CN106315575B - 3D printing material and 3D printing product based on graphene oxide and their preparation method - Google Patents
3D printing material and 3D printing product based on graphene oxide and their preparation method Download PDFInfo
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- CN106315575B CN106315575B CN201610695655.4A CN201610695655A CN106315575B CN 106315575 B CN106315575 B CN 106315575B CN 201610695655 A CN201610695655 A CN 201610695655A CN 106315575 B CN106315575 B CN 106315575B
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The 3D printing material and 3D printing product and their preparation method that the invention discloses a kind of based on graphene oxide.Wherein the main component of the 3D printing material based on graphene oxide is graphene oxide, aniline and water.The present invention, which utilizes, has electrostatic attraction between graphene oxide and aniline, the characteristics of hydrogen bond and π-π interactions, graphene oxide and aniline are together with each other and prepare 3D printing material, not only extend the raw material range of 3D printing material, and prepared 3D printing material also have viscosity it is suitable, at normal temperatures can molding advantage without heating, it can be suitable for 3D printing requirement, and corresponding 3D printing flow and apparatus structure can be simplified to reduce 3D printing cost, and then suitable for the scale of mass production of 3D printing product.
Description
Technical field
The present invention relates to 3D printing fields, and in particular, to a kind of 3D printing material and 3D based on graphene oxide are beaten
Print product and their preparation method.
Background technology
3D printing is known as overturning industrial revolution again of traditional manufacture, be mainly it is a kind of can with printed material
With, as the processing technology of numerical control, 3D printing technique has boundless answer the characteristics of extrusion and rapid shaping and using computer
Use foreground.
Existing 3D printing material is usually thermoplastic material or alloy material, and viscosity is very low at normal temperatures, mouldability
It is very poor, so current 3D printing material is in print procedure, it usually needs by material after high-temperature fusion, according to pre-set programs
It is extruded or tiles, final solidified molding.And exactly in view of this present situation of existing 3D printing material so that with 3D printing
The structure for the printing equipment that material matches is also relative complex, has in turn resulted in greatly improving for 3D printing product cost, limitation
The application of 3D printing technique.It would therefore be highly desirable to develop a kind of preferable 3D printing material of mouldability at normal temperatures, beaten with simplifying 3D
Bleeding off journey and corresponding apparatus structure, and then reduce the cost of 3D printing product.
Graphene is to pass through sp by carbon atom2The compound for the two-dimension plane structure that hydridization is formed.Since there is two dimension altogether
Yoke structure so that it, with superior electric conductivity, heat conductivility and stability, is a kind of good material of application prospect
Material.In recent years, graphene received the concern of people and was widely studied, and the application based on graphene also emerges one after another.
Graphene oxide is by introducing a variety of oxygen-containing groups on the surface of graphene and edge after graphite powder Strong oxdiative
The carbon nanomaterial of group.Graphene oxide is important one of the derivative of graphene, and it is mostly important to be that chemical method prepares graphene
Presoma.Also, since in graphene oxide, containing there are many oxygen-containing functional group, multiple functions modification can be carried out, thus
It is considered as the carbon nanomaterial of most foreground.
Invention content
The purpose of the present invention is being directed to the problem of current 3D printing material formability difference, provide a kind of based on oxidation
The 3D printing material and 3D printing product of graphene and their preparation method, to improve the formed at normal temp of 3D printing material
Property, simplify the technological process of 3D printing and corresponding apparatus structure.
To achieve the goals above, according to the first aspect of the invention, a kind of 3D based on graphene oxide is provided to beat
Material is printed, the main component of the 3D printing material is graphene oxide, aniline and water.
According to the second aspect of the invention, a kind of preparation side of the 3D printing material based on graphene oxide is provided
Method, the preparation method include the following steps：S1, graphene oxide water solution is prepared；S2, by the graphene oxide water solution with
Aniline mixes, and stir process is to form sediment.
According to the third aspect of the present invention, a kind of 3D printing material being prepared by the above method of the present invention is provided
Material.
According to the fourth aspect of the present invention, a kind of 3D printing product is provided, the main component of the 3D printing product is
Redox graphene, and the carbon-to-oxygen ratio in the redox graphene is 8-12.
According to the fifth aspect of the present invention, a kind of preparation method of 3D printing product is provided, which includes
Following steps：S1, at normal temperatures by 3D printing material machine-shaping of the present invention, obtain product green body；S2, original place is being gone back
Under the conditions of reason, the product green body and hydriodic acid aqueous solution are subjected to haptoreaction, obtain the 3D printing product.
Using above-mentioned technical proposal of the present invention, using having electrostatic attraction between graphene oxide and aniline, hydrogen bond and
The characteristics of π-π interactions, the 3D printing material for preparation that graphene oxide and aniline are together with each other not only extends
The raw material range of 3D printing material, and prepared 3D printing material also have viscosity it is suitable, without heating at normal temperatures
Molding advantage can be suitable for 3D printing requirement, and can simplify corresponding 3D printing flow and apparatus structure to drop
Low 3D printing cost, and then suitable for the scale of mass production of 3D printing product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Method prepares in 3D printing materials process mixture in isotope bottle during Fig. 1 shows according to embodiments of the present invention 1
Product changes with time figure；
Fig. 2 shows the product appearance shape appearance figures of 3D printing material prepared according to embodiments of the present invention 1；
Fig. 3 shows the crosssections in appearance shape appearance figure of 3D printing material prepared according to embodiments of the present invention 1；
Fig. 4 shows according to embodiments of the present invention 1 prepared 3D printing material in freeze-dried treated scanning electricity
Sub- microscope figure (SEM figures)；
Fig. 5 shows the exterior appearance figure of 3D printing material prepared according to embodiments of the present invention 4；
Fig. 6 shows the viscosity profile of the 3D printing material prepared by method in 1-3 according to embodiments of the present invention；
Fig. 7 shows the storage modulu of the 3D printing material prepared by method and loss in 1-3 according to embodiments of the present invention
Modulus change figure.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific implementation mode stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
A kind of 3D printing material based on graphene oxide, the main component of the 3D printing material are provided in the present invention
For graphene oxide, aniline and water.
The characteristics of present invention, which utilizes, has electrostatic attraction between graphene oxide and aniline, hydrogen bond and π-π interactions,
Graphene oxide and aniline are together with each other the 3D printing material of preparation, not only extend the raw material model of 3D printing material
Enclose, and prepared 3D printing material also have viscosity it is suitable, without heating at normal temperatures can molding advantage, can
Suitable for 3D printing requirement, and corresponding 3D printing flow and apparatus structure can be simplified to reduce 3D printing cost, Jin Ershi
Scale of mass production for 3D printing product.
3D printing material according to the present invention, under preferable case, the 3D printing material is 0.1S in shear rate-1Condition
Under 25 DEG C of viscosity be 5000-40000Pas, preferably 8000-35000Pas, more preferably 10000-25000Pas,
By controlling the viscosity of the 3D printing material, it is more advantageous to the mobility and processability for controlling the 3D printing material.
Rheological property (viscosity) is using the advanced rotating flows of MCR301 commercially available from German Anton Paar company in the present invention
Become instrument test to obtain, it is 25 DEG C, cone-plate cp25-2, shear rate 0.1S that wherein test condition, which includes temperature,-1。
3D printing material according to the present invention, wherein for graphene oxide and aniline content there is no particular/special requirement,
As long as enabling to the 3D printing material that there is certain plasticity.In the present invention preferably in the 3D printing material
In, the graphene oxide based on 100mg, the content of the aniline is 1.25-5g, preferably 1.25-3.75g, more preferably
1.25-2.5g。
Graphene oxide compound according to the present invention, under preferable case, with 100 weight of graphene oxide compound
On the basis of measuring %, the content of water is 10-35wt%.
3D printing material according to the present invention, using graphene oxide, aniline and water as main component, wherein can also contain
Other functional fillers.In the preferred case, on the basis of 100 weight % of the 3D printing material, the main component contains
Amount is 80-95 weight %.Wherein for the type of other functional fillers and dosage, there is no particular/special requirements, can be according to system
Demand in standby process or application process is rationally added, as long as ensureing the viscosity and main component of the 3D printing material
Content in above range, herein for the functional filler specific type and dosage without repeating.
Meanwhile a kind of preparation method of the 3D printing material based on graphene oxide, the system are additionally provided in the present invention
Preparation Method includes the following steps：S1, graphene oxide water solution is prepared；S2, the graphene oxide water solution and aniline are mixed
It closes, stir process is to form sediment.
The present invention is using surface of graphene oxide and edge due to introducing a large amount of polar group so that it can uniformly divide
Water or other organic solvent features are dispersed in, graphene oxide solution is first prepared, recycling has between aniline and graphene oxide
The characteristics of electrostatic attraction, hydrogen bond and π-π interactions so that aniline is combined with graphene oxide, forms sediment, in turn
3D printing material needed for obtaining.This method processing step is simple, easily operated, is suitable for large-scale production.
According to the above-mentioned preparation method of the present invention, under preferable case, a concentration of 6- of graphene oxide is prepared in step sl
The graphene oxide water solution of 10mg/mL.The concentration of graphene oxide is controlled in aforementioned range, oxidation stone is may advantageously facilitate
The combination of black alkene and aniline so that product has preferable mouldability.If graphene oxide in graphene oxide water solution
Content is very few preferably to make product not easily molded because of the mobility of solution, if oxygen in graphene oxide water solution
The content of graphite alkene may excessively disperse uneven because of aniline and product mechanical property is deteriorated.
According to the above-mentioned preparation method of the present invention, under preferable case, the graphene oxide is to remove graphite method by oxidation
(Hummers methods) is prepared.The S1 includes that graphene oxide water solution is prepared using oxidation stripping graphite method in S11；
S12, the concentration of the graphene oxide water solution is allocated to 6-10mg/mL.
According to the above-mentioned preparation method of the present invention, wherein the oxidation stripping graphite method is by by graphite powder and permanganic acid
Potassium haptoreaction in the concentrated sulfuric acid (a concentration of 98wt%) prepares graphene oxide.Such as by graphite powder, potassium permanganate and dense sulphur
Acid is according to 100g：250-350g：The ratio of 2000-3000mL mixes；Such as first under the conditions of ice bath stirring by graphite powder (mistake
320 mesh sieve particulate matter), potassium permanganate and the concentrated sulfuric acid mixing, then plus water and be warming up to 35-50 DEG C reaction 15-60min, so
After add water and be warming up to 85-95 DEG C of reaction 10-20min, then cooling plus water and be cooled to room temperature, suction filtration obtains filter cake；Again
Filter cake is cleaned by hydrochloric acid, is dispersed in water after cleaning, (preferably its molecular cut off is 8000-14000g/ with bag filter
Mol it) dialyses to obtain graphene oxide solution (the final pH value of dialysis product is 7).
According to the above-mentioned preparation method of the present invention, under preferable case, the graphene oxide based on 100mg, described in the S2
The additive amount of aniline is 1.25-5g, preferably 1.25-3.75g, more preferably 1.25-2.5g.By graphene oxide and aniline control
System within the above range, is conducive to obtain the relatively mild product of viscosity.
According to the above-mentioned preparation method of the present invention, not for graphene oxide water solution in S2 and aniline mixing temperature
Particular/special requirement, such as it can carry out at normal temperatures, can also be carried out under low temperature (25-60 DEG C) heating condition；For oxidation
There is no particular/special requirements with aniline mixing speed for graphene aqueous solution, can be according to the size selection stirring appropriate of device
Condition, for graphene oxide water solution and aniline incorporation time also there is no particular/special requirement, the production that can be mixed by stirring
Completed state (the structure of discrete state (liquid portion color is thin out, gradually clarifies) and sediment of sediment and liquid in object
More apparent spherical structure) judged, usual stir process 12-72h in practical operation.
A kind of 3D printing material being prepared by the above method is still further provided in the present invention.The 3D printing material
The main component of material is graphene oxide, aniline and water.This 3D printing material being prepared by the above method of the present invention
Component content and viscosity are described in preceding sections, and details are not described herein.
A kind of 3D printing product is additionally provided in the present invention, and the main component of the 3D printing product is reduction-oxidation graphite
Alkene, and the carbon-to-oxygen ratio in the redox graphene is 8-12.This 3D printing product provided by the present invention be pass through by
The aforementioned 3D printing material of the present invention passes through reduction treatment and obtains after shaping.
According to the above-mentioned 3D printing product of the present invention, under preferable case, the strength range of the 3D printing product is 50-
500kPa, preferably 200-500kPa, more preferably 400-500kPa.The conductivity of the 3D printing product is 15000-
25000S/m, preferably 20000-25000S/m.
According to the above-mentioned 3D printing product of the present invention, it can only contain redox graphene, can also contain
Functional filler refers to the explanation of the functional filler explanation of aforementioned 3D printing material part, and details are not described herein.
A kind of preparation method of above-mentioned 3D printing product is additionally provided in the present invention, which includes following step
Suddenly：S1, at normal temperatures by the above-mentioned 3D printing material machine-shaping of the present invention, obtain product green body；S2, in reduction treatment condition
Under, the product green body and hydriodic acid aqueous solution are subjected to haptoreaction, obtain the 3D printing product.It is provided by the present invention
The preparation method of this above-mentioned 3D printing product, in view of the above-mentioned 3D printing material of the present invention is used, without to 3D printing material
It is heated and softened, directly can be realized as, to the molding of above-mentioned 3D printing material, not only simplifying operating procedure at room temperature,
Also reduce equipment cost.
Above-mentioned preparation method according to the present invention, under preferable case, the reduction treatment condition includes：At 25-100 DEG C
At a temperature of, the product green body is immersed in the hydriodic acid aqueous solution of a concentration of 40-57wt%, reduction treatment 12-72h.
Above-mentioned preparation method according to the present invention further includes using after the step of completing reduction treatment in practical operation
The cleaning solution of second alcohol and water is respectively washed reduction treatment product so that the pH value of cleaning solution is 6.8-7.2 after reduction treatment, to obtain
Obtain the 3D printing product.
A kind of 3D printing product being prepared by the above method is further provided in the present invention.The main component is
Redox graphene, and the carbon-to-oxygen ratio in the redox graphene is 8-12.The composition transitivity of the 3D printing product
In aforementioned by the agency of mistake, details are not described herein.
The advantageous effect further illustrated the present invention below with reference to specific embodiment.
In the following example, used graphene oxide water solution is to remove graphite method (Hummers by oxidation
Method) it is prepared, specific preparation method includes：1g graphite powders (particulate matter for crossing 325 mesh sieve) are taken, the sulfuric acid that 23mL is added is (dense
Degree is 98wt%), be added 3g potassium permanganate under ice bath (0-5 DEG C) stirring condition, 40 DEG C of reaction half an hours, be added 50mL water it
Afterwards, 15min is reacted under the conditions of 90 DEG C, 150mL water etc. to room temperature is then added into system again, 5mL hydrogen peroxide is added
(30wt%).It filters above-mentioned solution and obtains filter cake, filter cake is with 1:Filter cake is dispersed in 300mL by 9 hydrochloric acid 50mL cleanings afterwards three times
In water, the bag filter for being finally 8000-14000g/mol with molecular cut off is dialysed one week, product final pH=7.It will be on part
State a concentration of 12g/L that graphene oxide in the graphene oxide water solution known to conversion is weighed after product is dried in an oven.
In the following example, the ingredient and content of prepared 3D printing material and 3D products are red by Raman spectrum
External spectrum and the general analysis of X-ray diffraction.
In the following example, involved test event and test method are as follows：
(1) scanning electron microscope test (JSM-7500F, Japanese Shimadzu Corporation)：The 3D printing material prepared is taken, is set
In vacuum freeze drier (- 50 DEG C, 60Pa), freeze-drying for 24 hours, the sample after drying is sticked on conducting resinl, metal spraying 30s
Sample is tested in scanning electron microscope afterwards.
(2) rheological property (viscosity)：It is obtained using the advanced rotational rheometer tests of German Anton Paar company MCR301, test
Condition includes：Temperature is 25 DEG C, cone-plate cp25-2, shear rate 0.1S-1。
(3) conductivity：It is measured using four probe sheet resistance tester of Kun De Science and Technology Ltd.s KDY-1 types.It will test
Sample is cut into 1cm × 1cm sizes.
(4) mechanical strength：Using Shimadzu Shimadzu AGS-X apparatus measures, loading speed 20mm/min.
Embodiment 1
For illustrating that the present invention is based on the 3D printing material of graphene oxide and 3D printing product and their preparation sides
Method.
Distilled water dilution will be added in the graphene oxide water solution of aforementioned preparation, prepares a concentration of 8mg/ of graphene oxide
The graphene oxide water solution of mL；
The aniline that the graphene oxide water solution 10mL and 1mL of above-mentioned preparation are added in the isotope bottle of 20mL is (opposite
Density is 1.02), to be stirred for 24 hours with stirrer (rotating speed 800rpm) under room temperature (25 DEG C), will be extra in the isotope bottle
Aqueous phase separation, it is required 3D printing material to take out sediment.Fig. 1 is the change of the product of mixture in the isotope bottle at any time
Change figure, as shown in Figure 1, the color of wherein graphene oxide water solution gradually becomes shallower as, while increasingly generating with sediment,
Produced in sediment be needed for 3D printing material.
(2) ingredient and characterization of 3D printing material：
The apparent form and Cross Section Morphology of the 3D printing material are as Figure 2-3, and the 3D printing material is in forming process
Gradually combine it is agglomerating, ultimately form spherical shape.The inside for (being stripped of water and aniline) after the freeze-drying of the 3D printing material
Structure is as shown in figure 4, the internal structure of material of the 3D printing material after freeze-drying removes internal solution is by oxidation stone
The layer structure of black alkene slice, thin piece assembling is constituted.Through analysis it is found that containing graphene oxide, aniline and water in the 3D printing material,
And in terms of 100 weight % of 3D printing material, wherein the aniline of the graphene oxide containing 5.1 weight %, 63.3 weight % and
The water of 31.6 weight %；And the viscosity of the 3D printing material is 30000Pas.
(3) preparation of 3D printing product：
At normal temperatures, the 3D printing material of the aforementioned preparation is made to the square products green body of 4 × 4 × 1.5cm；In room
The product green body is immersed in the hydriodic acid aqueous solution of a concentration of 57wt%, reduction treatment 72h takes out through reduction treatment under temperature
Product green body first with ethyl alcohol rinse 5 times, then wash with water to the pH of ejected wash water be 7 until to get 3D printing product.
(4) ingredient and characterization of 3D printing product
Ingredient through analyzing the 3D printing product is redox graphene, and carbon-to-oxygen ratio is in the redox graphene
The strength range of 10-12, the product are 500kPa, conductivity 18000S/m.
Embodiment 2
For illustrating that the present invention is based on the 3D printing material of graphene oxide and 3D printing product and their preparation sides
Method
(1) preparation of 3D printing material：With reference to embodiment 1, difference lies in be added above-mentioned match in the isotope bottle of 20mL
The aniline of the graphene oxide water solution 10mL and 2mL of system.
(2) ingredient and characterization of 3D printing material：
Through analysis it is found that containing graphene oxide, aniline and water in the 3D printing material, and with 100 weight of 3D printing material
% meters are measured, wherein the water of the graphene oxide containing 3.1 weight %, the aniline of 77.5 weight % and 19.4 weight %；And it should
The viscosity of 3D printing material is 10000Pas.
(3) preparation of 3D printing product：It is 3D printing product by aforementioned 3D printing material preparation with reference to embodiment 1.
(4) ingredient and characterization of 3D printing product：
Ingredient through analyzing the 3D printing product is redox graphene, and carbon-to-oxygen ratio is in the redox graphene
The strength range of 10-12, the product are 300kPa, conductivity 18000S/m.
Embodiment 3
For illustrating that the present invention is based on the 3D printing material of graphene oxide and 3D printing product and their preparation sides
Method
(1) preparation of 3D printing material：With reference to embodiment 1, difference lies in be added above-mentioned match in the isotope bottle of 20mL
The aniline of the graphene oxide water solution 10mL and 4mL of system.
(2) ingredient and characterization of 3D printing material：
Through analysis it is found that containing graphene oxide, aniline and water in the 3D printing material, and with 100 weight of 3D printing material
% meters are measured, wherein the water of the graphene oxide containing 1.8 weight %, the aniline of 87.3 weight % and 10.9 weight %；And it should
The viscosity of 3D printing material is 1540Pas.
(3) preparation of 3D printing product：It is 3D printing product by aforementioned 3D printing material preparation with reference to embodiment 1.
(4) ingredient and characterization of 3D printing product
Ingredient through analyzing the 3D printing product is redox graphene, and carbon-to-oxygen ratio is in the redox graphene
The strength range of 10-12, the product are 80kPa, conductivity 18000S/m.
Embodiment 4
For illustrating that the present invention is based on the 3D printing material of graphene oxide and 3D printing product and their preparation sides
Method
(1) preparation of 3D printing material：Reference embodiment 1, difference lies in,
The aniline of the graphene oxide water solution 100mL and 10mL of above-mentioned preparation are added in the beaker of 200mL, in room temperature
Under (25 DEG C) for 24 hours with stirrer (rotating speed 1000rpm) stirring, by aqueous phase separation extra in the beaker, sediment note is taken out
For required 3D printing material.
(2) ingredient and characterization of 3D printing material：
The apparent form of the 3D printing material as shown in figure 5,3D printing material raw material dosage in preparation process increasing
Adduction does not interfere with the molding of product, still forms spherical shape.And through analysis it is found that containing oxidation in the 3D printing material
Graphene, aniline and water, and in terms of 100 weight % of 3D printing material, wherein the graphene oxide containing 5.1 weight %, 63.3
The water of the aniline of weight % and 31.6 weight %.And the viscosity of the 3D printing material is 30000Pas.
(3) preparation of 3D printing product：It is 3D printing product by aforementioned 3D printing material preparation with reference to embodiment 1.
(4) ingredient and characterization of 3D printing product
Ingredient through analyzing the 3D printing product is redox graphene, and carbon-to-oxygen ratio is in the redox graphene
The strength range of 10-12, the product are 500kPa, conductivity 18000S/m.
Rheology testing：
(1) rheological property (viscosity) is tested：Using the advanced rotational rheometers of MCR301 commercially available from German Anton Paar company
Test obtains, and wherein test condition includes：Temperature is 25 DEG C, cone-plate cp25-2, shear rate 10-2-102S-1。
Test result：As shown in fig. 6, the 3D printing material prepared by embodiment 1 to embodiment 3 is with aniline in figure 6
The increase viscosity of content can decrease.
(2) storage modulus and loss modulus test：Using the advanced rotating flows of MCR301 commercially available from German Anton Paar company
Become instrument test to obtain, wherein test condition includes：Temperature is 25 DEG C, cone-plate cp25-2, constant frequency 1Hz, stress scans
Range is from 101-104Pa。
Test result：As shown in fig. 7, the 3D printing material prepared by embodiment 1 to embodiment 3 is with aniline in the figure 7
The increase storage modulus and loss modulus of content can continuously decrease.
In summary rheological property and storage modulus and loss modulus test result are it is found that with aniline in 3D printing material
The variation of content, the viscosity and modulus of material can change.Wherein by by graphene oxide and benzene in 3D printing material
In the graphene oxide based on 100mg, the content of the aniline is 1.25-5g, preferably 1.25-3.75g for the content control of amine,
When more preferably 1.25-2.5g, the viscosity and modulus of the 3D printing material can be balanced preferably, so that the 3D printing
Material ensures the intensity of corresponding 3D printing product while with certain plasticity (good moldability).
As shown in the above, the present invention, which utilizes, has electrostatic attraction, hydrogen bond and π-π between graphene oxide and aniline
The characteristics of interaction, the 3D printing material for preparation that graphene oxide and aniline are together with each other not only extend 3D
The raw material range of printed material, and prepared 3D printing material also have viscosity it is suitable, at normal temperatures can be at without heating
The advantage of type can be suitable for 3D printing requirement, and can simplify corresponding 3D printing flow and apparatus structure to reduce
3D printing cost, and then suitable for the scale of mass production of 3D printing product.Moreover, by the 3D prepared by 3D printing material of the present invention
The intensity of printed product can reach 50-500kPa, and conductivity can reach 15000-25000S/m.
The preferred embodiment of the present invention is described in detail above in association with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical scheme of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (18)
1. a kind of 3D printing material based on graphene oxide, which is characterized in that the main component of the 3D printing material is oxygen
Graphite alkene, aniline and water；
The content of graphene oxide based on 100mg, the aniline is 1.25-5g；
The graphene oxide and water are configured to the graphene oxide water solution of a concentration of 6-10mg/mL of graphene oxide.
2. 3D printing material according to claim 1, wherein the 3D printing material is 0.1S in shear rate-1Condition
Under 25 DEG C of viscosity be 5000-40000Pa.s.
3. 3D printing material according to claim 2, wherein the 3D printing material is 0.1S in shear rate-1Condition
Under 25 DEG C of viscosity be 10000-25000Pa.s.
4. 3D printing material according to claim 1, wherein the graphene oxide based on 100mg, the content of the aniline
For 1.25-3.75g.
5. 3D printing material according to claim 4, wherein the graphene oxide based on 100mg, the content of the aniline
For 1.25-2.5g.
6. a kind of preparation method of the 3D printing material based on graphene oxide, which is characterized in that the preparation method include with
Lower step：
S1, graphene oxide water solution is prepared；
S2, the graphene oxide water solution is mixed with aniline, stir process is to form sediment；
The graphene oxide water solution of a concentration of 6-10mg/mL of graphene oxide is prepared in the S1；
The additive amount of graphene oxide based on 100mg in the S2, the aniline is 1.25-5g.
7. preparation method according to claim 6, wherein the S1 includes：
S11, graphene oxide water solution is prepared using oxidation stripping graphite method；
S12, the concentration of the graphene oxide water solution is allocated to 6-10 mg/mL.
8. preparation method according to claim 6, wherein the graphene oxide based on 100mg in the S2, the aniline
Additive amount be 1.25-3.75g.
9. preparation method according to claim 8, wherein the graphene oxide based on 100mg in the S2, the aniline
Additive amount be 1.25-2.5g.
10. the 3D printing material that a kind of method by described in any one of claim 6 to 9 is prepared.
11. a kind of 3D printing product, which is characterized in that the main component of the 3D printing product is redox graphene, and
Carbon-to-oxygen ratio in the redox graphene is 8-12；
The strength range of the 3D printing product is 50-500kPa.
12. 3D printing product according to claim 11, wherein the strength range of the 3D printing product is 200-
500kPa。
13. 3D printing product according to claim 12, wherein the strength range of the 3D printing product is 400-
500kPa。
14. 3D printing product according to claim 11, wherein the conductivity of the 3D printing product is 15000-
25000S/m。
15. 3D printing product according to claim 14, wherein the conductivity of the 3D printing product is 20000-
25000S/m。
16. a kind of preparation method of 3D printing product, which is characterized in that the preparation method comprises the following steps：
S1, at normal temperatures by the 3D printing material machine-shaping described in any one of claim 1 to 5 and 10, produced
Product green body；
S2, under the conditions of reduction treatment, the product green body and hydriodic acid aqueous solution are subjected to haptoreaction, the 3D is obtained and beats
Print product.
17. preparation method according to claim 16, wherein the reduction treatment condition includes：In 25-100 DEG C of temperature
Under degree, the product green body is immersed in the hydriodic acid aqueous solution of a concentration of 40-57wt%, reduction treatment 12-72h.
18. the 3D printing product that a kind of method by described in claim 16 or 17 is prepared.
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| CN110044972A (en) * | 2019-04-18 | 2019-07-23 | 厦门理工学院 | A kind of graphene-based gas sensor and preparation method thereof |
| CN112973640B (en) * | 2021-03-24 | 2022-04-15 | 兰州大学 | Preparation method of 3D printing reduced graphene oxide filter element for treating uranium-containing wastewater |
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| CN104959613A (en) * | 2015-07-10 | 2015-10-07 | 北京科技大学 | Method for curing and shaping slurry spray used for 3D printing |
| CN105062219A (en) * | 2015-09-14 | 2015-11-18 | 北京理工大学 | Microcrystalline graphene conductive ink and preparation method |
| CN105504565A (en) * | 2015-12-25 | 2016-04-20 | 成都新柯力化工科技有限公司 | Graphene-containing conducting material used for 3D printing and preparation method of graphene-containing conducting material |
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