CN108545732A - A kind of graphene oxide 3D printing ink and preparation method thereof - Google Patents
A kind of graphene oxide 3D printing ink and preparation method thereof Download PDFInfo
- Publication number
- CN108545732A CN108545732A CN201810315616.6A CN201810315616A CN108545732A CN 108545732 A CN108545732 A CN 108545732A CN 201810315616 A CN201810315616 A CN 201810315616A CN 108545732 A CN108545732 A CN 108545732A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- crosslinking agent
- solvent
- printing ink
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
-
- 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
- B33Y80/00—Products made by additive manufacturing
Abstract
The present invention discloses a kind of graphene oxide 3D printing ink and preparation method, prepares raw material used and is made of graphene oxide, crosslinking agent and solvent, each raw material dosage, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.03‑1mmol：The ratio of 40ml calculates.Graphene oxide, crosslinking agent ultrasonic disperse are configured to solution by preparation method respectively with solvent first, then the graphene oxide solution of gained and cross-linking agent solution are mixed and carries out chemical crosslink reaction, the centrifugation of gained reaction solution, removal supernatant, up to graphene oxide 3D printing ink, when circular frequency is 0.9rad/s, its kinematic viscosity is measured up to 2,800 20800 Pa*s.The graphene oxide three-dimensional aeroge holder of gained after use, when deformation quantity is 60%, compression modulus is 0.42 MPa, 0.98 MPa.
Description
Technical field
The present invention relates to a kind of preparations of graphene oxide 3D printing ink, belong to the energy/biometric print inks field.
Background technology
Freely diversification in material and structure design may be implemented in three-dimensional printing technology, convenient for control contour structures and material
Component can effectively construct the three-dimensional macro network structure of more material components.However three-dimensional extruded type printing technology, to ink stream
Variant viscosity, which has, is strict with, and auxiliary additive (high polymer binder or silica flour) is needed to realize that high viscosity is adjusted.Tradition
The high polymer binder for 3D printing be mainly PCL, PVA, PEG, PGA etc., however this kind of material has processing temperature
Higher disadvantage；However the use of binder or additive, can influence the purity of graphene-structured, the high-temperature calcination in later stage or
Weak boundary interlayer introduces between causing graphene layer, seriously affects graphene-structured stability.
2015, Worsley M.A. et al. adjusted graphene oxide (GO) ink viscosity by adding silica flour, realize
Three-dimensional macro structure directly pulls writing.But silica flour additive is difficult thoroughly to etch away, influence graphene-structured purity and
Mechanical stability.3D printing ink prepared by this method, viscosity is with characteristic of the shear rate increase with shear shinning, when cutting
Cutting speed rate is 0.1S-1When, apparent viscosity is about that (the graphene oxide doped mass fraction of 20mg/ml is 10% to 1500Pa*s
Silica flour)；Its aeroge holder printed is 53mg/cm in bulk density3, strain when being 50%, incompressible intensity is 1.2MPa.
2016, the method that Lin Dong et al. are mutually assisted using drip-type ink-jet technology with cryogenic freezing moulding process,
It solves requirement of the ink to viscosity during 3D printing, realizes the 3 D-printing of pure GO structures, but increase to a certain extent
The complexity for adding preparation process, improves manufacturing cost.
Bibliography
[1]、L.Wu,L.Liu,B.Gao,R.-Carpena,M.Zhang,H.Chen,Z.H.Zhou,and
H.Wang,Langmuir 2013,29,15174.
[2]、J.Chen,F.Chi,L.Huang,M.Zhang,B.Yao,Y.Li,C.Li,G.Shi,Carbon 2016,
110,34.
[3]、C.Zhu,T.Y.J Han,E.B.Duoss,A.M.Golobic,J.D.Kuntz,C.M.Spadaccini,
M.A.Worsley,Nature Commun.2015,6,6962.
Invention content
An object of the present invention is to overcome the shortcomings of current graphene printing technique, provides a kind of graphene oxide 3D and beats
Printing ink, the graphene oxide 3D printing ink can directly be beaten in the case where no high polymer binder is additive-free
Print, i.e., can directly print excellent conductivity and the higher oxidation of precision using the graphene oxide ink by three-dimensional printer
Graphene flexible support or graphene oxide three-dimensional aeroge holder.
The two of the object of the invention are to provide a kind of preparation method of above-mentioned graphene oxide 3D printing ink, the preparation side
Method is environmentally friendly, production environmental protection.
Technical scheme of the present invention
A kind of graphene oxide 3D printing ink prepares raw material used by graphene oxide, crosslinking agent and solvent group
At the dosage of each raw material, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.03-1.0mmol：
The ratio of 40ml calculates；
Further, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.03-0.6mmol：40ml
Ratio calculate；
Further, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.2-0.3mmol：40ml
Ratio calculate；
The graphene oxide is to aoxidize to obtain using improved Hummers methods by natural flake graphite powder[1]；
The crosslinking agent is K+、Na+、Mg2+、Cu2+、Ca2+、Zn2+、Ni2+、Co2+、Fe3+、Al3+、Sn4+、Ti4+、Mn4+In
Any one metal cation hydrochloride, preferably cobalt chloride hexahydrate, ferric chloride hexahydrate or potassium chloride；
The solvent is water or alcohol, and the water is mineral water, pure water or deionized water；The alcohol be ethyl alcohol,
Butanediol, glycerine, half lactonaphthol, xylitol or ribitol.
A kind of preparation method of above-mentioned graphene oxide 3D printing ink, specifically comprises the following steps：
(1), graphene oxide solution configures
It adding graphene oxide into partial solvent, control power is 400W, frequency is that 25KHz carries out ultrasound 30min,
Obtain the graphene oxide solution of 2mg/ml；
(2), the configuration of cross-linking agent solution
Crosslinking agent is added in remaining solvent, control power is 400W, frequency is that 25KHz carries out ultrasonic disperse
10min obtains the cross-linking agent solution of 3-60mM；
(3), the graphene oxide solution obtained by step (1) and the cross-linking agent solution obtained by step (2) are added sequentially to
The use of whirlpool blending instrument control rotating speed is then that 600r/min carries out rotation mixing 5min so that graphene oxide sheet in centrifuge tube
Oxygenated functional group on layer carries out sufficient chemical crosslink reaction, the reaction solution centrifugation of gained with crosslinking agent, that is, metal cation
Machine, rotating speed are that 12000rpm carries out centrifugation 4h, remove supernatant, the precipitation of gained is graphene oxide 3D printing ink.
The graphene oxide 3D printing ink of above-mentioned gained, is being frequency scanned using the rotational rheometer with parallel plate fixtures
Under pattern, when circular frequency is 0.9rad/s, it is 2800-20800Pa*s, preferably 13270- to measure its kinematic viscosity
20800Pa*s, and in use, its print conditions is mild, print temperature is 0-40 DEG C, and air pressure is set as 0.5~2.0bar, beats
3~10mm/s of print-out rate.
Holder printing, the very high oxygen of finally obtained precision are carried out using the graphene oxide 3D printing ink of above-mentioned gained
Graphite alkene flexible support or graphene oxide three-dimensional aeroge holder.The graphene oxide three-dimensional aeroge holder of gained,
When deformation quantity is 60%, compression modulus 0.42MPa-0.98MPa.It is indicated above the graphene oxide 3D printing ink of the present invention
It can print out the graphene oxide three-dimensional aeroge holder with certain compression strength.
The advantageous effects of the present invention
A kind of graphene oxide 3D printing ink of the present invention, due to using metal cation salt as crosslinking agent, metal
Chemical crosslink reaction occurs for the oxygenated functional group of metal cation and graphene oxide in cationic salts, to reach regulation and control oxygen
The effect of the viscosity of graphite alkene ink.The metal cation solution of same concentrations, ionic valence condition is higher, finally obtained ink
Viscosity is bigger, then its chemical crosslinking effect becomes apparent from.To realize 3D printing ink directly beating without high polymer binder
Print.
Further, a kind of graphene oxide 3D printing ink of the invention, due to metal ion and graphene oxide layer
Oxygenated functional group is crosslinked, it is achieved that the preparation of high viscosity 3D printing graphene ink, the graphene oxide 3D of final gained
Marking ink under frequency sweep mode, when circular frequency is 0.9rad/s, is surveyed using the rotational rheometer with parallel plate fixtures
Its kinematic viscosity is obtained up to 2800-20800Pa*s, and in use, its print conditions is mild, print temperature is 0-40 DEG C, gas
Pressure is set as 0.5~2.0bar, 3~10mm/s of print speed, realizes the direct printing of filler-free.
Further, graphene oxide 3D printing ink of the invention, due to using metal cation salt as crosslinking agent, with
The 3D printing ink of high polymer binder is used to compare in the prior art, when use can effectively improve the electric conductivity of print carriage.
Further, graphene oxide 3D printing ink of the invention, due to using metal cation salt as crosslinking agent, with
The 3D printing ink of high polymer binder is used to compare in the prior art, so as to avoid high annealing removal in the prior art
The step of high polymer binder, thus it is simple with preparation process, energy consumption is reduced, and easy to use, can directly printed.
Further, in graphene oxide 3D printing ink preparation process of the invention, aqueous solvent used or alcohol are
Nontoxic, environmentally friendly, production environmental protection.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Raw material graphene oxide used in various embodiments of the present invention is by natural flake graphite powder using improved
Hummers methods[1]Oxidation obtains, and specifically comprises the following steps：
(1), the 3g graphite powders that grain size is 50 mesh are added in the concentrated sulfuric acid of the advance ice baths of 180ml and are uniformly mixed, control
200r/min stirs 30min, and 15g potassium permanganate is added in the rate for then pressing 1.5g/min, continues to control under the conditions of ice-water bath
200r/min stirs 30min, then heats to 40 DEG C, and it is that 600r/min carries out reaction 7h to control speed of agitator, is reacted
Liquid；
The graphite powder is 50 mesh natural flake graphite powder, purchases and rises Sheng up to the limited public affairs of carbon machinery in Qingdao
Department；
(2), the reaction solution obtained by step (1) is poured into the ice water of 1000ml, stopped reaction, control speed of agitator is
600r/min stirs 30min, and the mass percent concentration that 30ml is then added is 30% aqueous hydrogen peroxide solution, then controls stirring
Rotating speed is that 600r/min stirs 30min, is then allowed to stand, obtains bright yellow solution；
(3), the ice water of 90ml is added in the bright yellow solution obtained by step (2), is turned controlled at 40 DEG C, stirring
Speed is that 600r/min stirs 1h, obtains graphite oxide.
(4), the graphite oxide for obtaining step (3) first uses the aqueous hydrochloric acid solution that concentration of volume percent is 10% to centrifuge
After washing 2 times, then with the pH of deionized water centrifuge washing to efflux it is neutral, the precipitation of gained is scattered in 2L water, is controlled
Temperature is 37 DEG C, frequency 25KHz, and ultrasound stripping 1h under the conditions of ultrasonic power is 400W, it is 3000r/min then to control rotating speed
Centrifugation 15min is carried out, removal centrifugation bottom of the tube precipitates (unoxidized graphite powder), finally obtains various embodiments of the present invention on a small quantity
Graphene oxide used.
Other raw materials and reagent used in various embodiments of the present invention, no specified otherwise are commercially available.
Device name used in various embodiments of the present invention, model and manufacturer's information are as follows：
Embodiment 1
A kind of graphene oxide 3D printing ink, raw material are made of graphene oxide, crosslinking agent and solvent, and each raw material is used
Amount, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.1mmol：The ratio of 40ml calculates；
The crosslinking agent is cobalt chloride hexahydrate；
The solvent is deionized water.
A kind of preparation method of above-mentioned graphene oxide 3D printing ink, specifically comprises the following steps：
(1), graphene oxide solution configures
It weighs 60mg graphene oxides to be dissolved into 30ml solvents, it is 400W, frequency that power is controlled in supersonic cleaning machine
Ultrasound 30min is carried out for 25KHz, obtains the graphene oxide solution of 2mg/ml；
(2), the configuration of cross-linking agent solution
The crosslinking agent of 23.8mg (0.1mmol) is taken to be dissolved into 10ml solvents, being placed in control power in supersonic cleaning machine is
400W, frequency are that 25KHz carries out ultrasonic disperse 10min, obtain the cross-linking agent solution of 10mM；
(3), the graphene oxide solution obtained by step (1) and the cross-linking agent solution obtained by step (2) are all added successively
Enter into 50ml centrifuge tubes, then using whirlpool blending instrument rotation mixing 5min so that the oxidation function in graphene oxide layer
Group carries out sufficient chemical crosslink reaction with crosslinking agent, that is, metal cation, and the reaction solution Centrifugal Machine Control temperature of gained is 25
DEG C, rotating speed be to centrifuge 4h under 12000rpm, remove supernatant, the precipitation of gained is graphene oxide 3D printing ink.
The graphene oxide 3D printing ink of above-mentioned gained, is being frequency scanned using the rotational rheometer with parallel plate fixtures
Under pattern[2], when it is 0.9rad/s to shear circular frequency, kinematic viscosity 2800Pa*s.
Application Example 1
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 1 gained of above-described embodiment is utilized
Three-dimensional aeroge holder, be as follows：
It takes above-mentioned ink to be placed in the barrel of 3D printer, using a diameter of 400 microns of syringe needle, runs 3D printing journey
Sequence, it is respectively 10mm to print length, width and height, and the distance of the rick model support of 10mm, 5mm, adjacent lines is 0.8mm；
The rick model support of above-mentioned preparation is placed in freeze drier controlled at -100 DEG C, control pressure is
12MPa, drying is for 24 hours, you can obtains the three-dimensional aeroge holder of graphene oxide；
The three-dimensional aeroge holder of the graphene oxide of above-mentioned gained is resisted using 2.5 thousand Ns of universal testing machines
Compressive Strength measures[3], when deformation quantity is 60%, compression modulus 0.78MPa.
Application Example 2
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 1 gained of above-described embodiment is utilized
Flexible support, be as follows：
The graphene oxide 3D printing ink of 1 gained of Example is placed in the barrel of 3D printer, uses a diameter of 400
The syringe needle of micron runs 3D printing program, and it is respectively 10mm, the 1-6 layer holders of 10mm to print length and width；
Length and width by above-mentioned gained is respectively 10mm, and the 1-6 layers branch of 10mm, which is placed in air, to be spontaneously dried for 24 hours, you can
Obtain the flexible support of graphene oxide.
Embodiment 2
A kind of graphene oxide 3D printing ink prepares raw material used by graphene oxide, crosslinking agent and solvent group
At each raw material dosage, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.3mmol：The ratio of 40ml
It calculates；
The crosslinking agent is cobalt chloride hexahydrate；
The solvent is deionized water.
A kind of preparation method of above-mentioned graphene oxide 3D printing ink, specifically comprises the following steps：
(1), graphene oxide solution configures
It weighs 60mg graphene oxides to be dissolved into 30ml solvents, it is 400W, frequency that power is controlled in supersonic cleaning machine
Ultrasound 30min is carried out for 25KHz, obtains the graphene oxide solution of 2mg/ml；
(2), the configuration of cross-linking agent solution
It takes the crosslinking agent of 71.4mg (0.3mmol) to be dissolved into 10ml solvent deionized waters, is placed in supersonic cleaning machine and controls
Power processed is 400W, frequency is that 25KHz carries out ultrasonic disperse 10min, obtains the cross-linking agent solution of 30mM；
(3), by the graphene oxide solution obtained by 30ml steps (1) and the cross-linking agent solution obtained by 10ml steps (2) according to
It is secondary to be added in 50ml centrifuge tubes, then using whirlpool blending instrument rotation mixing 5min so that the oxidation in graphene oxide layer
Functional group carries out sufficient chemical crosslink reaction with crosslinking agent, that is, metal cation, and the reaction solution of gained is with centrifuge speed
4h is centrifuged under 12000rpm, removes supernatant, the precipitation of gained is graphene oxide 3D printing ink.
The graphene oxide 3D printing ink of above-mentioned gained, is being frequency scanned using the rotational rheometer with parallel plate fixtures
Under pattern[2], when it is 0.9rad/s to shear circular frequency, kinematic viscosity 20800Pa*s.
Application Example 3
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 2 gained of above-described embodiment is utilized
Three-dimensional aeroge holder, be as follows：
It takes above-mentioned ink to be placed in the barrel of 3D printer, using a diameter of 400 microns of syringe needle, runs 3D printing journey
Sequence prints the rick model support that length is respectively 10mm, 10mm, 5mm, and the distance of adjacent lines is 0.8mm；
The rick model support of above-mentioned preparation is placed in freeze drier controlled at -100 DEG C, control pressure is
12MPa is dried for 24 hours, can be obtained the three-dimensional aeroge holder of graphene oxide；
The three-dimensional aeroge holder of the graphene oxide of above-mentioned gained is resisted using 2.5 thousand Ns of universal testing machines
Compressive Strength measures[3], when deformation quantity is 60%, compression modulus 0.85MPa.
Application Example 4
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 2 gained of above-described embodiment is utilized
Flexible support, be as follows：
The graphene oxide 3D printing ink of 2 gained of Example is placed in the barrel of 3D printer, uses a diameter of 400
The syringe needle of micron runs 3D printing program, prints the holder that length and width is respectively the 1-6 layers of 10mm, 10mm；
Length and width by above-mentioned gained is respectively that the branch of the 1-6 layers of 10mm, 10mm is placed in air, naturally dry at room temperature
It is dry for 24 hours, can be obtained the flexible support of graphene oxide.
Embodiment 3
A kind of graphene oxide 3D printing ink, raw material are made of graphene oxide, crosslinking agent and solvent, and each raw material is used
Amount, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.6mmol：The ratio of 40ml calculates；
The crosslinking agent is KCl；
The solvent is deionized water.
A kind of preparation method of above-mentioned graphene oxide 3D printing ink, specifically comprises the following steps：
(1), graphene oxide solution configures
It weighs 60mg graphene oxides to be dissolved into 30ml solvents, it is 400W, frequency that power is controlled in supersonic cleaning machine
Ultrasound 30min is carried out for 25KHz, obtains the graphene oxide solution of 2mg/ml；
(2), the configuration of cross-linking agent solution
The crosslinking agent of 44.7mg (0.6mmol) is taken to be dissolved into 10ml solvents, being placed in control power in supersonic cleaning machine is
400W, frequency are that 25KHz carries out ultrasonic disperse 10min, obtain the cross-linking agent solution of 60mM；
(3), by the graphene oxide solution obtained by 30ml steps (1) and the cross-linking agent solution obtained by 10ml steps (2) according to
It is secondary to be added in 50ml centrifuge tubes, then using whirlpool blending instrument rotation mixing 5min so that the oxidation in graphene oxide layer
Functional group carries out sufficient chemical crosslink reaction with crosslinking agent, that is, metal cation, and the reaction solution of gained is controlled with refrigerated centrifuge
Temperature is 25 DEG C, rotating speed centrifuges 4h under being 12000rpm, removes supernatant, the precipitation of gained is graphene oxide 3D printing ink
Water.
The graphene oxide 3D printing ink of above-mentioned gained, is being frequency scanned using the rotational rheometer with parallel plate fixtures
Under pattern[2], when it is 0.9rad/s to shear circular frequency, kinematic viscosity 5268Pa*s.
Application Example 5
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 3 gained of above-described embodiment is utilized
Three-dimensional aeroge holder, be as follows：
It takes above-mentioned ink to be placed in the barrel of 3D printer, using a diameter of 400 microns of syringe needle, runs 3D printing journey
Sequence prints the rick model support that length is respectively 10mm, 10mm, 5mm, and the distance of adjacent lines is 0.8mm；
The rick model support of above-mentioned preparation is placed in freeze drier controlled at -100 DEG C, control pressure is
12MPa, drying is for 24 hours, you can obtains the three-dimensional aeroge holder of graphene oxide；
The three-dimensional aeroge holder of the graphene oxide of above-mentioned gained is resisted using 2.5 thousand Ns of universal testing machines
Compressive Strength measures[3], when deformation quantity is 60%, compression modulus 0.42MPa.
Application Example 6
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 3 gained of above-described embodiment is utilized
Flexible support, be as follows：
The graphene oxide 3D printing ink of 3 gained of Example is placed in the barrel of 3D printer, uses a diameter of 400
The syringe needle of micron runs 3D printing program, prints the holder that length and width is respectively the 1-6 layers of 10mm, 10mm；
Length and width by above-mentioned gained is respectively that the branch of the 1-6 layers of 10mm, 10mm is placed in air and spontaneously dries for 24 hours, i.e.,
The flexible support of graphene oxide can be obtained.
Embodiment 4
A kind of graphene oxide 3D printing ink, raw material are made of graphene oxide, crosslinking agent and solvent, and each raw material is used
Amount, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.03mmol：The ratio of 40ml calculates；
The crosslinking agent is Iron(III) chloride hexahydrate；
The solvent is deionized water.
A kind of preparation method of above-mentioned graphene oxide 3D printing ink, specifically comprises the following steps：
(1), graphene oxide solution configures
It weighs 60mg graphene oxides to be dissolved into 30ml solvents, it is 400W, frequency that power is controlled in supersonic cleaning machine
Ultrasound 30min is carried out for 25KHz, obtains the graphene oxide solution of 2mg/ml；
(2), the configuration of cross-linking agent solution
(0.03mmol) crosslinking agent of 8.1mg is taken to be dissolved into 10ml solvents 2, being placed in control power in supersonic cleaning machine is
400W, frequency are that 25KHz carries out ultrasonic disperse 10min, obtain the cross-linking agent solution of 3mM；
(3), by the graphene oxide solution obtained by 30ml steps (1) and the cross-linking agent solution obtained by 10ml steps (2) according to
It is secondary to be added in 50ml centrifuge tubes, then using whirlpool blending instrument rotation mixing 5min so that the oxidation in graphene oxide layer
Functional group carries out sufficient chemical crosslink reaction with crosslinking agent, that is, metal cation, and the reaction solution of gained is controlled with refrigerated centrifuge
Temperature is 25 DEG C, rotating speed centrifuges 4h under being 12000rpm, removes supernatant, the precipitation of gained is graphene oxide 3D printing ink
Water.
The graphene oxide 3D printing ink of above-mentioned gained, is being frequency scanned using the rotational rheometer with parallel plate fixtures
Under pattern[2], when it is 0.9rad/s to shear circular frequency, kinematic viscosity 2738Pa*s.
Application Example 7
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 4 gained of above-described embodiment is utilized
Three-dimensional aeroge holder, be as follows：
It takes above-mentioned ink to be placed in the barrel of 3D printer, using a diameter of 400 microns of syringe needle, runs 3D printing journey
Sequence prints the rick model support that length is respectively 10mm, 10mm, 5mm, and the distance of adjacent lines is 0.8mm；
The rick model support of above-mentioned preparation is placed in freeze drier controlled at -100 DEG C, control pressure is
12MPa, drying is for 24 hours, you can obtains the three-dimensional aeroge holder of graphene oxide；
The three-dimensional aeroge holder of the graphene oxide of above-mentioned gained is resisted using 2.5 thousand Ns of universal testing machines
Compressive Strength measures[3], when deformation quantity is 60%, compression modulus 0.94MPa.
Application Example 8
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 4 gained of above-described embodiment is utilized
Flexible support, be as follows：
The graphene oxide 3D printing ink of 4 gained of Example is placed in the barrel of 3D printer, uses a diameter of 400
The syringe needle of micron runs 3D printing program, prints the holder that length and width is respectively the 1-6 layers of 10mm, 10mm；
Length and width by above-mentioned gained is respectively that the branch of the 1-6 layers of 10mm, 10mm is placed in air and spontaneously dries for 24 hours, i.e.,
The flexible support of graphene oxide can be obtained.
Embodiment 5
A kind of graphene oxide 3D printing ink, raw material are made of graphene oxide, crosslinking agent and solvent, and each raw material is used
Amount, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.2mmol：The ratio of 40ml calculates；
The crosslinking agent is cobalt chloride hexahydrate；
The solvent is deionized water.
A kind of preparation method of above-mentioned graphene oxide 3D printing ink, specifically comprises the following steps：
(1), graphene oxide solution configures
Weigh 60mg graphene oxides to be dissolved into 30ml solvents, in supersonic cleaning machine) in control power be 400W, frequency
Ultrasound 30min is carried out for 25KHz, obtains the graphene oxide solution of 2mg/ml；
(2), the configuration of cross-linking agent solution
The crosslinking agent of 47.6mg (0.2mmol) is taken to be dissolved into 10ml solvents, being placed in control power in supersonic cleaning machine is
400W, frequency are that 25KHz carries out ultrasonic disperse 10min, obtain the cross-linking agent solution of 20mM；
(3), the graphene oxide solution obtained by step (1) and the cross-linking agent solution obtained by step (2) are all added successively
Enter into 50ml centrifuge tubes, the rotation mixing of whirlpool blending instrument is then used to carry out cross-linking reaction 5min so that graphene oxide layer
On oxygenated functional group and crosslinking agent, that is, metal cation carry out sufficient chemical crosslink reaction, the reaction solution of gained freeze from
Scheming is that 4h is centrifuged under 12000rpm controlled at 25 DEG C, rotating speed, removes supernatant, the precipitation of gained is graphene oxide
3D printing ink.
The graphene oxide 3D printing ink of above-mentioned gained, is being frequency scanned using the rotational rheometer with parallel plate fixtures
Under pattern[2], when it is 0.9rad/s to shear circular frequency, kinematic viscosity 13270Pa*s.
Application Example 9
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 5 gained of above-described embodiment is utilized
Three-dimensional aeroge holder, be as follows：
It takes above-mentioned ink to be placed in the barrel of 3D printer, using a diameter of 400 microns of syringe needle, runs 3D printing journey
Sequence prints the rick model support that length is respectively 10mm, 10mm, 5mm, and the distance of adjacent lines is 0.8mm；
The rick model support of above-mentioned preparation is placed in freeze drier and controls temperature, controlled at -100 DEG C, control
Pressure processed is 12MPa, and drying is for 24 hours, you can obtains the three-dimensional aeroge holder of graphene oxide；
The three-dimensional aeroge holder of the graphene oxide of above-mentioned gained is resisted using 2.5 thousand Ns of universal testing machines
Compressive Strength measures[3], when deformation quantity is 60%, compression modulus 0.84MPa.
Application Example 10
Using 3D printer, the graphene oxide 3D printing ink printed graphene oxide of 5 gained of above-described embodiment is utilized
Three-dimensional aeroge holder, be as follows：
The graphene oxide 3D printing ink of 1 gained of Example is placed in the barrel of 3D printer, uses a diameter of 400
The syringe needle of micron runs 3D printing program, and it is respectively 10mm, the holder of the 1-6 layers of 10mm to print length and width；
Length and width by above-mentioned gained is respectively that the branch of the 1-6 layers of 10mm, 10mm is placed in air and spontaneously dries for 24 hours, i.e.,
The flexible support of graphene oxide can be obtained.
In conclusion a kind of graphene oxide 3D printing ink provided by the invention, due to being made using metal cation salt
For crosslinking agent, chemical crosslink reaction occurs for the oxygenated functional group of metal cation and graphene oxide in metal cation salt,
To have the function that regulate and control the viscosity of graphene oxide ink.To realize 3D printing ink without high polymer binder,
The direct printing of filler-free.Using the rotational rheometer with parallel plate fixtures under frequency sweep mode, when circular frequency is
When 0.9rad/s, its kinematic viscosity is measured up to 2800-20800Pa*s, and in use, its print conditions is mild, printing is warm
Degree is 0-40 DEG C, and air pressure is set as 0.5~2.0bar, 3~10mm/s of print speed.
The above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improve and become
Type also should be regarded as protection scope of the present invention.
Claims (12)
1. a kind of graphene oxide 3D printing ink, it is characterised in that the graphene oxide 3D printing ink by walking as follows
Rapid method is prepared：
Graphene oxide, crosslinking agent ultrasonic disperse are configured to solution respectively with solvent first, then by the graphite oxide of gained
Row chemical crosslink reaction is infiltrated in alkene solution and cross-linking agent solution rotation, and the reaction solution centrifugation of gained removes supernatant to get oxidation stone
Black alkene 3D printing ink；
The graphene oxide is to aoxidize to obtain using improved Hummers methods by natural flake graphite powder；
The crosslinking agent is K+、Na+、Mg2+、Cu2+、Ca2+、Zn2+、Ni2+、Co3+、 Fe3+、Al3+、Sn4+、Ti4+、Mn4+In
The hydrochloride of any one metal cation；
The solvent is water or alcohol, wherein the water is mineral water, pure water or deionized water, the alcohol be ethyl alcohol,
Butanediol, glycerine, half lactonaphthol, xylitol or ribitol；
The dosage of raw material graphene oxide, crosslinking agent and solvent used in above-mentioned preparation, by graphene oxide：Gold in crosslinking agent
Belong to cation：Solvent is 60mg：0.03-1.0mmol：The ratio of 40ml calculates.
2. a kind of graphene oxide 3D printing ink as described in claim 1, it is characterised in that prepare raw material oxidation used
The dosage of graphene, crosslinking agent and solvent, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.03-
0.6mmol：The ratio of 40ml calculates；
The crosslinking agent is potassium chloride, cobalt chloride hexahydrate or ferric chloride hexahydrate；
The solvent is deionized water.
3. a kind of graphene oxide 3D printing ink as claimed in claim 2, it is characterised in that prepare raw material oxidation used
The dosage of graphene, crosslinking agent and solvent, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.03
mmol：The ratio of 40ml calculates；
The crosslinking agent is ferric chloride hexahydrate.
4. a kind of graphene oxide 3D printing ink as claimed in claim 2, it is characterised in that prepare raw material oxidation used
The dosage of graphene, crosslinking agent and solvent, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg： 0.1-
0.2mmol：The ratio of 40ml calculates；
The crosslinking agent is cobalt chloride hexahydrate.
5. a kind of graphene oxide 3D printing ink as claimed in claim 2, it is characterised in that prepare raw material oxidation used
The dosage of graphene, crosslinking agent and solvent, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：0.2-
0.3mmol：The ratio of 40ml calculates；
The crosslinking agent is cobalt chloride hexahydrate.
6. a kind of graphene oxide 3D printing ink as claimed in claim 5, it is characterised in that prepare raw material oxidation used
The dosage of graphene, crosslinking agent and solvent, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：
0.3mmol：The ratio of 40ml calculates.
7. a kind of graphene oxide 3D printing ink as claimed in claim 5, it is characterised in that prepare raw material oxidation used
The dosage of graphene, crosslinking agent and solvent, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：
0.2mmol：The ratio of 40ml calculates.
8. a kind of graphene oxide 3D printing ink as claimed in claim 2, it is characterised in that prepare raw material oxidation used
The dosage of graphene, crosslinking agent and solvent, by graphene oxide：Metal cation in crosslinking agent：Solvent is 60mg：
0.6mmol：The ratio of 40ml calculates；
The crosslinking agent is potassium chloride.
9. a kind of graphene oxide 3D printing ink as described in claim 1, it is characterised in that using with parallel plate fixtures
Rotational rheometer is under frequency sweep mode, when circular frequency is 0.9rad/s, measures the graphene oxide 3D printing ink
The kinematic viscosity of water is up to 2800-20800 Pa*s.
10. a kind of graphene oxide 3D printing ink as claimed in claim 9, it is characterised in that using with parallel plate fixtures
Rotational rheometer is under frequency sweep mode, when circular frequency is 0.9rad/s, measures the graphene oxide 3D printing ink
The kinematic viscosity of water is up to 13270-20800 Pa*s.
11. a kind of preparation method of graphene oxide 3D printing ink as described in claim 1, it is characterised in that specifically include
Following steps：
（1）, graphene oxide solution configuration
It adds graphene oxide into partial solvent, control power is 400W, frequency is that 25KHz carries out ultrasound 30min, is obtained
The graphene oxide solution of 2mg/ml；
（2）, cross-linking agent solution configuration
Crosslinking agent is added in remaining solvent, control power is 400W, frequency is that 25KHz carries out ultrasonic disperse 10min, is obtained
To the cross-linking agent solution of 3-60mM；
（3）, by step（1）The graphene oxide solution and step of gained（2）The cross-linking agent solution of gained is added sequentially to centrifuge
Guan Zhong, it is that 600r/min rotations mix 5min to carry out chemical crosslink reaction, institute then to use whirlpool blending instrument control rotating speed
The reaction solution control rotating speed obtained is that 12000 rpm centrifuge 4h, removes supernatant, the precipitation of gained is graphene oxide 3D printing
Ink.
12. a kind of graphene oxide 3D printing ink as described in claim 1 for print graphene oxide flexible support or
Graphene oxide three-dimensional aeroge holder；
The graphene oxide three-dimensional aeroge holder of gained, using 2.5 thousand Ns of universal testing machines of German Zwick/Roell
It is tested, when deformation quantity is 60%, compression modulus is 0.42 MPa-0.98 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810315616.6A CN108545732A (en) | 2018-04-10 | 2018-04-10 | A kind of graphene oxide 3D printing ink and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810315616.6A CN108545732A (en) | 2018-04-10 | 2018-04-10 | A kind of graphene oxide 3D printing ink and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108545732A true CN108545732A (en) | 2018-09-18 |
Family
ID=63514625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810315616.6A Pending CN108545732A (en) | 2018-04-10 | 2018-04-10 | A kind of graphene oxide 3D printing ink and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108545732A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109732918A (en) * | 2018-12-25 | 2019-05-10 | 清华大学 | Gradient porous graphene oxide three-dimensional microorganism electrode of 3D printing and preparation method thereof |
| CN112480746A (en) * | 2020-11-23 | 2021-03-12 | 苏州千里眼医疗科技有限公司 | 3D printing ink with fish skin collagen as matrix and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277592A (en) * | 2014-09-16 | 2015-01-14 | 中国科学院化学研究所 | Graphene-based water-based ink and application thereof in ink-jet printing of patterning transparent conducting electrode |
| CN104801286A (en) * | 2015-05-14 | 2015-07-29 | 安徽大学 | Graphene oxide hydroxy propyl cellulose composite hydrogel as well as preparing method and application thereof |
| US20160368772A1 (en) * | 2015-05-20 | 2016-12-22 | Yu-Chen Chen | Efficient NanoMaterials manufacturing process and equipment |
| CN106946581A (en) * | 2017-04-20 | 2017-07-14 | 哈尔滨工业大学 | A kind of method that use 3D printing technique prepares conductive graphene/inorganic polymer composite material |
| WO2018017369A2 (en) * | 2016-07-12 | 2018-01-25 | William Marsh Rice University | Three-dimensional (3d) printing of graphene materials |
-
2018
- 2018-04-10 CN CN201810315616.6A patent/CN108545732A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277592A (en) * | 2014-09-16 | 2015-01-14 | 中国科学院化学研究所 | Graphene-based water-based ink and application thereof in ink-jet printing of patterning transparent conducting electrode |
| CN104801286A (en) * | 2015-05-14 | 2015-07-29 | 安徽大学 | Graphene oxide hydroxy propyl cellulose composite hydrogel as well as preparing method and application thereof |
| US20160368772A1 (en) * | 2015-05-20 | 2016-12-22 | Yu-Chen Chen | Efficient NanoMaterials manufacturing process and equipment |
| WO2018017369A2 (en) * | 2016-07-12 | 2018-01-25 | William Marsh Rice University | Three-dimensional (3d) printing of graphene materials |
| CN106946581A (en) * | 2017-04-20 | 2017-07-14 | 哈尔滨工业大学 | A kind of method that use 3D printing technique prepares conductive graphene/inorganic polymer composite material |
Non-Patent Citations (1)
| Title |
|---|
| YANQIU JIANG ET AL.: "Direct 3D Printing of Ultralight Graphene Oxide Aerogel Microlattices", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109732918A (en) * | 2018-12-25 | 2019-05-10 | 清华大学 | Gradient porous graphene oxide three-dimensional microorganism electrode of 3D printing and preparation method thereof |
| CN112480746A (en) * | 2020-11-23 | 2021-03-12 | 苏州千里眼医疗科技有限公司 | 3D printing ink with fish skin collagen as matrix and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104167302B (en) | Preparation method for grapheme/melamine resin hollow ball composite material | |
| CN104627994B (en) | Preparation method of reduced graphene oxide/phenol formaldehyde resin-base activated carbon in-situ composite material | |
| CN108545732A (en) | A kind of graphene oxide 3D printing ink and preparation method thereof | |
| CN104229768B (en) | Method for preparing porous carbon with three-dimensional structure | |
| CN105836742B (en) | A kind of preparation method with three-dimensional network-like structure graphene | |
| JP6779784B2 (en) | Conductive polymer material and molded products using it | |
| CN108550856A (en) | Carbon nano tube/graphene composite conducting slurry and preparation method thereof | |
| CN109904451A (en) | A kind of graphene composite material and its preparation method and application | |
| CN106237993B (en) | A kind of Fe3O4The preparation method of@MOF-199@C18 nanocomposite | |
| JP2012500771A5 (en) | ||
| CN106732729B (en) | Polybenzimidazoles with pyridine groups prepares the three-dimensional nitrogen-doped graphene of high nitrogen-containing | |
| CN107623137A (en) | A kind of preparation method of functional graphene oxide doping polybenzimidazole membrane | |
| CN105838086A (en) | Preparation method of sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material | |
| CN106057485A (en) | Method for preparing super capacitor aerogel electrode material | |
| CN107556510A (en) | A kind of preparation method of flexible sensor electrode | |
| CN107572498A (en) | A kind of carbide doping porous charcoal and preparation method thereof | |
| CN105949536A (en) | {0><}0{>Preparation method of high-strength natural rubber (NR)/carbon nano tube (CNT) conductive composite film | |
| CN107501612A (en) | 3D printing graphene oxide/cellulose composite material and preparation method and application | |
| JP2017141370A (en) | Conductive polymer material and molded article using the same | |
| CN106379893A (en) | Method for preparing sulfonated graphene material | |
| CN110182792A (en) | A kind of self-stabilization dispersed graphite alkene nano material and preparation method | |
| CN107501853B (en) | A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof | |
| CN106930151A (en) | A kind of fuel cell electrode preparation method of graphene carbon cellulose fiber conductive paper | |
| CN108384043A (en) | A kind of molecular imprinted polymer on surface material | |
| CN106898802A (en) | A kind of high-performing car hydrogen fuel cell composite nano-powder material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |