30mm sections of granule contents are no less than 40%, and clay content is small
In 1.0%.
Further, the polycarboxylate water-reducer be TPEG type mother liquor, solid content be 40~50%, water-reducing rate be 25~
30%；The workability regulator is VPEG type mother liquor, and solid content is 30~40%.
Further, the sodium gluconate is white powder；The defoaming agent be emulsion type defoaming agent, pH value be 7~
8；The solid content of the sodium methyl silicate is not less than 30%；The thickener is cellulose thickener, preferably hydroxylmethyl cellulose
Element, hydroxyethyl cellulose, hydroxypropyl methyl cellulose one or more.
Further, the water-absorbing resin is a kind of new functional macromolecule material with a large amount of hydrophilic radicals, has height
Absorbent function, water absorbent rate are greater than 100ml/g, preferably graft acrylamide class, starch grafted acrylate class, sulfonated starch base
Grafted propylene acids, dimethyl diallyl ammonium chloride class, cross-linked carboxymethyl cellulose graft acrylamide class, cross-linking type hydroxyl second
Base cellulose graft acrylamide polymer class, the one or more of high substituted degree cross-linked carboxymethyl cellulose class.
Further, the thixotropic agent is that its consistency can be reduced when printed material is sheared, and it is thick to increase its when static again
Degree maintains its globality stability after being conducive to printed material discharging, is aluminium-magnesium silicate, zeolite powder, bentonitic one kind or several
Kind.
A kind of preparation method of Self-curing cement base 3D printing material, comprising the following steps:
1) additive is deployed: successively by polycarboxylate water-reducer, workability regulator, accelerator, sodium gluconate, defoaming agent
And thickener is added to the mixer mixed at high speed；
2) raw material mixes: after carrying out profit pot to blender inner wall with match ratio cement mortar with volume, successively by fine aggregate, water
Mud, microballon, mineral powder, fiber, thixotropic agent, which are put into, dry in blender to be stirred to obtain mixture；
3) mixing water is weighed, 40~60% that mixing water is added are stirred into blender, additional by what is deployed in step 1)
Agent, water-absorbing resin, sodium methyl silicate and remaining mixing water are added in mixture together, and stirring forms Self-curing cement base 3D
Printed material.
Further, in step 1), the mixed at high speed time is 30~50s, and temperature is 20 ± 2 DEG C；
Further, in step 2), it is described it is dry stir the time be 60~90s；
Further, in step 3), the mixing time into blender of the 40~60% of the addition mixing water is 40~60s,
The time that stirring forms Self-curing cement base 3D printing material is 90s~120s.
Fine aggregate in Self-curing cement base 3D printing material of the present invention is natural sand or the preferable Machine-made Sand of particle shape, can be mentioned
Mobility is risen, reduces transporting resistance, and natural sand elasticity modulus is high, is conducive to the volume stability of type-script；Agstone
Its adhesive property and consistency can be improved, there is certain thixotropic transformation, be able to ascend its stability；Microballon is a kind of fine
Change flyash, particle shape is preferable, has " ball effect ", on the one hand can increase mobility with diminishing, reduce transporting resistance, another
Aspect can promote its caking property, improve type-script layer stability energy；Water-absorbing resin is specifically a kind of to have a large amount of hydrophilic radicals
New functional macromolecule material, have the function of high water absorption, can concrete stir when absorb and store moisture, printing material
Slow release moisture again after material condensation hardening, provides internal curing water for type-script, further promotion type-script degree of hydration, changes
The generation of kind type-script contraction fissure；Sodium methyl silicate has excellent penetrant crystalline performance, the silanol group in molecular structure
Dehydrated crosslinking can be reacted with the silanol group in silicate material, realize that " anti-capillary effect " formation is excellent in printed material and hate
Water layer significantly reduces the evaporation of printed material surface moisture, type-script internal moisture is prevented to scatter and disappear outward, reduces type-script and receives
Contract the risk to crack.
In additive in Self-curing cement base 3D printing material of the present invention, printed material is greatly reduced in polycarboxylate water-reducer
Water consumption promotes its mechanical property, to guarantee the intensity of type-script；Thickener is able to ascend the caking property of printed material and whole
Body maintains type-script stability；Workability regulator uses VPEG type, can effectively promote high water reduction type polycarboxylate water-reducer
Effect, and make printed material soft, improve concrete workability, promote flowing of the printed material in conveyance conduit
Property；Accelerator adjusts the hydration reaction of cement by the volume of regulation accelerator, when regulating and controlling the condensation of cement base 3D printing material
Between, effectively promote printing effect；Sodium gluconate is capable of the setting time of appropriate delay gelatinizing material, and sodium gluconate is added can
Cooperate the setting time of accelerator regulation printed material；Defoaming agent is in order to eliminate printed material air entrapment, so that type-script
It is more closely knit, be conducive to improve type-script and stability.
The thixotropic agent being added in Self-curing cement base 3D printing material of the present invention, is on the one hand able to ascend type-script in pipeline
In mobility, the stability after being on the other hand able to ascend discharging ensures type-script not unstable failure, being conducive to type-script can
Lasting printing increases；Thickener by have hydroxyl macromolecular chain, by the winding of molecule interchain, or in cement slurry
Moisture strong aquation occurs, increase the viscosity of cement slurry, thus promoted type-script interlayer adhesive property and
Increase the overall stability of type-script；Fiber tensile strength with higher and elasticity modulus replace in reinforcing bar in printed material
Play a part of enhancing muscle, promotes the toughness and anti-folding and anti-pressing ability of printed material, the generation of effective control critical eigenvalue.
Compared with prior art, the invention has the following advantages:
Self-curing cement base 3D printing material of the present invention is more soft, caking property is excellent, good flowing properties, transporting resistance
It is small, mechanical property is good, setting time it is controllable (initial set be 10~60min, final set be 20~120min), thixotropic property it is obvious, heavy
Drop difference is small, discharging rear stability is high, spontaneous can conserve, the discharging spray nozzle for being 5~60mm suitable for diameter.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The various raw materials of precise, weighing error are not more than 1% to embodiment according to the ratio, and each raw material component can be from the market
Purchase obtains.
In following embodiment, used raw material and source are as follows:
Cement is middle ordinary portland cement P.O 42.5；
Microballon selects the microballon of Henan Hebi production；
Mineral powder selects 600 mesh limestone micropowder of Lingshou；
Thickener selects the hydroxypropyl methyl cellulose ether of Hebei Yan Xing Chemical Co., Ltd. production, density 0.45g/cm3。
The aluminium-magnesium silicate that thixotropic agent selects Guangzhou Jia Liang mineral products Co., Ltd to produce, dioxide-containing silica 60%, carefully
Degree is 400 mesh.
Fine aggregate selects Leshan hongda natural sand, and partial size is not more than 0.6mm, fineness modulus 1.2, and clay content is not more than 1%；
The polycarboxylate water-reducer and workability regulator that additive is selected are built construction of the West Region new material science and technology and are had in being respectively
The ZJ-1001 and ZJ-3001 of limit company production, solid content are respectively 50% and 40%, and the defoaming agent of selection is BASF defoaming
Agent；
Fiber selects the basalt fibre of Jiangsu Condar husband's new material Science and Technology Ltd. production, diameter 0.1mm, single fibre
The length 20mm of dimension；
Sodium gluconate is the sodium gluconate that the purity of Wujiang perseverance up to Fine Chemical Co., Ltd's production is greater than 98%；
Water-absorbing resin selects the SAP hydroscopic high-molecular resin of Renqiu Hui Xiang Chemical Co., Ltd. production, active constituent content
Greater than 30%；
Sodium methyl silicate selects Nanchang City's high official position to set a song to music the sodium methyl silicate of extra large rhythm building materials anti-water factory production, and solid content is
31 ± 1%, pH value is greater than 13；
The Self-curing cement base 3D printing material of embodiment 1~15, raw material proportioning are shown in Table 1,
Raw material component proportion (kg/m in 1 embodiment of table, 1~15 Self-curing cement base 3D printing material3)
The Self-curing cement base 3D printing material of embodiment 1~15, the preparation method is as follows:
1) it deploys additive: weighing polycarboxylate water-reducer, workability regulator, sodium gluconate, accelerator, defoaming agent,
Thickener sequentially adds polycarboxylate water-reducer, workability regulator, accelerator, sodium gluconate, defoaming agent and thickener and arrives
In YLT -100A high-speed mixer, 30~50s of mixed at high speed under the conditions of 20 ± 2 DEG C.
2) raw material mixes: weighing cement, microballon, mineral powder, fine aggregate, thixotropic agent, fiber, with volume with match ratio cement bonded sand
After slurry carries out profit pot to blender inner wall, fine aggregate, cement, microballon, mineral powder, fiber, thixotropic agent are successively put into blender
In dry stir 60~90s；
3) weighed mixing water, water-absorbing resin, sodium methyl silicate, and be added the 40~60% of mixing water and stirred into blender
After mixing 40~60s, additional agent solution, water-absorbing resin, sodium methyl silicate and the remaining mixing water deployed in step 1) add together
Enter into mixture, stirring 90s~120s forms Self-curing cement base 3D printing material.
The cement base 3D printing material property testing result (20~25 DEG C of environment temperature) of 2 embodiment of table 1~15
From table 2 it can be seen that Self-curing cement base 3D printing strength of materials grade of the present invention is in C60 or more, mechanical property
Good, setting time, controllably (initial set was 10~60min, and final set is 20~120min), thixotropic property is obvious, differential settlement is small, discharging
Rear stability is high, can reduce water evaporation rate, realizes spontaneous maintenance, the discharging spray nozzle for being 5~60mm suitable for diameter.
Comparative example 6 and 7, it can be seen that it vibrates divergence less than embodiment 7 after embodiment 6 mixes thixotropic agent, and
And mix the printed material vibration divergence after thixotropic agent and all maintain between 160~170mm, it can be seen that thixotropic agent can increase
Big static rear viscosity, improves overall stability；Embodiment 5 does not add water-absorbing resin and sodium methyl silicate, moisture loss rate compared with
Greatly, and later strength is also low compared with other embodiments, it can be seen that, other are mixed with the component of water-absorbing resin and sodium methyl silicate
Moisture can be preferably kept, water evaporation rate is reduced, the later period has good spontaneous maintenance, promotes concrete 28d intensity；Initial set
Time is from effective embodiment 2~4,6,8,9~15 as can be seen that the presetting period is 10~55min, substantially it can be assumed that 10
Adjustable in~60min, similarly, final setting time can also be assert adjustable in 20~120min；Comparative example 1 and 2, embodiment 1
Non- adding of fiber, bending and compressive strength are more similar low, it can be seen that, the incorporation of fiber, which has, is substantially improved its mechanical property
Effect.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of Self-curing cement base 3D printing material, which is characterized in that in terms of mass fraction, comprising: 600~800 parts of cement,
250~300 parts of microballon, 50~80 parts of mineral powder, 1000~1200 parts of fine aggregate, 250~300 parts of water, polycarboxylate water-reducer 12
~20 parts, 9~12 parts of workability regulator, 0.20~0.50 part of sodium gluconate, 4~18 parts of accelerator, defoaming agent 0.005~
0.006 part, 18~36 parts of thixotropic agent, 0.5~1 part of water-absorbing resin, 3~6 parts of sodium methyl silicate, 4~10 parts of fiber, thickener
0.04~0.05 part.
2. a kind of Self-curing cement base 3D printing material as described in claim 1, which is characterized in that the cement is common silicic acid
Salt cement or portland cement, performance meet " common portland cement " GB 175-2007 requirement；The microballon is ultra-fine fine coal
The grey fine microballon of alumino-silicate, performance meet " flyash for cement and concrete " GB/T 1596-2017 requirement；It is described
Mineral powder is the limestone micropowder of 600~800 mesh.
3. a kind of Self-curing cement base 3D printing material as described in claim 1, which is characterized in that the fiber is nothing flexible
The composite fibre of machine fiber, organic fiber or both；The diameter of the fiber is not more than 0.5mm, the length range of single fiber
For 5~25mm.
4. a kind of Self-curing cement base 3D printing material as claimed in claim 3, which is characterized in that the inorfil is the Black Warrior
One or more of rock fiber, glass fibre, asbestos fibre, boron fibre, ceramic fibre, carbon fiber, the organic fiber are
Polyethylene fibre, polypropylene fibre, polyacrylonitrile fibre, vinal, polyester fiber, cellulose fibre, lignin are fine
The one or more of dimension.
5. a kind of Self-curing cement base 3D printing material as described in claim 1, which is characterized in that the fine aggregate is natural sand
Or the Machine-made Sand of particle shape almost spherical, the fineness modulus of the fine aggregate are 1.0~1.4, nominal maximum aggregate size is not more than
0.60mm, 0.15~0.30mm a section granule content are no less than 40%, and clay content is less than 1.0%.
6. a kind of Self-curing cement base 3D printing material as described in claim 1, which is characterized in that the polycarboxylate water-reducer is
TPEG type mother liquor, solid content are 40~50%, and water-reducing rate is 25~30%；The workability regulator is that VPEG type is female
Liquid, solid content are 30~40%.
7. a kind of Self-curing cement base 3D printing material as described in claim 1, which is characterized in that the sodium gluconate is white
Color is powdered；The defoaming agent is emulsion type defoaming agent, and pH value is 7~8；The solid content of the sodium methyl silicate is not less than
30%；The thickener is cellulose thickener, preferably hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl fiber
The one or more of element.
8. a kind of Self-curing cement base 3D printing material as described in claim 1, which is characterized in that the water-absorbing resin is grafting
Acrylic amide, starch grafted acrylate class, sulfonated starch base grafted propylene acids, dimethyl diallyl ammonium chloride class,
Cross-linked carboxymethyl cellulose graft acrylamide class, cross-linking type hydroxyethyl cellulose graft acrylamide polymerization species, high substitution
Spend the one or more of cross-linked carboxymethyl cellulose class.
9. a kind of Self-curing cement base 3D printing material as described in claim 1, which is characterized in that the thixotropic agent is magnesium silicate
Aluminium, zeolite powder, bentonitic one or more.
10. a kind of preparation method of Self-curing cement base 3D printing material, feature exist as described in any one of claim 1 to 9
In, comprising the following steps:
1) additive is deployed: successively by polycarboxylate water-reducer, workability regulator, accelerator, sodium gluconate, defoaming agent and increasing
Thick dose is added to the mixer mixed at high speed；
2) raw material mix: after carrying out profit pot to blender inner wall with match ratio cement mortar with volume, successively by fine aggregate, cement,
Microballon, mineral powder, fiber, thixotropic agent, which are put into, dry in blender to be stirred to obtain mixture；
3) mixing water is weighed, 40~60% that mixing water is added are stirred into blender, by the additive deployed in step 1), are inhaled
Water-resin, sodium methyl silicate and remaining mixing water are added in mixture together, and stirring forms Self-curing cement base 3D printing
Material.
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| CN111517715A (en) * | 2020-04-15 | 2020-08-11 | 济南大学 | 3D printing thermal insulation mortar and preparation method and application thereof |
| CN111517740A (en) * | 2020-05-09 | 2020-08-11 | 深圳大学 | Cement-based composite material for 3D printing and preparation method thereof |
| CN111517740B (en) * | 2020-05-09 | 2022-05-27 | 深圳大学 | Cement-based composite material for 3D printing and preparation method thereof |
| CN114790090A (en) * | 2021-01-25 | 2022-07-26 | 重庆大学 | Curing agent for 3D printing concrete and preparation method thereof |
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| CN115057702A (en) * | 2022-06-22 | 2022-09-16 | 山东海之德新材料有限公司 | Zirconia powder molding material for additive manufacturing and preparation method and construction process thereof |
| CN115057702B (en) * | 2022-06-22 | 2023-09-01 | 山东海之德新材料有限公司 | Zirconia powder molding material for additive manufacturing and preparation method and construction process thereof |
| CN117534419A (en) * | 2023-12-29 | 2024-02-09 | 内蒙古众合增材制造科技有限公司 | 3D printing concrete, 3D printing high-mixing-amount fly ash mortar and application thereof |
| CN117534419B (en) * | 2023-12-29 | 2024-03-12 | 内蒙古众合增材制造科技有限公司 | 3D printing concrete, 3D printing high-mixing-amount fly ash mortar and application thereof |
| CN117510161A (en) * | 2024-01-04 | 2024-02-06 | 河北盛卓建筑设备制造有限公司 | 3D printing mortar capable of preventing cracks and preparation method thereof |
| CN117510161B (en) * | 2024-01-04 | 2024-03-22 | 河北盛卓建筑设备制造有限公司 | 3D printing mortar capable of preventing cracks and preparation method thereof |
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Application publication date: 20191025 |