CN108275924A - Fly ash-based geopolymer capable of being printed in 3D mode and preparation and use methods thereof - Google Patents
Fly ash-based geopolymer capable of being printed in 3D mode and preparation and use methods thereof Download PDFInfo
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- CN108275924A CN108275924A CN201810102082.9A CN201810102082A CN108275924A CN 108275924 A CN108275924 A CN 108275924A CN 201810102082 A CN201810102082 A CN 201810102082A CN 108275924 A CN108275924 A CN 108275924A
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- printing
- flyash
- sodium
- base polymers
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Classifications
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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
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention relates to a fly ash-based geopolymer capable of 3D printing and preparation and use methods thereof. The geopolymer is prepared from the following components in parts by weight: 0.4 to 0.6 part of fly ash, 0.275 to 0.5 part of metakaolin, 0.05 to 0.1 part of gypsum powder, 0.05 to 0.175 part of blast furnace slag powder, 1 to 1.5 parts of machine-made sand, 0.01 to 0.03 part of viscosity modifier, 0.4 to 0.6 part of compound alkali activator, 0.05 to 0.125 part of water, 0.0075 to 0.03 part of basalt fiber with the length of 6 to 18mm and 0.01 to 0.03 part of sodium bentonite, wherein the average particle size of the machine-made sand is 125 to 430 microns. The geopolymer takes the fly ash as a main raw material, so that the use amount of cement can be effectively reduced, and the problems of land occupation and environment pollution caused by storage of the fly ash also can be solved.
Description
Technical field
The present invention relates to concrete material technical field, in particular to it is a kind of can 3D printing flyash base it is poly-
Object and its preparation, application method.
Background technology
3D printing technique obtained significant development, 3D printing bridge, 3D printing house etc. in civil construction field in recent years
Example it is commonly reported that, these largely confirm the feasibility that 3D printing technique is applied to civil construction field.3D
Design liberalization that printing concrete technology also has by it, build flexibility, speed of application is fast, cost of labor is low, automation
Many advantages, such as degree is high, environmental pollution is small and receive extensive attention and promote.
So far, 3D printing concrete technology mainly uses cement-based material, and such as application No. is 201510225639.4
Chinese patent a kind of 3D printing cement-based material and preparation method thereof is disclosed, application No. is 201610681060.3 China specially
Profit discloses a kind of Carbon Fiber Reinforced Cement Composites for 3D printing technique.However 1 ton of cement is often produced, discharge dioxy
Change about 1 ton of carbon, 0.74 kilogram of sulfur dioxide, 30 kilograms of dust causes serious air environmental pollution and soil vegetative cover to destroy, directly
Connect influence ecological environment.Currently, people just actively develop research and development it is various it is energy saving, section materials, comprehensive utilization resource and with life
State environment harmonious coexistence and be conducive to human health function admirable green new material.3D printing technique it is fast-developing also from
A kind of replacement material of the cement with higher force intensity and satisfaction construction requirement is sought in the innovation for not opening high performance building materials
Material has a very important significance to prepare 3D printing building structure.
Ground polymers be one kind using clay, flyash, industrial residue as primary raw material, through appropriate process in alkali-activated carbonatite
Green glue similar in the functions such as one kind and cement, the ceramics that polymerisation is formed occurs under the conditions of (sodium hydroxide, waterglass etc.)
Gel material.Ground polymers generally use mineral waste as raw material, not only will not generation environment pollution, moreover it is possible to solve flyash etc.
The storage of mineral waste, process problem, belong to environmentally friendly material.It also has intensity height, high temperature resistant, acid and alkali-resistance and durable
The good advantage of property, is the favorable substitutes of cement.
Flyash is a kind of mineral waste, and in China, yield is big, storage is difficult, utilization rate is low, the main component of flyash
Including SiO2、Al2O3, CaO etc., can be used for preparing ground polymers.Application No. is the Chinese patents of 201410856420.X to disclose one
Kind flyash base polymers concrete material and preparation method thereof, although selecting using flyash as primary raw material, in the material
Still part of cement is used, and material cannot carry out 3D printing.Therefore there is no using flyash be main raw material(s) preparation can 3D beat
The relevant report of the ground polymers of print.In consideration of it, the invention discloses it is a kind of can 3D printing flyash base polymers and its preparation,
Application method.
Invention content
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve be to provide it is a kind of can 3D printing flyash
Base polymers and its preparation, application method.The ground polymers can not only effectively reduce cement consumption by primary raw material of flyash,
It can also solve flyash and store land occupation, the problem of environmental pollution brought.Ground polymers printing performance height, the setting rate
Soon, caking property is good, intensity is high, and the open hour are adjustable, has good future in engineering applications.The preparation method is swollen by sodium base first
3 profit soil, other powders and basalt fibre point input blenders, are then added composite exciting agent and viscosity modifier, in this way
The dispersibility of basalt fibre and sodium bentonite can be improved, be conducive to the smooth extrusion of prepared ground polymer material.In user
Ground polymers in the parameters that method limits prepared by printing, it is ensured that the smooth and 3D printing of print procedure ground polymers
The stability of structure.
The present invention solve the technical problem the technical solution adopted is that：
It is a kind of can 3D printing flyash base polymers, count in parts by weight, the composition and content of ground polymers are respectively：
0.4~0.6 part of flyash；
0.275~0.5 part of metakaolin；
0.05~0.1 part of land plaster；
0.05~0.175 part of ground granulated blast furnace slag；
The average grain diameter of 1~1.5 part of Machine-made Sand, the Machine-made Sand is 125~430 μm；
0.01~0.03 part of viscosity modifier；
0.4~0.6 part of compound alkali-activator；
0.05~0.125 part of water；
Length is 0.0075~0.03 part of the basalt fibre of 6~18mm；
0.01~0.03 part of sodium bentonite (thixotropic agent).
It is above-mentioned can 3D printing flyash base polymers, the compound alkali-activator is by sodium silicate solution and sodium hydroxide
Solution composition.
It is a kind of it is above-mentioned can 3D printing flyash base polymers preparation method, which includes the following steps：
(1) count in parts by weight, above-mentioned raw materials be divided into three groups, first group be 0.4~0.6 part of flyash, 0.275~
0.5 part of metakaolin, 0.05~0.1 part of land plaster, 0.05~0.175 part of ground granulated blast furnace slag, 1~1.5 part of Machine-made Sand and
0.0075~0.03 part of basalt fibre, 0.01~0.03 part of sodium bentonite；Second group is 0.0359~0.0675 part of hydrogen-oxygen
Change sodium solid, 0.077~0.191 part of distilled water, 0.23~0.429 part of sodium silicate solution；Third group is 0.01~0.03 part viscous
Spend modifying agent and 0.05~0.125 part of water；
(2) all raw materials in first group in addition to sodium bentonite and basalt fibre are sent into planetary mortar mixer
In, after stirring, then sodium bentonite is gradually added into blender, continues stirring to being uniformly mixed, finally slowly
Be added basalt fibre, continue stirring until material be uniformly mixed, obtain mixed dry material；
(3) 0.0359~0.0675 part of sodium hydroxide powder in second group is dissolved in 0.077~0.191 part of distilled water and is filled
Sodium hydroxide solution is obtained after dividing mixing；Then use water-bath cooling to room temperature, finally by 0.23~0.429 part of sodium silicate solution
It is added in the sodium hydroxide solution of above-mentioned preparation and mixes, be prepared compound alkali-activator, and for use, storage after storing 24 hours
It is 25 ± 2 DEG C to deposit temperature；
(4) 0.05~0.125 part of water is weighed, and is slowly added into 0.01~0.03 part of viscosity modifier, it is stirring while adding, directly
To formation stable colloid；
(5) compound alkali-activator prepared by step (3) is added to the mixed dry material that step (2) obtains when field print
In, continue stirring until being uniformly mixed after being sufficiently stirred, after colloid prepared by step (4) is added, is described after stirring
Can 3D printing flyash base polymers.
It is a kind of it is above-mentioned can 3D printing flyash base polymers application method, the process of the application method is：By ground
Polymers pumps or machinery is delivered in the printing head of 3D printer, and the time for terminating the printing to since stirring is no more than 5 points
Clock, setting printing head cross sectional shape are circle, and bore is 10~20mm, and extruded velocity is 0.5~1.0m3/ h, plane is interior to beat
Print-out rate is 180~210m/h.
Compared with existing 3D printing concrete material, the beneficial effects of the invention are as follows：
1) preparation method of the present invention it is prepared can 3D printing flyash base polymers can with printer coordinate it is compatible, can
Ensure that material is continuously extruded, does not interrupt in print procedure, stable structure in banking process, without moderate finite deformation (see Fig. 1~figure
2)。
2) flyash base polymers itself does not have a printability, the present invention using sodium bentonite as thixotropic agent, this
Kind thixotropic agent can keep activity in the high alkali environment of alkali-activator, improve solubility property, flyash base polymers is made to have
Good water-retaining property and thixotropy, prepared flyash base polymers have good printability；The water conservation of metakaolin
Property and activity compared with flyash height, grain size is small compared with flyash, and a small amount of metakaolin, which has, improves the ground intensity of polymers, water conservation, excellent
Change the effect of size grading；Slag powders activity is taller compared with metakaolin, and suitable slag powders can accelerate polymerisation, promotes
The growth of early strength, this is conducive to the constructability for improving ground polymers；The present invention uses activity of the land plaster as flyash
Exciting agent is conducive to the intensity after the activity for improving flyash and the hardening of ground polymers；The present invention using polymer dispersion powder as
Viscosity modifier, such viscosity modifier, which is added, can improve the caking property of material；On the one hand the addition of basalt fibre can carry
The fracture toughness of concrete, on the other hand can improve the constructability of material after height hardening.The mutual cooperation of multiple material is made
With making flyash base polymers show good 3D printabilities, 3D printing can be used for.
3) present invention can open hour (time that can smoothly squeeze out) of flyash base polymers of 3D printing can root
It is adjusted within the scope of 30~60 minutes according to the speed of 3D printing.Within the scope of above-mentioned 0.05~0.175 part of ground granulated blast furnace slag,
The present invention need to only adjust the volume i.e. open hour of adjustable material of slag powders, and as volume increases, the open hour are by 60 points
Clock is reduced to 30 minutes.
4) sodium bentonite and basalt fibre are not easy to be uniformly dispersed in material of the invention composition, system using the present invention
When preparing mineral mixed dry material, all raw materials in first group in addition to sodium bentonite and basalt fibre are sent into for Preparation Method
In planetary mortar mixer, first it is mixed 2 minutes.Then sodium bentonite is gradually added into blender, continues stirring 2
Minute, it is finally slowly added into basalt fibre, continues to stir, total mixing time is not less than 8 minutes, it is ensured that sodium bentonite
It is evenly dispersed in siccative with basalt fibre, compound alkali-activator and viscosity modifier is then added, this can ensure institute
The ground polymers of preparation can pass through print head and be extruded, not interrupt.
5) it is of the invention can 3D printing flyash base polymers with flyash for main siulica-alumina mineral source, consumption is a large amount of
Industrial waste --- flyash, this can bring huge benefits of environment and economy.
Description of the drawings
Fig. 1 is that the flyash base polymers of embodiment 1 carries out the design sketch of extrudability evaluation test.
Fig. 2 is that the flyash base polymers of embodiment 1 carries out the design sketch of constructiveness evaluation test.
Fig. 3 be embodiment 1 flyash base polymers age up to 28 days when stress-displacement curve figure.
Specific implementation mode
The present invention is explained further with reference to embodiment and attached drawing, the embodiment recorded herein is the specific of the present invention
Specific implementation mode, the design for illustrating the present invention, is explanatory and illustrative, should not be construed as protecting the present invention
The limitation of range.
The present invention can 3D printing flyash base polymers, count in parts by weight, the composition and content of ground polymers are respectively：
0.4~0.6 part of flyash；
0.275~0.5 part of metakaolin；
0.05~0.175 part of ground granulated blast furnace slag；
0.05~0.1 part of land plaster；
The average grain diameter of 1.0~1.5 parts of Machine-made Sand, the Machine-made Sand is 125~430 μm；
0.01~0.03 part of viscosity modifier (polymer dispersion powder)
Composite exciting agent 0.4~0.6；
0.05~0.125 part of water；
Length is 0.0075~0.03 part of the basalt fibre of 6~18mm；
0.01~0.03 part of sodium bentonite (thixotropic agent).
The compound alkali-activator is made of sodium silicate solution and sodium hydroxide solution, by 0.0359~0.0675 part of hydrogen-oxygen
Change sodium solid powder be dissolved in be sufficiently mixed in 0.077~0.191 part of distilled water after obtain sodium hydroxide solution, sodium hydroxide solution
Concentration control in 25~33% ranges.Then water-bath cooling finally adds 0.23~0.429 part of sodium silicate solution to room temperature
Enter into the sodium hydroxide solution of above-mentioned preparation and mix, the modulus of prepared compound alkali-activator is controlled in 1.2~1.4 ranges
It is interior.
The modulus of the sodium silicate solution is preferably 3.2, and solid content is preferably 35%.
The loss on ignition of the flyash is 7.1%, moisture content 0.1%, calcium oxide content 3.7%, and water demand ratio is
104%, fineness is that 45 μm of square hole screens tail over 17.5%.
The density of the metakaolin is 2.65g/cm3, specific surface area is 26~28m2/ g, moisture content 0.9%.
The density of the ground granulated blast furnace slag is 2.8g/cm3, specific surface area is 350~500m2/ kg, moisture content 0.8%.
The land plaster is calcium sulphate dihydrate, and fineness is 100~300 mesh.
The Machine-made Sand is 277.5 μm of average grain diameter, specific surface area 0.125m2The quartz sand of/g；
The length of the basalt fibre be 6~18mm, tensile strength be 3300~4500MPa, elasticity modulus be 95~
115GPa, elongation at break are 2.4~3.0%.
It is handled using preceding coping mechanism sand, ensures that its particle size range is 125~430 μm, you can meeting production makes
With requiring.
It is a kind of it is above-mentioned can 3D printing flyash base polymers preparation method, which includes the following steps：
(1) count in parts by weight, above-mentioned raw materials be divided into three groups, first group be 0.4~0.6 part of flyash, 0.275~
0.5 part of metakaolin, 0.05~0.1 part of land plaster, 0.05~0.175 part of ground granulated blast furnace slag, 1~1.5 part of Machine-made Sand and
0.0075~0.03 part of basalt fibre, 0.01~0.03 part of sodium bentonite.Second group is 0.0359~0.0675 part of hydrogen-oxygen
Change sodium solid, 0.077~0.191 part of distilled water, 0.23~0.429 part of sodium silicate solution；Third group can for 0.01~0.03 part
Dispersed latex powder and 0.05~0.125 part of water.
(2) all raw materials in first group in addition to sodium bentonite, basalt fibre are sent into planetary mortar mixer
In, blender capacity is 30 liters, and rotating speed is 60 revs/min, is first mixed 2 minutes.Then sodium bentonite is gradually added into
In blender, continue stirring 2 minutes, be finally slowly added into basalt fibre, continue stirring until material be uniformly mixed, mixed
Close siccative, it is desirable that total mixing time is not less than 8 minutes.Each amount of agitation can be controlled according to print speed.
(3) 0.0359~0.0675 part of sodium hydroxide in second group is dissolved in 0.077~0.191 part of distilled water, fully
Sodium hydroxide solution is obtained after mixing, since sodium hydroxide can release a large amount of heat in course of dissolution, therefore uses water-bath cooling
To room temperature, sodium hydroxide solution and 0.23~0.429 part of sodium silicate solution are finally mixed with compound alkali-activator, and store
For use after 24 hours, storage temperature is 25 ± 2 DEG C；
(4) 0.05~0.125 part of water is weighed, and is slowly added into 0.01~0.03 part of polymer dispersion powder, it is stirring while adding,
Until forming stable colloid.
(5) compound alkali-activator prepared by step (3) is added to the mixed dry material that step (2) obtains when field print
In, continue stirring until uniformly mixed after stirring 2 minutes, after colloid prepared by step (4) is added, total mixing time is 5~6 points
Clock, be after stirring it is described can 3D printing flyash base polymers.
It is a kind of it is above-mentioned can 3D printing flyash base polymers application method, the process of the application method is：It will be above-mentioned
Ground polymers pumping or machinery are delivered in the printing head of 3D printer, and the time for terminating the printing to since stirring is no more than 5
Minute, setting printing head cross sectional shape is circle, and bore is 10~20mm, and extruded velocity is 0.5~1.0m3/ h, in plane
Print speed is 180~210m/h.
The ground polymers obtained according to formula provided by the present invention and preparation method is printed, to the structure after printing
Body carries out correlated performance test, i.e., extrudability evaluation, constructiveness evaluation, compression strength evaluation use coagulation of the present invention after tested
Soil can guarantee being smoothed out for print procedure under the premise of meeting proposed printing and requiring, and resulting structures are steady after printing
It is fixed.
Embodiment 1
The present embodiment can 3D printing flyash base polymers, count in parts by weight, the composition and content of ground polymers difference
For：
0.5 part of flyash；
0.375 part of metakaolin；
0.1 part of ground granulated blast furnace slag；
0.1 part of land plaster；
The average grain diameter of 1.25 parts of Machine-made Sand, the Machine-made Sand is 125~430 μm；
0.02 part of polymer dispersion powder；
0.4 part of composite exciting agent；
0.075 part of water；
Length is 0.0075 part of the basalt fibre of 18mm；
0.01 part of sodium bentonite (thixotropic agent).
The compound alkali-activator is made of sodium silicate solution and sodium hydroxide solution, by 0.045 part of sodium hydrate solid
Powder is dissolved in be sufficiently mixed in 0.092 part of distilled water after obtain sodium hydroxide solution, a concentration of the 33% of sodium hydroxide solution.So
0.263 part of sodium silicate solution is finally added in the sodium hydroxide solution of above-mentioned preparation and mixes to room temperature by water-bath cooling afterwards, institute
The modulus of the compound alkali-activator prepared is 1.2.The modulus of the sodium silicate solution is 3.2, solid content 35%.
The loss on ignition of the flyash is 7.1%, moisture content 0.1%, calcium oxide content 3.7%, and water demand ratio is
104%, fineness is that 45 μm of square hole screens tail over 17.5%.
The density of the metakaolin is 2.65g/cm3, specific surface area is 26~28m2/ g, moisture content 0.9%.
The density of the ground granulated blast furnace slag is 2.8g/cm3, specific surface area 350m2/ kg, moisture content 0.8%.
The land plaster is calcium sulphate dihydrate, and fineness is 200 mesh.
The Machine-made Sand is 277.5 μm of average grain diameter, specific surface area 0.125m2The mechanism quartz sand of/g；
The length of the basalt fibre be 18mm, tensile strength be 3300~4500MPa, elasticity modulus be 95~
115GPa, elongation at break are 2.4~3.0%；
The polymer dispersion powder is German watt gram 5044N types.
The present embodiment can the preparation method of flyash base polymers of 3D printing be：
(1) it counts in parts by weight, above-mentioned raw materials is divided into three groups, first group is 0.5 part of flyash, 0.375 part of higher ridge
Soil, 0.1 part of land plaster, 0.1 part of ground granulated blast furnace slag, 1.25 parts of Machine-made Sands and 0.0075 part of basalt fibre, 0.01 part of sodium base are swollen
Profit soil.Second group is 0.045 part of sodium hydrate solid, 0.092 part of distilled water, 0.263 part of sodium silicate solution；Third group is 0.02
Part polymer dispersion powder and 0.075 part of water.
(2) all raw materials in first group in addition to sodium bentonite, basalt fibre are sent into planetary mortar mixer
In, blender capacity is 30 liters, and rotating speed is 60 revs/min, is first mixed 2 minutes.Then sodium bentonite is gradually added into
In blender, continue stirring 2 minutes, be finally slowly added into basalt fibre, continues stirring until material is uniformly mixed, it is desirable that total
Mixing time is not less than 8 minutes.Each amount of agitation can be controlled according to print speed.
(3) 0.0045 part of sodium hydroxide in second group is dissolved in 0.092 part of distilled water, since sodium hydroxide was dissolving
Cheng Zhonghui releases a large amount of heat, therefore uses water-bath cooling to room temperature, finally by sodium hydroxide solution and 0.263 part of sodium silicate solution
It is mixed with compound alkali-activator, and for use after storing 24 hours, storage temperature is 25 ± 2 DEG C；
(4) 0.075 part of water is weighed, and is slowly added into 0.02 part of polymer dispersion powder, it is stirring while adding, stablize until being formed
Colloid.
(5) compound alkali-activator prepared by step (3) is added to the mixed dry material that step (2) obtains when field print
In, continue stirring until uniformly mixed after stirring 2 minutes, after colloid prepared by step (4) is added, total mixing time is 5~6 points
Clock, be after stirring it is described can 3D printing flyash base polymers.
Using the present embodiment can the flyash base polymers of 3D printing carry out 3D printing, detailed process is：By above-mentioned gather
Object pumps or machinery is delivered in the printing head of 3D printer, and slice and path planning are carried out in Slic3r Slice Softwares,
It is circle, bore 12mm, extruded velocity 0.6m that printing head cross sectional shape, which is arranged,3/ h, horizontal direction print speed are 190m/
H, thickness 6mm, then generates G code, and G code is poured into and controls printing in computer control software Repetier~Host
Machine prints.It is printed according to the above print parameters, obtains print structure body.Print procedure is well on, and prints knot
Globality, the stability of structure are preferable.
Ground polymers and the above-mentioned structure printed to the present embodiment carry out correlated performance test：
Extrudability evaluation：
It is extrudability to refer to that material printing head section from the ability that continuously squeezes out of setting nozzle, the present embodiment is circle
Shape, bore 12mm, extruded velocity 0.6m3/ h, horizontal print speed are 190m/h, the results showed that the material of this example can be held
Continuous ground continuously prints, and occurs without interrupting and blocking, as shown in Figure 1.
Constructiveness is evaluated：
Constructiveness characterization is that material has been stacked certain height without the ability caved in, and material is made vertically to accumulate
9 layers, carry out constructiveness evaluation.Printing head section is circle, bore 12mm, extruded velocity 0.6m in the present embodiment3/ h,
Horizontal print speed is 190m/h, and print structure is 4 row, this example vertically without interruption, nothing collapse by 9 layers of printing, per thick base layer by layer
This is consistent, and verticality is high, and printing precision is high.As shown in Fig. 2, illustrating that the present embodiment concrete shows excellent constructiveness and knot
Structure stability.
Open hour are evaluated：
Ground polymers occurs polymerisation under the action of compound alkali-activator and gradually hardens, with polymerisation into
Row, material starts to lose plasticity and the hardening that becomes.Open hour, which are materials, to be terminated from stirring to cannot continuously be squeezed by printer
The time gone out.In order to ensure that material is smoothly printed, it is necessary to which control completes file printing within the open hour.Through printing
The open hour of test, this example are 50min.
Compression strength is evaluated：
Reference《Standard for test methods of mechanical properties of ordinary concrete》(GB/T50081~2002) are to the present embodiment concrete
Carry out intensity test.Test result is：Stress~displacement curve is as shown in figure 3, compression strength is when age is 28 days
49MPa。
With can be seen that the present embodiment from above-mentioned test result Parameter Conditions of the polymers in the 3D printer of setting
Under, the extrusion that can not blocked continuously (squeezing out sex chromosome mosaicism, attached drawing 1), can vertical heap (built without caving in
Make sex chromosome mosaicism, attached drawing 2), and this structure of printing shaping has enough compression strength after the hardening.That is
The extrudability of the ground polymers, constructiveness, compression strength are preferable.
Embodiment 2
The present embodiment can 3D printing flyash base polymers, count in parts by weight, the composition and content of ground polymers difference
For：
0.45 part of flyash；
0.4 part of metakaolin；
0.05 part of ground granulated blast furnace slag；
The average grain diameter of 1.3 parts of Machine-made Sand, the Machine-made Sand is 125~430 μm；
0.1 part of land plaster；
0.01 part of polymer dispersion powder；
0.4 part of composite exciting agent；
0.1 part of water；
Length is 0.0075 part of the basalt fibre of 18mm；
0.01 part of sodium bentonite (thixotropic agent).
The compound alkali-activator is made of sodium silicate solution and sodium hydroxide solution, by 0.0359 part of sodium hydrate solid
Powder is dissolved in be sufficiently mixed in 0.108 part of distilled water after obtain sodium hydroxide solution, a concentration of the 25% of sodium hydroxide solution.So
0.256 part of sodium silicate solution is finally added in the sodium hydroxide solution of above-mentioned preparation and mixes to room temperature by water-bath cooling afterwards, institute
The modulus of the compound alkali-activator prepared is 1.4.The modulus of the sodium silicate solution is 3.2, solid content 35%.
The loss on ignition of the flyash is 7.1%, moisture content 0.1%, calcium oxide content 3.7%, and water demand ratio is
104%, fineness is that 45 μm of square hole screens tail over 17.5%.
The density of the metakaolin is 2.65g/cm3, specific surface area is 26~28m2/ g, moisture content 0.9%.
The density of the ground granulated blast furnace slag is 2.8g/cm3, specific surface area 350m2/ kg, moisture content 0.8%.
The land plaster is calcium sulphate dihydrate, and fineness is 200 mesh.
The Machine-made Sand is 277.5 μm of average grain diameter, specific surface area 0.125m2The mechanism quartz sand of/g；
The length of the basalt fibre be 18mm, tensile strength be 3300~4500MPa, elasticity modulus be 95~
115GPa, elongation at break are 2.4~3.0%；
The polymer dispersion powder is German watt gram 5044N types.
The present embodiment can the preparation method of flyash base polymers of 3D printing be：
(1) it counts in parts by weight, above-mentioned raw materials is divided into three groups, first group is 0.45 part of flyash, 0.4 part of higher ridge
Soil, 0.1 part of land plaster, 0.05 part of ground granulated blast furnace slag, 1.3 parts of Machine-made Sands and 0.0075 part of basalt fibre, 0.01 part of sodium base are swollen
Profit soil.Second group is 0.0359 part of sodium hydrate solid, 0.108 part of distilled water, 0.256 part of sodium silicate solution；Third group is
0.01 part of polymer dispersion powder and 0.1 part of water.
(2) all raw materials in first group in addition to sodium bentonite, basalt fibre are sent into planetary mortar mixer
In, blender capacity is 30 liters, and rotating speed is 60 revs/min, is first mixed 2 minutes.Then sodium bentonite is gradually added into
In blender, continue stirring 2 minutes, be finally slowly added into basalt fibre, continues stirring until material is uniformly mixed, it is desirable that total
Mixing time is not less than 8 minutes.Each amount of agitation can be controlled according to print speed.
(3) 0.0359 part of sodium hydroxide in second group is dissolved in 0.108 part of distilled water, since sodium hydroxide was dissolving
Cheng Zhonghui releases a large amount of heat, therefore uses water-bath cooling to room temperature, finally by sodium hydroxide solution and 0.256 part of sodium silicate solution
It is mixed with compound alkali-activator, and for use after storing 24 hours, storage temperature is 25 ± 2 DEG C；
(4) 0.1 part of water is weighed, and is slowly added into 0.01 part of polymer dispersion powder, it is stirring while adding, stablize glue until being formed
Body.
(5) compound alkali-activator prepared by step (3) is added to the mixed dry material that step (2) obtains when field print
In, continue stirring until uniformly mixed after stirring 2 minutes, after colloid prepared by step (4) is added, total mixing time is 5~6 points
Clock, be after stirring it is described can 3D printing flyash base polymers.
Using the present embodiment can the flyash base polymers of 3D printing carry out 3D printing, detailed process is：By above-mentioned gather
Object machinery is delivered in the printing head of 3D printer, and slice and path planning are carried out in Slic3r Slice Softwares, and setting is beaten
It is circle, bore 10mm, extruded velocity 0.53m to print nozzle cross sectional shape3/ h, horizontal direction print speed are 180m/h, layer
Thickness is 5mm, then generates G code, and G code is poured into and controls printer in computer control software Repetier~Host and beats
Print.It is printed according to the above print parameters, obtains print structure body.Print procedure is well on, and institute's print structure
Globality, stability are preferable.This example open hour are 60min.Compression strength is 36MPa when age is 28 days.
Embodiment 3
The present embodiment can the flyash base polymers of 3D printing count in parts by weight, composition and the content difference of ground polymers
For：
0.5 part of flyash；
0.375 part of metakaolin；
0.175 part of ground granulated blast furnace slag；
0.05 part of land plaster；
The average grain diameter of 1.3 parts of Machine-made Sand, the Machine-made Sand is 125~430 μm；
0.5 part of composite exciting agent；
0.08 part of water；
0.02 part of polymer dispersion powder；
Length is 0.0075 part of the basalt fibre of 18mm；
0.01 part of sodium bentonite (thixotropic agent).
The compound alkali-activator is made of sodium silicate solution and sodium hydroxide solution, by 0.0525 part of sodium hydrate solid
Powder is dissolved in be sufficiently mixed in 0.159 part of distilled water after obtain sodium hydroxide solution, a concentration of the 33% of sodium hydroxide solution.So
0.288 part of sodium silicate solution is finally added in the sodium hydroxide solution of above-mentioned preparation and mixes to room temperature by water-bath cooling afterwards, institute
The modulus of the compound alkali-activator prepared is 1.2.The modulus of the sodium silicate solution is 3.2, solid content 35%.
The loss on ignition of the flyash is 7.1%, moisture content 0.1%, calcium oxide content 3.7%, and water demand ratio is
104%, fineness is that 45 μm of square hole screens tail over 17.5%.
The density of the metakaolin is 2.65g/cm3, specific surface area is 26~28m2/ g, moisture content 0.9%.
The density of the ground granulated blast furnace slag is 2.8g/cm3, specific surface area 350m2/ kg, moisture content 0.8%.
The land plaster is calcium sulphate dihydrate, and fineness is 200 mesh.
The Machine-made Sand is 277.5 μm of average grain diameter, specific surface area 0.125m2The mechanism quartz sand of/g；
The length of the basalt fibre be 18mm, tensile strength be 3300~4500MPa, elasticity modulus be 95~
115GPa, elongation at break are 2.4~3.0%；
The polymer dispersion powder is German watt gram 5044N types.
The present embodiment can the preparation method of flyash base polymers of 3D printing be：
(1) it counts in parts by weight, above-mentioned raw materials is divided into three groups, first group is 0.5 part of flyash, 0.375 part of higher ridge
Soil, 0.175 part of ground granulated blast furnace slag, 0.05 part of land plaster, 1.3 parts of Machine-made Sands and 0.0075 part of basalt fibre, 0.01 part of sodium base
Bentonite.Second group is 0.0525 part of sodium hydrate solid, 0.159 part of distilled water, 0.288 part of sodium silicate solution；Third group is
0.02 part of polymer dispersion powder and 0.075 part of water.
(2) all raw materials in first group in addition to sodium bentonite, basalt fibre are sent into planetary mortar mixer
In, blender capacity is 30 liters, and rotating speed is 60 revs/min, is first mixed 2 minutes.Then sodium bentonite is gradually added into
In blender, continue stirring 2 minutes, be finally slowly added into basalt fibre, continues stirring until material is uniformly mixed, it is desirable that total
Mixing time is not less than 8 minutes.Each amount of agitation can be controlled according to print speed.
(3) 0.0525 part of sodium hydroxide in second group is dissolved in 0.159 part of distilled water, since sodium hydroxide was dissolving
Cheng Zhonghui releases a large amount of heat, therefore uses water-bath cooling to room temperature, finally by sodium hydroxide solution and 0.288 part of sodium silicate solution
It is mixed with compound alkali-activator, and for use after storing 24 hours, storage temperature is 25 ± 2 DEG C；
(4) 0.075 part of water is weighed, and is slowly added into 0.02 part of polymer dispersion powder, it is stirring while adding, stablize until being formed
Colloid.
(5) compound alkali-activator prepared by step (3) is added to the mixed dry material that step (2) obtains when field print
In, after stirring 2 minutes, continue stirring until uniformly mixed after viscosity modifier prepared by step (4) is added, total mixing time is
5~6 minutes, be after stirring it is described can 3D printing flyash base polymers.
Using the present embodiment can the flyash base polymers of 3D printing carry out 3D printing, detailed process is：By above-mentioned gather
Object machinery is delivered in the printing head of 3D printer, and slice and path planning are carried out in Slic3r Slice Softwares, and setting is beaten
It is circle, bore 15mm, extruded velocity 0.8m to print nozzle cross sectional shape3/ h, horizontal direction print speed are 200m/h, thickness
For 7mm, G code is then generated, G code is poured into and controls printer in computer control software Repetier~Host and beats
Print.It is printed according to the above print parameters, obtains print structure body.Print procedure is well on, and institute's print structure
Globality, stability are preferable.This example open hour are 30min.Compression strength is 53MPa when age is 28 days.
Comparative example 1
Especially except sodium bentonite 0.005, other material categories, additive amount, be stirred mode and print parameters
It is same as Example 1.Test result is shown：Print procedure can be well on, but because ground polymers mobility is too strong, thixotropy compared with
Weak, the structure of printing is tilted so that being caved in, and structure can not be molded.
Comparative example 2
Except ground granulated blast furnace slag volume is adjusted to 0.2 part, other material categories, additive amount, preparation method and printing
Parameter is same as Example 2.Test result is shown：Since blast-furnace cinder volume is too many, polymer material condensation hardening in ground is too fast,
Open hour are only 20min.It is unsatisfactory for the requirement of extrusion type printer corresponding to the present invention, print procedure can not be successfully progress.
Comparative example 3
Especially except basalt fibre 0.035, other material categories, additive amount, preparation method and print parameters with
Embodiment 3 is identical.Test result is shown：Since the incorporation of fiber is larger, leads the fiber in concrete mix and occur armful
Group's phenomenon, in print procedure, occur the phenomenon that blocking at nozzle, print procedure can not be successfully progress.
To sum up, the present invention can the flyash base polymers of 3D printing can not only reduce cement by primary raw material of flyash
Dosage can also solve the pollution problem that flyash is brought.Material printing performance is high, setting rate is fast, the open hour can
It adjusts, and there is thixotropy, the good feature of caking property.Under the conditions of room temperature curing temperature, 28d compression strength can reach
53MPa or so disclosure satisfy that mechanical property requirements of the building 3D printing to material.
The present invention does not address place and is suitable for the prior art, and involved raw material are commercially available or obtain by conventional method
It arrives.
Claims (7)
1. it is a kind of can 3D printing flyash base polymers, count in parts by weight, the composition and content of ground polymers are respectively：
0.4~0.6 part of flyash；
0.275~0.5 part of metakaolin；
0.05~0.1 part of land plaster；
0.05~0.175 part of ground granulated blast furnace slag；
The average grain diameter of 1~1.5 part of Machine-made Sand, the Machine-made Sand is 125~430 μm；
0.01~0.03 part of viscosity modifier；
0.4~0.6 part of compound alkali-activator；
0.05~0.125 part of water；
Length is 0.0075~0.03 part of the basalt fibre of 6~18 mm；
0.01~0.03 part of sodium bentonite.
2. it is according to claim 1 can 3D printing flyash base polymers, it is characterised in that the viscosity modifier is
Polymer dispersion powder；The modulus of the compound alkali-activator controls in 1.2~1.4 ranges.
3. it is according to claim 1 can 3D printing flyash base polymers, it is characterised in that the burning of the flyash is lost
Amount is 7.1%, moisture content 0.1%, calcium oxide content 3.7%, water demand ratio 104%, and fineness is that 45 μm of square hole screens tail over
17.5%；
The density of the metakaolin is 2.65 g/cm3, specific surface area is 26~28 m2/ g, moisture content 0.9%；
The density of the ground granulated blast furnace slag is 2.8 g/cm3, specific surface area is 350~500 m2/ kg, moisture content 0.8%；
The land plaster is calcium sulphate dihydrate, and fineness is 100~300 mesh；
The Machine-made Sand is 277.5 μm of average grain diameter, 0.125 m of specific surface area2The quartz sand of/g；
The tensile strength of the basalt fibre is 3300~4500MPa, and elasticity modulus is 95~115GPa, and elongation at break is
2.4~3.0%.
4. it is according to claim 1 can 3D printing flyash base polymers, it is characterised in that the compound alkali-activator
It is made of sodium silicate solution and sodium hydroxide solution.
5. described in a kind of claim 4 can 3D printing flyash base polymers preparation method, the preparation method include with
Lower step：
（1）Count in parts by weight, above-mentioned raw materials be divided into three groups, first group be 0.4~0.6 part of flyash, 0.275~0.5 part
Metakaolin, 0.05~0.1 part of land plaster, 0.05~0.175 part of ground granulated blast furnace slag, 1~1.5 part of Machine-made Sand and 0.0075~
0.03 part of basalt fibre, 0.01~0.03 part of sodium bentonite；Second group for 0.0359~0.0675 part of sodium hydrate solid,
0.077~0.191 part of distilled water, 0.23~0.429 part of sodium silicate solution；Third group be 0.01~0.03 part of viscosity modifier and
0.05~0.125 part of water；
（2）All raw materials in first group in addition to sodium bentonite and basalt fibre are sent into planetary mortar mixer,
After stirring, then sodium bentonite is gradually added into blender, continues stirring to being uniformly mixed, be finally slowly added into
Basalt fibre, continue stirring until material be uniformly mixed, obtain mixed dry material；
（3）0.0359~0.0675 part of sodium hydroxide powder in second group is dissolved in 0.077~0.191 part of distilled water fully mixed
Sodium hydroxide solution is obtained after conjunction；Then it uses water-bath cooling to room temperature, finally 0.23~0.429 part of sodium silicate solution is added
To being mixed in the sodium hydroxide solution of above-mentioned preparation, it is prepared compound alkali-activator, and for use, storage temperature after storing 24 hours
Degree is 25 ± 2 DEG C；
（4）0.05~0.125 part of water is weighed, and is slowly added into 0.01~0.03 part of viscosity modifier, it is stirring while adding, until shape
At stable colloid；
（5）By step when field print（3）The compound alkali-activator prepared is added to step（2）In obtained mixed dry material, fill
After dividing stirring, step is added（4）Continue stirring after the colloid of preparation until being uniformly mixed, be after stirring it is described can 3D
The flyash base polymers of printing.
6. it is according to claim 5 can 3D printing flyash base polymers preparation method, it is characterised in that the silicon
The modulus of acid sodium solution is 3.2, solid content 35%.
7. a kind of claim 1-6 it is any it is described can 3D printing flyash base polymers application method, the application method
Process be：Ground polymers is pumped or machinery is delivered in the printing head of 3D printer, terminates to printing since stirring
Time is no more than 5 minutes, and setting printing head cross sectional shape is circle, and bore is 10~20 mm, and extruded velocity is 0.5~1.0
m3/ h, print speed is 180~210m/h in plane.
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| CN109400031A (en) * | 2018-12-29 | 2019-03-01 | 河北工业大学 | 3D printing The Zhaozhou Bridge plant fiber enhances ground polymers and preparation method thereof |
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Families Citing this family (1)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015072609A1 (en) * | 2013-11-18 | 2015-05-21 | 한국지질자원연구원 | Three-dimensional measuring method for porous geopolymer using electronic tomography |
| CN106082898A (en) * | 2016-06-16 | 2016-11-09 | 中国建筑股份有限公司 | Geopolymer composite material that 3D prints and its production and use |
-
2018
- 2018-02-01 CN CN201810102082.9A patent/CN108275924B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015072609A1 (en) * | 2013-11-18 | 2015-05-21 | 한국지질자원연구원 | Three-dimensional measuring method for porous geopolymer using electronic tomography |
| CN106082898A (en) * | 2016-06-16 | 2016-11-09 | 中国建筑股份有限公司 | Geopolymer composite material that 3D prints and its production and use |
Non-Patent Citations (1)
| Title |
|---|
| 赵云龙、徐洛屹: "《石膏干混建材生产及应用技术》", 31 August 2016 * |
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