CN106946581A - A kind of method that use 3D printing technique prepares conductive graphene/inorganic polymer composite material - Google Patents

A kind of method that use 3D printing technique prepares conductive graphene/inorganic polymer composite material Download PDF

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CN106946581A
CN106946581A CN201710263533.2A CN201710263533A CN106946581A CN 106946581 A CN106946581 A CN 106946581A CN 201710263533 A CN201710263533 A CN 201710263533A CN 106946581 A CN106946581 A CN 106946581A
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inorganic polymer
composite material
printing
polymer composite
temperature
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CN106946581B (en
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贾德昌
钟晶
周国相
杨治华
何培刚
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

A kind of method that use 3D printing technique prepares conductive graphene/inorganic polymer composite material, is related to a kind of method for preparing conductive graphene/inorganic polymer composite material.The present invention is in order to solve the problem of preparation method of existing FRCMC is difficult that complex shaped components, preparation technology complexity, high cost, low electrical conductivity is made.The present invention：First, marking ink is prepared；2nd, 3D printing；3rd, solidify；4th, it is heat-treated.The graphene oxide solution with large-sized large stretch of footpath is employed herein, and the concentration range of graphene oxide is more wide in range, in the preparation process of marking ink, in the present invention and it is not added with deionized water to improve the rheological characteristic of ink, after sample is printed successfully, moisture evaporation is prevented using plastic culture dish sealing, it is entirely different that this is placed in wide-open space the moisture that volatilizees with sample.

Description

One kind prepares conductive graphene/inorganic polymer composite material using 3D printing technique Method
Technical field
The present invention relates to a kind of method for preparing conductive graphene/inorganic polymer composite material.
Background technology
FRCMC is widely used because of its excellent performance, but its preparation technology complexity, High cost, it is difficult to be prepared into labyrinth.At the same time, 3D printing will automatically, quickly, directly and relatively accurately can be calculated Three dimensional design in machine is converted into mock-up, or even direct manufacturing parts or mould, with saving material, high accuracy, Gao Fu Miscellaneous degree, the advantage such as the research and development of products cycle is short.
The content of the invention
The present invention in order to solve the preparation method of existing FRCMC is difficult that complicated shape structure is made The problem of part, preparation technology complexity, high cost, low electrical conductivity, and provide it is a kind of using 3D printing technique prepare conductive graphene/ The method of inorganic polymer composite material.
A kind of use 3D printing technique method for preparing conductive graphene/inorganic polymer composite material of the present invention be by Carried out according to following steps：
First, strengthened inorganic polymer base composite material of continuous fiber and graphene oxide solution are mixed under conditions of 0 DEG C Merge mechanical agitation 20min~30min, obtain marking ink；The concentration of described graphene oxide solution be 0.5wt%~ 4wt%；Graphene oxide and strengthened inorganic polymer base composite material of continuous fiber in described graphene oxide solution Mass ratio is 1:(26~250)；
The preparation method of described graphene oxide solution is as follows:
1., it will be existed after the nitric acid of 100g graphite flakes, the 540mL concentrated sulfuric acid and 70mL uniformly mixing with 200r/min speed 24h is stirred at room temperature, with deionized water filtering and washing three times, solid is taken, and is then to dry 24h under conditions of 60 DEG C in temperature, Obtain compound between graphite layers；The mass concentration of described nitric acid is 69%；The mass concentration of the described concentrated sulfuric acid is 95.5%； Described graphite flake is 50 mesh graphite flakes；Described graphite flake is 50 mesh graphite flakes；
2. compound between graphite layers, are incubated 15s under conditions of temperature is 1050 DEG C, expanded graphite is obtained；
3., by the potassium permanganate of 1g expanded graphite, the 200mL concentrated sulfuric acid and 10g, normal temperature mixes equal in three-neck flask It is even, 250mL hydrogen peroxide solution is then slowly added into, continues to stir 30min after solution is changed into glassy yellow from yellow green, uses salt Aqueous acid filtering and washing 3 times, obtains solid, and solid is put into bag filter and sealed；The mass concentration of the described concentrated sulfuric acid is 95.5%；The concentration of described hydrogen peroxide solution is 7.5%；The mass concentration of described aqueous hydrochloric acid solution encloses for 9.5%~ 10.5%；
4., by step 3. in bag filter place in deionized water stand 5 days~7 days, measure deionized water pH value；
If the pH that 5. 4. step measures is not 5~6, deionized water is changed, repeat step is 4. to the deionized water of measurement PH is 5~6, i.e., graphene oxide solution is obtained in bag filter；
2nd, 3D printing：The marking ink that step 2 is obtained is printed into 3-dimensional component using 3D printer；
3rd, solidify：The 3-dimensional component that step 3 is obtained is placed in culture dish and sealed, and is then 15 DEG C~20 DEG C in temperature Under conditions of solidify 12h~24h；
4th, it is heat-treated：Component after step 3 is solidified takes out from culture dish, is then carried out under inert gas shielding High-temperature process, the temperature of high-temperature process is 550 DEG C~1000 DEG C, and the time of high-temperature process is 30min~100min, that is, is led Graphene/inorganic polymer composite material.
The preparation technology of the present invention is simple, low cost, can make complex shaped components, and heat resistance is good, and electrical conductivity is high.
The graphene oxide solution with large-sized large stretch of footpath, and the concentration of graphene oxide is employed herein Scope is more wide in range, in the preparation process of marking ink, the present invention in and deionized water is not added with to improve the rheology of ink Property, after sample is printed successfully, moisture evaporation is prevented using plastic culture dish sealing, this is placed in wide-open space with sample Interior volatilization moisture is entirely different.Conductive graphene/inorganic polymer composite material prepared by the present invention has good power Learn performance.
The particle diameter of the graphene oxide layer prepared in the application step one is 10 μm~100 μm, and thickness is 2.7nm.
Strengthened inorganic polymer base composite material of continuous fiber and graphene oxide solution are mixed in the application step one, Deionized water is not added with, can make it that graphene oxide disperses in strengthened inorganic polymer base composite material of continuous fiber more preferable, The material of final molding can have more excellent electric property.
Sealing and curing prevents the volatilization of moisture in culture dish in the application step 3, and the volatilization of moisture can cause outside sample Surface portion water content is reduced, and is caused its solidification incomplete, so as to cause sample state of cure inconsistent, is influenceed sample mechanical property Energy；Component strength after solidifying in testing procedure three is 100Mpa~200Mpa.
The application step one 2. middle expanded graphite thickness be 5nm~100nm.
Embodiment
Embodiment one：Present embodiment prepares conductive graphene/inorganic polymeric to be a kind of using 3D printing technique The method of thing composite, is specifically followed the steps below：
First, strengthened inorganic polymer base composite material of continuous fiber and graphene oxide solution are mixed under conditions of 0 DEG C Merge mechanical agitation 20min~30min, obtain marking ink；The concentration of described graphene oxide solution be 0.5wt%~ 4wt%；Graphene oxide and strengthened inorganic polymer base composite material of continuous fiber in described graphene oxide solution Mass ratio is 1:(26~250)；
The preparation method of described graphene oxide solution is as follows:
1., it will be existed after the nitric acid of 100g graphite flakes, the 540mL concentrated sulfuric acid and 70mL uniformly mixing with 200r/min speed 24h is stirred at room temperature, with deionized water filtering and washing three times, solid is taken, and is then to dry 24h under conditions of 60 DEG C in temperature, Obtain compound between graphite layers；The mass concentration of described nitric acid is 69%；The mass concentration of the described concentrated sulfuric acid is 95.5%； Described graphite flake is 50 mesh graphite flakes；Described graphite flake is 50 mesh graphite flakes；
2. compound between graphite layers, are incubated 15s under conditions of temperature is 1050 DEG C, expanded graphite is obtained；
3., by the potassium permanganate of 1g expanded graphite, the 200mL concentrated sulfuric acid and 10g, normal temperature mixes equal in three-neck flask It is even, 250mL hydrogen peroxide solution is then slowly added into, continues to stir 30min after solution is changed into glassy yellow from yellow green, uses salt Aqueous acid filtering and washing 3 times, obtains solid, and solid is put into bag filter and sealed；The mass concentration of the described concentrated sulfuric acid is 95.5%；The concentration of described hydrogen peroxide solution is 7.5%；The mass concentration of described aqueous hydrochloric acid solution encloses for 9.5%~ 10.5%；
4., by step 3. in bag filter place in deionized water stand 5 days~7 days, measure deionized water pH value；
If the pH that 5. 4. step measures is not 5~6, deionized water is changed, repeat step is 4. to the deionized water of measurement PH is 5~6, i.e., graphene oxide solution is obtained in bag filter；
2nd, 3D printing：The marking ink that step 2 is obtained is printed into 3-dimensional component using 3D printer；
3rd, solidify：The 3-dimensional component that step 3 is obtained is placed in culture dish and sealed, and is then 15 DEG C~20 DEG C in temperature Under conditions of solidify 12h~24h；
4th, it is heat-treated：Component after step 3 is solidified takes out from culture dish, is then carried out under inert gas shielding High-temperature process, the temperature of high-temperature process is 550 DEG C~1000 DEG C, and the time of high-temperature process is 30min~100min, that is, is led Graphene/inorganic polymer composite material.
Embodiment two：Present embodiment from unlike embodiment one：It is continuous described in step one The preparation method of fiber reinforcement inorganic polymer base composite material is as follows：
1), kaolin calcines 1.5~2.5h under the conditions of 700~800 DEG C and obtains metakaolin；
2), the silicate solutions that metakaolin and mass concentration are 46~62% are 1 according to weight ratio：1.5~5.5 ratio Example is mixed to prepare inorganic polymer matrix, and ceramic particle is then added into inorganic polymer matrix is mixed to get inorganic polymer Batch, wherein inorganic polymer matrix are 1 with ceramic particle weight ratio：0.1~1；Silicate in the silicate solutions For potassium silicate, sodium metasilicate or cesium silicate；Described ceramic particle is silica, aluminum oxide, zirconium oxide, zirconium boride, mullite, carbon SiClx or silicon nitride, and a diameter of 0.5mm~5mm of ceramic particle；
3) continuous fiber one-way fabric, is added to 5~12min of sonic oscillation in inorganic polymer batch, ultrasound is shaken The frequency swung is 15~50KHz, that is, prepreg is made；Described continuous fiber is carbon fiber, silicon carbide fibre, steel fibre or oxygen Change aluminum fiber；
4), by the laying of step 3 prepreg in a mold, 20~120min is solidified under the conditions of 50~90 DEG C；
5) step 4 product, is subjected to high-temperature process under vacuum or inert gas shielding, treatment temperature is 800~ 1300 DEG C, treatment time is 30~120min, that is, obtains strengthened inorganic polymer base composite material of continuous fiber.
It is other identical with embodiment one.
Embodiment three：Present embodiment from unlike embodiment one：3-dimensional structure described in step 2 Part is shaped as cylinder, netted, triangle honeycomb or rectangle honeycomb.It is other identical with embodiment one.
Embodiment four：Present embodiment from unlike embodiment one：3D described in step 2 is beaten The air pressure of print is 5psi~80psi, and the syringe needle internal diameter of 3D printing is 0.06mm~1.55mm, and the syringe needle material of 3D printing is moulded for PE The flexible syringe needle of material, metal needle or PP.It is other identical with embodiment one.
Embodiment five：Present embodiment from unlike embodiment one：3D described in step 2 is beaten The mode of print prints for extruded type.It is other identical with embodiment one.
Embodiment six：Present embodiment from unlike embodiment one：Step one 4. described in it is saturating The molecular cut off that analysis bag is is 14000.It is other identical with embodiment one.
Embodiment seven：Present embodiment from unlike embodiment one：Inertia described in step 4 Gas is nitrogen or argon gas.It is other identical with embodiment one.
The effect of the present invention is verified by tests below：
Experiment one：This experiment prepares conductive graphene/inorganic polymer composite material for a kind of use 3D printing technique Method, is specifically followed the steps below：
First, strengthened inorganic polymer base composite material of continuous fiber and graphene oxide solution are mixed under conditions of 0 DEG C Merge mechanical agitation 20min, obtain marking ink；The concentration of described graphene oxide solution is 2wt%；Described oxidation stone The mass ratio of graphene oxide and strengthened inorganic polymer base composite material of continuous fiber in black alkene solution is 1:30；
The preparation method of described graphene oxide solution is as follows:
1., it will be existed after the nitric acid of 100g graphite flakes, the 540mL concentrated sulfuric acid and 70mL uniformly mixing with 200r/min speed 24h is stirred at room temperature, with deionized water filtering and washing three times, solid is taken, and is then to dry 24h under conditions of 60 DEG C in temperature, Obtain compound between graphite layers；The mass concentration of described nitric acid is 69%；The mass concentration of the described concentrated sulfuric acid is 95.5%； Described graphite flake is 50 mesh graphite flakes；Described graphite flake is 50 mesh graphite flakes；
2. compound between graphite layers, are incubated 15s under conditions of temperature is 1050 DEG C, expanded graphite is obtained；
3., by the potassium permanganate of 1g expanded graphite, the 200mL concentrated sulfuric acid and 10g, normal temperature mixes equal in three-neck flask It is even, 250mL hydrogen peroxide solution is then slowly added into, continues to stir 30min after solution is changed into glassy yellow from yellow green, uses salt Aqueous acid filtering and washing 3 times, obtains solid, and solid is put into bag filter and sealed；The mass concentration of the described concentrated sulfuric acid is 95.5%；The concentration of described hydrogen peroxide solution is 7.5%；The mass concentration of described aqueous hydrochloric acid solution is enclosed for 10%；
4., by step 3. in bag filter place in deionized water stand 5 days, measure deionized water pH value；
If the pH that 5. 4. step measures is not 5~6, deionized water is changed, repeat step is 4. to the deionized water of measurement PH is 5~6, i.e., graphene oxide solution is obtained in bag filter；
2nd, 3D printing：The marking ink that step 2 is obtained is printed into 3-dimensional component using 3D printer；
3rd, solidify：The 3-dimensional component that step 3 is obtained is placed in culture dish and sealed, then in the condition that temperature is 15 DEG C Lower solidification 20h；
4th, it is heat-treated：Component after step 3 is solidified takes out from culture dish, is then carried out under inert gas shielding High-temperature process, the temperature of high-temperature process is 1000 DEG C, and the time of high-temperature process is 1h, that is, obtains conductive graphene/inorganic polymeric Thing composite.
Sealing and curing prevents the volatilization of moisture in culture dish in this test procedure three, and the volatilization of moisture can cause outside sample Surface portion water content is reduced, and is caused its solidification incomplete, so as to cause sample state of cure inconsistent, is influenceed sample mechanical property Energy；Component strength after solidifying in testing procedure three is 200Mpa.
The average grain diameter of the graphene oxide layer prepared in this test procedure one is about 100 μm, and thickness is about 2.7nm.
Table 1 is the mechanical test data after testing in one after step 3 solidification and being heat-treated in step 4, it can be seen that 3D Print component is handled after 1h under 1000 DEG C of hot conditions, and structure remains unchanged completely, and elastic modelling quantity is improved close to 250%, and it resists Compressive Strength and failure strain are still considerable, and mechanical property remains unchanged well, have shown preferable heat resistance.
Table 1

Claims (7)

1. a kind of method that use 3D printing technique prepares conductive graphene/inorganic polymer composite material, it is characterised in that make The method that conductive graphene/inorganic polymer composite material is prepared with 3D printing technique is to follow the steps below：
First, strengthened inorganic polymer base composite material of continuous fiber and graphene oxide solution are mixed simultaneously under conditions of 0 DEG C Mechanical agitation 20min~30min, obtains marking ink；The concentration of described graphene oxide solution is 0.5wt%~4wt%； The mass ratio of graphene oxide and strengthened inorganic polymer base composite material of continuous fiber in described graphene oxide solution For 1:(26~250)；
The preparation method of described graphene oxide solution is as follows:
1. with 200r/min speed in room temperature after, the nitric acid of 100g graphite flakes, the 540mL concentrated sulfuric acid and 70mL is uniformly mixed Lower stirring 24h, with deionized water filtering and washing three times, takes solid, is then to dry 24h under conditions of 60 DEG C in temperature, obtains Compound between graphite layers；The mass concentration of described nitric acid is 69%；The mass concentration of the described concentrated sulfuric acid is 95.5%；It is described Graphite flake be 50 mesh graphite flakes；Described graphite flake is 50 mesh graphite flakes；
2. compound between graphite layers, are incubated 15s under conditions of temperature is 1050 DEG C, expanded graphite is obtained；
3., by the potassium permanganate of 1g expanded graphite, the 200mL concentrated sulfuric acid and 10g, normal temperature is well mixed in three-neck flask, so 250mL hydrogen peroxide solution is slowly added to afterwards, is continued to stir 30min after solution is changed into glassy yellow from yellow green, is used hydrochloric acid water Solution filtering and washing 3 times, obtains solid, and solid is put into bag filter and sealed；The mass concentration of the described concentrated sulfuric acid is 95.5%； The concentration of described hydrogen peroxide solution is 7.5%；The mass concentration of described aqueous hydrochloric acid solution is enclosed for 9.5%~10.5%；
4., by step 3. in bag filter place in deionized water stand 5 days~7 days, measure deionized water pH value；
If the pH that 5. 4. step measures is not 5~6, deionized water is changed, 4. repeat step is 5 to the deionized water pH of measurement ~6, i.e., graphene oxide solution is obtained in bag filter；
2nd, 3D printing：The marking ink that step 2 is obtained is printed into 3-dimensional component using 3D printer；
3rd, solidify：The 3-dimensional component that step 3 is obtained is placed in culture dish and sealed, then in the bar that temperature is 15 DEG C~20 DEG C Solidify 12h~24h under part；
4th, it is heat-treated：Component after step 3 is solidified is taken out from culture dish, and high temperature is then carried out under inert gas shielding Processing, the temperature of high-temperature process is 550 DEG C~1000 DEG C, and the time of high-temperature process is 30min~100min, that is, obtains conductive stone Black alkene/inorganic polymer composite material.
2. one kind according to claim 1 prepares conductive graphene/inorganic polymer composite material using 3D printing technique Method, it is characterised in that the preparation method of the strengthened inorganic polymer base composite material of continuous fiber described in step one is such as Under：
1), kaolin calcines 1.5~2.5h under the conditions of 700~800 DEG C and obtains metakaolin；
2), the silicate solutions that metakaolin and mass concentration are 46~62% are 1 according to weight ratio：1.5~5.5 ratio is mixed Close and inorganic polymer matrix is made, ceramic particle is then added into inorganic polymer matrix and is mixed to get inorganic polymer cooperation Material, wherein inorganic polymer matrix are 1 with ceramic particle weight ratio：0.1~1；Silicate in the silicate solutions is silicon Sour potassium, sodium metasilicate or cesium silicate；Described ceramic particle is silica, aluminum oxide, zirconium oxide, zirconium boride, mullite, carborundum Or silicon nitride, and a diameter of 0.5mm~5mm of ceramic particle；
3) continuous fiber one-way fabric, is added to 5~12min of sonic oscillation in inorganic polymer batch, sonic oscillation Frequency is 15~50KHz, that is, prepreg is made；Described continuous fiber is carbon fiber, silicon carbide fibre, steel fibre or aluminum oxide Fiber；
4), by the laying of step 3 prepreg in a mold, 20~120min is solidified under the conditions of 50~90 DEG C；
5) step 4 product, is subjected to high-temperature process under vacuum or inert gas shielding, treatment temperature is 800~1300 DEG C, treatment time is 30~120min, that is, obtains strengthened inorganic polymer base composite material of continuous fiber.
3. one kind according to claim 1 prepares conductive graphene/inorganic polymer composite material using 3D printing technique Method, it is characterised in that 3-dimensional component described in step 2 is shaped as cylinder, netted, triangle honeycomb or rectangle honeycomb.
4. one kind according to claim 1 prepares conductive graphene/inorganic polymer composite material using 3D printing technique Method, it is characterised in that the air pressure of the 3D printing described in step 2 is 5psi~80psi, and the syringe needle internal diameter of 3D printing is 0.06mm~1.55mm, the syringe needle material of 3D printing is the flexible syringe needle of PE plastics, metal needle or PP.
5. one kind according to claim 1 prepares conductive graphene/inorganic polymer composite material using 3D printing technique Method, it is characterised in that the mode of the 3D printing described in step 2 be extruded type printing.
6. one kind according to claim 1 prepares conductive graphene/inorganic polymer composite material using 3D printing technique Method, it is characterised in that step one 4. described in the bag filter molecular cut off that is be 14000.
7. one kind according to claim 1 prepares conductive graphene/inorganic polymer composite material using 3D printing technique Method, it is characterised in that inert gas described in step 4 is nitrogen or argon gas.
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CN114988787A (en) * 2021-04-13 2022-09-02 兰州大学 Preparation method of cement-based strengthening and toughening material based on 3D coaxial printing molding
CN114988787B (en) * 2021-04-13 2023-03-21 兰州大学 Preparation method of cement-based strengthening and toughening material based on 3D coaxial printing molding
CN114835499A (en) * 2022-06-17 2022-08-02 哈尔滨工业大学 Preparation method of silicon carbide ceramic with complex shape and high forming precision
CN114944491A (en) * 2022-07-14 2022-08-26 天津工业大学 Three-dimensional gradient carbon skeleton composite material for inhibiting growth of lithium dendrites and preparation method thereof

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