Two-dimensional laminar flow graphene coating and titanium sheet composite material composed of graphene nanosheets and preparation method thereof
阅读说明：本技术 一种由石墨烯纳米片组成的二维层流石墨烯涂层与钛片的复合材料及其制备方法 (Two-dimensional laminar flow graphene coating and titanium sheet composite material composed of graphene nanosheets and preparation method thereof ) 是由 丁书凯 陈婧怡 杨英俊 于 2020-12-25 设计创作，主要内容包括：本发明公开了一种由石墨烯纳米片组成的二维层流石墨烯涂层与钛片的复合材料及其制备方法,该复合材料以钛基材料作为基体,纳米级二维层流石墨烯涂层完全覆盖基体表面,所述涂层面积与基体相同,厚度为10～100nm,涂层由0.5～4nm大小的石墨烯片组成。本发明具有生物相容性好、制作工艺简单、应用简便、成本低廉的特点。(The invention discloses a composite material of a two-dimensional laminar flow graphene coating and a titanium sheet, which is composed of graphene nanosheets, and a preparation method of the composite material. The invention has the characteristics of good biocompatibility, simple manufacturing process, simple and convenient application and low cost.)
1. The composite material of the two-dimensional laminar flow graphene coating and the titanium sheet is composed of graphene nanosheets, and is characterized in that the composite material takes a titanium-based material as a substrate, the nanoscale two-dimensional laminar flow graphene coating completely covers the surface of the substrate, the area of the coating is the same as that of the substrate, the thickness of the coating is 10-100 nm, and the coating is composed of graphene sheets with the size of 0.5-4 nm.
2. A preparation method of a composite material of a two-dimensional laminar flow graphene coating composed of graphene nano sheets and titanium sheets is characterized by comprising the following steps;
(1) mutually dissolving acrylic resin monomer, medium-chain glycerol or medium-chain triglyceride, photoinitiator and modified castor oil at 25-40 ℃ to obtain an oil phase solution;
(2) at room temperature, adding deionized water into the oil phase solution obtained in the step (1) in a certain proportion, and performing mechanical stirring, homogeneous emulsification, ultrasonic emulsification or microfluidization emulsification to obtain emulsion;
(3) injecting the emulsion obtained in the step (2) by using a propelling device at room temperature for UV light radiation curing to prepare a mixed solution;
(4) putting the mixed solution prepared in the step (3) into a dialysis bag, sealing the dialysis bag, and putting the dialysis bag into deionized water for dialysis to prepare a mixed solution;
(5) freeze-drying the mixed solution prepared in the step (4) to prepare polymer gel;
(6) sequentially washing TC4 tablets with acetone, ethanol and distilled water by ultrasonic waves for 20 minutes respectively, and drying;
(7) treating the TC4 sheet treated in the step (6) in oxygen plasma;
(8) uniformly coating the TC4 pieces treated in the step (7) with the polymer gel prepared in the step (5);
(9) and (4) calcining the TC4 sheet coated with the polymer gel prepared in the step (8) for a period of time under inert gas to prepare the composite material of the two-dimensional laminar graphene coating and the titanium sheet.
3. The method for preparing the composite material of the titanium sheet and the two-dimensional laminar graphene coating composed of the graphene nanoplatelets as claimed in claim 2, wherein the propylene resin monomer in the step (1) is one of 1, 6-hexanediol diacrylate and tripropylene glycol diacrylate;
the medium-chain glycerol or medium-chain triglyceride in the step (1) is one of Labrafac CC and Labrafac WL 1349;
the photoinitiator in the step (1) is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone;
the modified castor oil in the step (1) is one of Cremopher EL, Cremopher ELP and Cremopher RH 40.
4. The preparation method of the composite material of the two-dimensional laminar graphene coating composed of graphene nanoplatelets and the titanium sheet according to claim 2, wherein the acrylic resin monomer, medium-chain glycerol or medium-chain triglyceride, the photoinitiator and the modified castor oil in the step (1) are mixed in a ratio of (1-25): (1-30): (0.1-0.9): (3-50) in a mass ratio.
5. The preparation method of the composite material of the two-dimensional laminar graphene coating composed of graphene nanoplatelets and the titanium sheet according to claim 2, wherein the oil phase solution in the step (2) is mixed with deionized water in a ratio of (1-3): (2-5) mixing and stirring;
and (3) stirring in the step (2) is vortex stirring, magnetic stirring and microflow emulsification.
6. The method for preparing the composite material of the two-dimensional laminar graphene coating composed of the graphene nanoplatelets and the titanium sheet according to claim 2, wherein the radiation curing technology in the step (3) is ultraviolet radiation light irradiation curing;
the injection speed in the step (3) is 100 mu m/min-2 ml/min;
the irradiation intensity of the radiant light in the step (3) is 10-100%.
7. The preparation method of the composite material of the two-dimensional laminar flow graphene coating composed of the graphene nanoplatelets and the titanium sheet according to claim 2, wherein the cut-off molecular weight of the dialysis bag in the step (4) is 8000-14000;
the dialysis time in the step (4) is 2-10 days;
the processing time in the step (4) is 10-500 s.
8. The method for preparing the composite material of the two-dimensional laminar graphene coating composed of the graphene nanoplatelets and the titanium sheet according to claim 2, wherein the processing power in the step (7) is 10 w-500 w.
9. The preparation method of the composite material of the titanium sheet and the two-dimensional laminar graphene coating composed of the graphene nanoplatelets as claimed in claim 2, wherein the calcination temperature in the step (9) is 400-2000 ℃;
the calcination time in the step (9) is 1-4 h.
10. The method for preparing the composite material of the two-dimensional laminar graphene coating composed of the graphene nanoplatelets and the titanium sheet according to claim 2, wherein the inert atmosphere in the step (9) is nitrogen, argon, hydrogen and argon mixture.
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a composite material of a two-dimensional laminar graphene coating and a titanium sheet, which is composed of graphene nano sheets, and a preparation method thereof.
Background
Titanium (Ti) -based materials have been widely used in artificial implants such as dental implants, micro-implants and metal plates due to their excellent mechanical properties, corrosion resistance and low bio-toxicity. On the other hand, the titanium can not be fused with the bone tissue interface after being directly implanted into the body, so that the interface instability is caused, and the success rate of the implant is influenced. Currently, bioinert is the biggest obstacle to the use of titanium-based materials in biomedical applications.
The graphene is a compound of having sp2A hexagonal honeycomb two-dimensional nano material formed by hybridized orbital carbon atoms. In recent years, graphene has been widely used in the biomedical field due to its low biotoxicity, excellent mechanical properties and ability to regulate the bioelectrochemical microenvironment. For example; drug delivery systems, biosensors and tissue regeneration. On the other hand, graphene is reported to have not only biocompatibility but also the ability to induce osteogenic and chondrogenic differentiation of stem cells. Therefore, the interface instability of the titanium-based implant can be effectively improved by modifying the surface of the titanium-based implant with the graphene.
How to simply and efficiently prepare the graphene @ titanium biological composite material becomes an important problem in the direction of biological materials. The existing method for preparing the graphene @ titanium biological composite material mainly comprises a powder metallurgy method, an in-situ synthesis method and a hydrothermal reduction method. For example: in the powder metallurgy method, firstly, graphene oxide and titanium powder are uniformly mixed in a powder mixer. Then, the molding is performed by press molding or static pressure pre-pressing. And finally, reducing the graphene oxide by adopting methods such as hot pressing, hot isostatic pressing or spark plasma sintering and the like, and preparing the bulk composite material. Although the processes are complex, the preparation period is long, and the process parameters are not controllable, the application of the graphene @ titanium biological composite material is greatly hindered due to the influence on the performance of the composite material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the composite material of the two-dimensional laminar flow graphene coating and the titanium sheet, which is composed of the graphene nanosheets, and the preparation method thereof, and the composite material has the characteristics of good biocompatibility, simple manufacturing process, simplicity and convenience in application and low cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
the composite material of the two-dimensional laminar flow graphene coating and the titanium sheet comprises a graphene nanosheet, wherein the titanium-based material is used as a substrate, the nanoscale two-dimensional laminar flow graphene coating completely covers the surface of the substrate, the area of the coating is the same as that of the substrate, the thickness of the coating is 10-100 nm, and the coating is composed of graphene sheets with the size of 0.5-4 nm.
A preparation method of a composite material of a two-dimensional laminar flow graphene coating composed of graphene nano sheets and titanium sheets comprises the following steps;
(1) mutually dissolving acrylic resin monomer, medium-chain glycerol or medium-chain triglyceride, photoinitiator and modified castor oil at 25-40 ℃ to obtain an oil phase solution;
(2) at room temperature, adding deionized water into the oil phase solution obtained in the step (1) in a certain proportion, and performing mechanical stirring, homogeneous emulsification, ultrasonic emulsification or microfluidization emulsification to obtain emulsion;
(3) injecting the emulsion obtained in the step (2) by using a propelling device at room temperature for UV light radiation curing to prepare a mixed solution;
(4) putting the mixed solution prepared in the step (3) into a dialysis bag, sealing the dialysis bag, and putting the dialysis bag into deionized water for dialysis to prepare a mixed solution;
(5) freeze-drying the mixed solution prepared in the step (4) to prepare polymer gel;
(6) sequentially washing TC4 tablets with acetone, ethanol and distilled water by ultrasonic waves for 20 minutes respectively, and drying;
(7) treating the TC4 sheet treated in the step (6) in oxygen plasma;
(8) uniformly coating the TC4 pieces treated in the step (7) with the polymer gel prepared in the step (5);
(9) and (4) calcining the TC4 sheet coated with the polymer gel prepared in the step (8) for a period of time under inert gas to prepare the composite material of the two-dimensional laminar graphene coating and the titanium sheet.
The propylene resin monomer in the step (1) is one of 1, 6-hexanediol diacrylate (HDDA) and tripropylene glycol diacrylate (TPGDA).
The medium-chain glycerol or medium-chain triglyceride in the step (1) is one of Labrafac CC and Labrafac WL 1349;
the photoinitiator in the step (1) is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone;
the modified castor oil in the step (1) is one of Cremopher EL, Cremopher ELP and Cremopher RH 40.
The acrylic resin monomer, the medium-chain glycerol or the medium-chain triglyceride, the photoinitiator and the modified castor oil in the step (1) are as follows (1-25): (1-30): (0.1-0.9):
(3-50) in a mass ratio.
The oil phase solution in the step (2) and deionized water are mixed according to the ratio of (1-3): (2-5) mixing and stirring.
And (3) stirring in the step (2) is vortex stirring, magnetic stirring and microflow emulsification.
The radiation curing technology in the step (3) is Ultraviolet (UV) radiation light irradiation curing.
The injection speed in the step (3) is 100 mu m/min-2 ml/min.
The irradiation intensity of the radiant light in the step (3) is 10-100%.
The cut-off molecular weight of the dialysis bag in the step (4) is 8000-14000.
And (4) the dialysis time in the step (4) is 2-10 days.
The processing time in the step (4) is 10-500 s.
The processing power in the step (7) is 10 w-500 w.
The calcination temperature in the step (9) is 400-2000 ℃.
The calcination time in the step (9) is 1-4 h.
And (4) the inert atmosphere in the step (9) is a mixed gas of nitrogen, argon and hydrogen argon.
The invention has the beneficial effects that:
the organic coating graphene precursor obtained by the method can be directly and uniformly coated on the surface of titanium. In the oxidation-reduction calcination process, a two-dimensional laminar graphene coating (2 DLM) is directly synthesized on the surface of the titanium alloyG). The preparation methodThe method has low cost, uses green and easily-obtained raw materials, and has simple preparation process; and the application is simple and convenient, the material is environment-friendly, and secondary pollution can not be caused.
Synthetic two-dimensional laminar flow matrix carbon material (2 DLM)G) Has compact section and smooth surface, and is favorable to cell adhesion, biocompatibility improvement and stem cell differentiation regulation.
The nano emulsion can be coated on other special-shaped titanium alloys before the composite material is calcined, and two-dimensional laminar graphene coatings are uniformly distributed on the surfaces of the special-shaped titanium alloys.
Drawings
FIG. 1 is a schematic representation of a TC4 titanium sheet uniformly coated with a gel polymer.
FIG. 2 is calcined 2DLMGSchematic representation of @ TC4 biocomposite.
FIG. 3 is a 2DLMGSchematic SEM image of @ TC4 biocomposite.
FIG. 4 is a 2DLMGRaman spectrum diagram of @ TC4 biological composite material.
FIG. 5 is the adhesion of mesenchymal stem cells to 2DLMGTypical fluorescence scheme at @ TC 4.
Detailed Description
The present invention will be described in further detail with reference to examples.
A preparation method of a composite material of a two-dimensional laminar flow graphene coating composed of graphene nano sheets and titanium sheets comprises the following steps;
(1) mutually dissolving acrylic resin monomer, medium-chain glycerol or medium-chain triglyceride, photoinitiator and modified castor oil at 25-40 ℃ to obtain an oil phase solution; the acrylic resin monomer is a monomer forming a polymer organic framework; the medium-chain glycerol or the medium-chain triglyceride is used as a nano-droplet stabilizer, the photoinitiator can initiate acrylic resin monomers to react to form an organic nano-bulk polymer, and the modified castor oil is used for stabilizing the nano-emulsion.
(2) At room temperature, adding deionized water into the oil phase solution obtained in the step (1) in a certain proportion, and performing mechanical stirring, homogeneous emulsification, ultrasonic emulsification or microfluidization emulsification to obtain emulsion; after the oil phase and the water phase are mixed, the hydrophobic group of the modified castor oil is positioned on the inner side of the oil phase, and the hydrophilic group is positioned on the outer side of the oil phase, so that the structural stability of the modified castor oil is maintained.
(3) Injecting the emulsion obtained in the step (2) by using a propelling device at room temperature for UV light radiation curing to prepare a mixed solution; and (3) irradiating the nano emulsion formed in the step (2) by ultraviolet rays and Ultraviolet (UV) light, and initiating an acrylic resin monomer to react by using a photoinitiator to form a nano polymer organic framework.
(4) Putting the mixed solution prepared in the step (3) into a dialysis bag, sealing the dialysis bag, and putting the dialysis bag into deionized water for dialysis to prepare a mixed solution; due to the different osmotic pressure inside and outside the dialysis bag, the modified castor oil was removed.
(5) Freeze-drying the mixed solution prepared in the step (4) to prepare polymer gel;
(6) sequentially washing TC4 tablets with acetone, ethanol and distilled water by ultrasonic waves for 20 minutes respectively, and drying;
(7) treating the TC4 sheet treated in the step (6) in oxygen plasma;
(8) uniformly coating the TC4 pieces treated in the step (7) with the polymer gel prepared in the step (5);
(9) and (4) calcining the TC4 sheet prepared in the step (8) for a period of time under inert gas to prepare the composite material of the two-dimensional laminar flow graphene coating and the titanium sheet.
The propylene resin monomer in the step (1) is one of 1, 6-hexanediol diacrylate (HDDA) and tripropylene glycol diacrylate (TPGDA).
The medium-chain glycerol or medium-chain triglyceride in the step (1) is one of Labrafac CC and Labrafac WL 1349;
the photoinitiator in the step (1) is one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone;
the modified castor oil in the step (1) is one of Cremopher EL, Cremopher ELP and Cremopher RH 40.
The acrylic resin monomer, the medium-chain glycerol or the medium-chain triglyceride, the photoinitiator and the modified castor oil in the step (1) are as follows (1-25): (1-30): (0.1-0.9): (3-50) in a mass ratio.
The oil phase solution in the step (2) and deionized water are mixed according to the ratio of (1-3): (2-5) mixing and stirring.
And (3) stirring in the step (2) is vortex stirring, magnetic stirring and microflow emulsification.
The radiation curing technology in the step (3) is Ultraviolet (UV) radiation light irradiation curing.
The injection speed in the step (3) is 100 mu m/min-2 ml/min.
The irradiation intensity of the radiant light in the step (3) is 10-100%.
The cut-off molecular weight of the dialysis bag in the step (4) is 8000-14000.
And (4) the dialysis time in the step (4) is 2-10 days.
The processing time in the step (4) is 10-500 s.
The processing power in the step (7) is 10 w-500 w.
The calcination temperature in the step (9) is 400-2000 ℃.
The calcination time in the step (9) is 1-4 h.
And (4) the inert atmosphere in the step (9) is a mixed gas of nitrogen, argon and hydrogen argon.
Example 1
5g of propylene resin monomer 1, 6-hexanediol diacrylate (HDDA), 5g of Labrafac CC were mixed homogeneously at room temperature, and 4% of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl]-1-acetone photoinitiator, and then 4g of modified castor oil Cremopher RH 40 to prepare an oil phase mixture. And 2g of the 14g of oil-phase mixture is divided into 7 parts, and the oil phase and the water are mixed according to the mass ratio of 5:3 and are swirled to prepare the nano emulsion. The nano emulsion is irradiated and solidified by ultraviolet light at the advancing speed of 0.2ml/min in an injection pump to prepare the organic nano body type polymer. Putting the UV-cured substance into a dialysis bag, sealing, dialyzing in deionized water for 5 days to remove Cremopher RH 40, freeze-drying to obtain polymerAnd (4) gelling. Respectively ultrasonically cleaning Ti-6Al-4V (TC4) sheets with the thickness of 10 multiplied by 1mm in acetone, ethanol and distilled water for 20 minutes, and then drying. The titanium sheet was treated in a plasma cleaner at an oxygen plasma power of 50w for 100 s. After treatment, the titanium sheet was uniformly coated with a gel polymer. In the argon atmosphere, titanium sheet coated with nanogel polymer is calcined at the temperature of 500 ℃ for 20 hours to obtain 2DLMG@ TC4 biocomposite.
Example 2
1g of acrylic resin monomer 1, 6-hexanediol diacrylate (HDDA) and 1g of Labrafac CC were mixed homogeneously at room temperature, 0.1g of photoinitiator 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl-]1-acetone, and then 10g of modified castor oil Cremopher RH 40 to prepare an oil phase mixture. The oil phase mixture is divided into 10 parts, and the oil phase and the water are mixed according to the mass ratio of 1:5 and are swirled to prepare the nano emulsion. The nano emulsion is irradiated and solidified by Ultraviolet (UV) radiation with 10 percent of irradiation intensity at the advancing speed of 100 mu m/min in an injection pump to prepare the nano organic framework emulsion. Putting the UV-cured substance into a dialysis bag with a carrying and remaining molecular weight of 8000, sealing, putting into deionized water, dialyzing for 10 days to remove Cremopher RH 40, and freeze-drying to obtain the gel polymer of the nano organic framework. A5X 2mm industrial pure titanium (TA3) sheet was ultrasonically cleaned in acetone, ethanol and distilled water for 20 minutes, respectively, and then dried. TA3 sheet 100s was treated in a plasma cleaner at an oxygen plasma power of 50 w. After treatment, the gel polymer was uniformly coated on a sheet of TA 3. Calcining TA3 sheet coated nano organic frame gel polymer at 1000 deg.C for 4h in hydrogen argon atmosphere to obtain 2DLMG@ TA3 biocomposite.
Example 3
25g of the acrylic monomer tripropylene glycol diacrylate (TPGDA) and 30g of Labrafac WL 1349 are mixed homogeneously at room temperature, 0.9g of the photoinitiator 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl]1-acetone, and then adding 50g of modified castor oil Cremopher ELP to prepare an oil phase mixture. The oil phase mixture is divided into 10 parts, and the oil phase and the water are mixed according to the mass ratio of 3:2 and are swirled to prepare the nano emulsion. The nano emulsion is injected into a pump at a speed of 2mThe nano organic frame emulsion is prepared by irradiating and curing Ultraviolet (UV) radiation with 100 percent of irradiation intensity at the advancing speed of l/min. Putting the UV-cured substance into a dialysis bag with a residual molecular weight of 14000, sealing, putting into deionized water, dialyzing for 2 days to remove Cremopher ELP, and freeze-drying to obtain the gel polymer of the nano organic framework. Respectively ultrasonically cleaning Ti-6Al-4V (TC4) sheets with the size of 5 multiplied by 2mm in acetone, ethanol and distilled water for 20 minutes, and then drying. After treatment, the sheets of TC4 were uniformly coated with gel polymer. Calcining the nanometer organic frame gel polymer in nitrogen atmosphere at 2000 ℃ for 1h to obtain 2DLMG@ TC4 biocomposite.
As shown in fig. 1: the gel polymer may be uniformly coated on the TC4 titanium sheet.
As shown in fig. 2: calcined 2DLMGThe @ TC4 biological composite material has uniform coating, rich luster and good bonding strength.
As shown in fig. 3: 2DLMGThe @ TC4 biological composite material can see the texture of the substrate, and the coating is thin and the thickness reaches the nanometer level.
As shown in fig. 4: 2DLMGRaman spectrum 1348cm of @ TC4 biological composite material-1The D peak appearing nearby is used to characterize structural defects or edges in the graphene sample. 1580cm-1The G peak appearing nearby reflects the symmetry and order of the material. I isD/IG0.95 indicates a higher degree of graphitization.
As shown in fig. 5: 2DLMGThe mesenchymal stem cells on the surface of the @ TC4 biological composite material are spindle-shaped, and the cell activity and adhesion condition are better.
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