CN115368766B - Fluorinated graphene/titanium dioxide composite anti-corrosion filler and preparation method thereof - Google Patents
Fluorinated graphene/titanium dioxide composite anti-corrosion filler and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 162
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 81
- 239000000945 filler Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000005260 corrosion Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012153 distilled water Substances 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 229920006334 epoxy coating Polymers 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 12
- 238000011049 filling Methods 0.000 abstract description 10
- 239000011229 interlayer Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 13
- 239000011737 fluorine Substances 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000003682 fluorination reaction Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention discloses a preparation method of a fluorinated graphene/titanium dioxide composite anti-corrosion filler, which comprises the following steps: s1: dispersing graphene oxide in distilled water, and performing ultrasonic treatment; s2: adding a fluorotitanate solution and a boric acid solution into the solution obtained in the step S1, and uniformly stirring; s3: transferring the mixed solution obtained in the step S2 into a polytetrafluoroethylene lining in a hydrothermal kettle for hydrothermal reaction; s4: washing the product after the reaction in the step S3 with distilled water, and drying to obtain the fluorinated graphene/titanium dioxide composite anticorrosive filler. The preparation method is simple in process and short in time consumption, and the prepared titanium dioxide of the fluorinated graphene/titanium dioxide composite anti-corrosion filler grows on the fluorinated graphene in situ, and the fluorinated graphene/titanium dioxide composite anti-corrosion filler and the titanium dioxide are mutually overlapped to form an interlayer punctiform filling structure, so that the barrier property and the anti-corrosion property are excellent.
Description
Technical Field
The invention belongs to the field of preparation of anti-corrosion fillers, and particularly relates to a fluorinated graphene/titanium dioxide composite anti-corrosion filler and a preparation method thereof.
Background
The report issued by the national corrosion and protection society in 2014 indicates that the total cost of the corrosion in China is up to 3.24% of that of GDP, so that not only is the economic loss caused, but also various safety accidents are caused by the corrosion. Organic coating protection is an important corrosion protection method, wherein the filler plays a role in blocking penetration of corrosive media, and plays an important role in coating corrosion protection.
Graphene is a two-dimensional planar carbon material, the ultra-thin thickness and the excellent barrier property of the graphene lead the graphene to be widely used in the field of anti-corrosion fillers, but the excellent conductivity of the graphene can lead the corrosion speed of a coating to be increased, so that the protective effect of the coating is greatly reduced, and the reduction of the conductivity of the graphene has become a key problem for popularizing the application of the graphene coating. The fluorinated graphene is a product of partially or completely fluorinated graphene, is one of important components of graphene derivatives, has low conductivity, and has theoretical calculation, so that compared with the graphene, the fluorinated graphene has a larger barrier potential to oxygen atoms and chloride ions (Applied Surface Science,2020 (499): 143962), and has huge application potential as a corrosion barrier filler.
The preparation method of the fluorinated graphene comprises a mechanical stripping method, a gas fluorination method, a modified Hummer method, a hydrothermal fluorination method and the like. Some of these methods are capable of producing fluorinated graphene that is structurally intact, or high in fluorine content, but suffer from a number of drawbacks. Most of grinding aids used in the mechanical stripping method are harmful to the body and can also cause the shedding of fluorine atoms on the fluorinated graphene; the gas fluorination method has high requirements on equipment, and a gas fluorine source is expensive and is not easy to store; the modified Hummer method needs to use a series of raw materials of strong acid and strong oxidant, special attention is required to be paid to personal safety during operation, and the prepared fluorinated graphene has an incomplete structure; the fluorination rate of the fluorinated graphene prepared by the hydrothermal fluorination method is relatively low, and the preparation period is long. These drawbacks limit the large-scale application and further research of fluorinated graphene.
Disclosure of Invention
Aiming at the technical problems to be solved, the invention provides a preparation method of a fluorinated graphene/titanium dioxide composite anti-corrosion filler, wherein titanium dioxide in the prepared fluorinated graphene/titanium dioxide composite anti-corrosion filler grows on the fluorinated graphene in situ, and the fluorinated graphene/titanium dioxide composite anti-corrosion filler and the fluorinated graphene are mutually overlapped to form an interlayer punctiform filling structure. The preparation method also has the advantages of simple preparation process, in-situ compounding, short time, no toxicity of fluorine source, easy storage and the like.
In order to achieve the aim of the invention, the invention provides a preparation method of a fluorinated graphene/titanium dioxide composite anti-corrosion filler, which comprises the following steps:
s1: dispersing graphene oxide in distilled water, and performing ultrasonic treatment;
s2: adding a fluorotitanate solution and a boric acid solution into the solution obtained in the step S1, and uniformly stirring;
s3: transferring the mixed solution obtained in the step S2 into a polytetrafluoroethylene lining in a hydrothermal kettle for hydrothermal reaction;
s4: washing the product after the reaction in the step S3 with distilled water, and drying to obtain the fluorinated graphene/titanium dioxide composite anticorrosive filler.
Compared with the prior art, the preparation method selects fluorotitanate as a fluorine source, prepares the fluorinated graphene/titanium dioxide composite anti-corrosion filler through a hydrothermal method, and has the advantages of simple preparation process, in-situ compounding, short time, non-toxicity of the fluorine source, easiness in storage and the like. The titanium dioxide of the graphene fluoride/titanium dioxide composite anticorrosive filler prepared by the method grows in situ on the graphene fluoride, plays a role in physical separation between the graphene fluoride, avoids mutual agglomeration of the graphene fluoride, and enables the large-plane structure of more graphene fluoride to be utilized, so that the excellent separation performance of the graphene fluoride is fully exerted. Furthermore, the fluorinated graphene and the titanium dioxide are mutually alternated to form an interlayer punctiform filling structure, and the structure combines the high barrier potential of the fluorinated graphene and the stable chemical property of the titanium dioxide, so that the corrosive medium is difficult to penetrate deeply and deeply layer by layer and damage. In addition, the fluorinated graphene and the titanium dioxide have low conductivity, electrons are difficult to transfer between the fluorinated graphene and the titanium dioxide, and the occurrence probability of electrochemical corrosion is reduced.
Preferably, in step S1, the dosage ratio of the graphene oxide to the distilled water is 100 mg/60 ml. Compared with other organic solvents, distilled water is nontoxic and easy to obtain, and the graphene oxide is better in dispersion stability in distilled water after ultrasonic delamination, so that agglomeration in a short time can be avoided, and uniform preparation of the fluorinated graphene and titanium dioxide is ensured.
Preferably, in step S1, the sonication time is 1h.
Preferably, in step S2, the mass concentration of the fluorotitanate solution is 0.0125-0.1 g/mL, and the mass concentration of the boric acid solution is 0.0125-0.1 g/mL; the weight ratio of graphene oxide to fluorotitanate to boric acid in the mixed solution is 1 (2.5-20) to 2.5-20.
Preferably, in step S2, the fluorotitanate is one or more of ammonium fluorotitanate, sodium fluorotitanate and potassium fluorotitanate. Compared with the traditional fluorine source hydrofluoric acid, fluorine gas and diethylaminosulfur trifluoride, the fluorotitanate is convenient to store as a solid and is not easy to change due to external influence.
Preferably, in step S3, the temperature of the hydrothermal reaction is 160-200 ℃, and the hydrothermal reaction time is 4-12 hours.
Preferably, in step S4, the product is washed 5 to 10 times with distilled water and then dried at 100℃for 2 hours.
The invention also provides the fluorinated graphene/titanium dioxide composite anticorrosive filler prepared by the preparation method of the fluorinated graphene/titanium dioxide composite anticorrosive filler, which has excellent barrier property and anticorrosive property.
Further, the fluorinated graphene/titanium dioxide composite anticorrosive filler has a multilayer structure, and titanium dioxide grows on the fluorinated graphene in situ and is uniformly distributed.
The invention also provides application of the fluorinated graphene/titanium dioxide composite anti-corrosion filler in an epoxy coating, wherein the filler is added into epoxy resin and coated on the surface of a substrate to be protected to form a 50-70 mu m coating, so that the substrate can be effectively protected, and the corrosion resistance of the substrate is greatly improved.
According to the invention, graphene oxide, fluotitanate and boric acid are used as raw materials, and the fluorinated graphene/titanium dioxide composite anti-corrosion filler is prepared by a hydrothermal method, wherein titanium dioxide grows on the fluorinated graphene in situ and alternates with the fluorinated graphene, so that an interlayer punctiform filling structure is formed. The in-situ growth of the titanium dioxide effectively prevents aggregation between the fluorinated graphene layers, so that the fluorinated graphene with a large-area planar structure is widely distributed, and the excellent barrier property of the fluorinated graphene is fully utilized. The interlayer punctiform filling structure formed by the staggered fluorinated graphene with excellent barrier property and the low-chemical-activity titanium dioxide improves the difficulty of penetration and damage of the corrosive medium to the structure. In addition, the low conductivity of the fluorinated graphene and the titanium dioxide is not beneficial to electron transmission between interlayer punctiform filling structures, so that the electrochemical corrosion process is inhibited. Therefore, the fluorinated graphene/titanium dioxide composite anticorrosive filler has excellent barrier property and excellent anticorrosive effect.
Drawings
Fig. 1 is a schematic diagram of the preparation principle of the fluorinated graphene/titanium dioxide composite anticorrosive filler.
Fig. 2 is an SEM image of the fluorinated graphene/titanium dioxide composite anticorrosive filler prepared in example 2.
FIG. 3 is a FTIR spectrum of the fluorinated graphene/titanium dioxide composite anticorrosive filler prepared in examples 1 to 4.
FIG. 4 is a graph of salt spray test surfaces of two epoxy coatings at different time periods; wherein fig. 4a is a surface diagram of a pure epoxy coating 0h, and fig. 4b is a surface diagram of the pure epoxy coating after 144h salt spray test; fig. 4c is a surface view of an epoxy coating 0h containing the fluorinated graphene/titanium dioxide composite anti-corrosion filler prepared in example 2, and fig. 4d is a surface view of an epoxy coating 144h salt spray tested containing the fluorinated graphene/titanium dioxide composite anti-corrosion filler prepared in example 2.
Detailed Description
The invention will be further illustrated with reference to specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form or modification thereof.
Example 1:
referring to fig. 1, the preparation method of the graphene fluoride/titanium dioxide composite anticorrosive filler comprises the following steps:
adding 100mg of graphene oxide into 60mL of distilled water, and performing ultrasonic treatment for 60min; then sequentially adding 20mL of sodium fluotitanate and 20mL of boric acid solution with mass concentration of 0.05g/mL, and stirring for 5min; transferring the obtained solution into a polytetrafluoroethylene lining in a hydrothermal kettle, reacting for 6 hours at 185 ℃, and finally washing and drying the reacted product to obtain the fluorinated graphene/titanium dioxide composite anti-corrosion filler. The fluorine element content of the prepared fluorinated graphene/titanium dioxide composite anti-corrosion filler is 4.54% by EDS characterization measurement.
Example 2:
the preparation method comprises the following steps of:
adding 100mg of graphene oxide into 60mL of water, and performing ultrasonic treatment for 60min; then sequentially adding 20mL of ammonium fluotitanate and 20mL of boric acid solution with mass concentration of 0.05g/mL, and stirring for 5min; transferring the obtained solution into a polytetrafluoroethylene lining in a hydrothermal kettle, reacting for 6 hours at 180 ℃, and finally washing and drying the reacted product to obtain the fluorinated graphene/titanium dioxide composite anti-corrosion filler. The fluorine element content of the prepared fluorinated graphene/titanium dioxide composite anticorrosive filler is 4.84% by EDS characterization measurement.
Example 3:
the preparation method comprises the following steps of:
adding 100mg of graphene oxide into 60mL of distilled water, and performing ultrasonic treatment for 60min; then sequentially adding 20mL of potassium fluotitanate solution with the mass concentration of 0.05g/mL and 20mL of boric acid solution with the mass concentration of 0.1g/mL, and stirring for 5min; transferring the obtained solution into a polytetrafluoroethylene lining in a hydrothermal kettle, reacting for 6 hours at 180 ℃, and finally washing and drying the reacted product to obtain the fluorinated graphene/titanium dioxide composite anti-corrosion filler. The fluorine element content of the prepared fluorinated graphene/titanium dioxide composite anticorrosive filler is 4.35% by EDS characterization measurement.
Example 4:
the preparation method comprises the following steps of:
adding 100mg of graphene oxide into 60mL of distilled water, and performing ultrasonic treatment for 60min; then sequentially adding 20mL of sodium fluotitanate and 20mL of boric acid solution with mass concentration of 0.025g/mL, and stirring for 5min; transferring the obtained solution into a polytetrafluoroethylene lining in a hydrothermal kettle, reacting for 6 hours at 180 ℃, and finally washing and drying the reacted product to obtain the fluorinated graphene/titanium dioxide composite anti-corrosion filler. The fluorine element content of the prepared fluorinated graphene/titanium dioxide composite anticorrosive filler is 3.84% by EDS characterization measurement.
Examples 5 to 20
The following formulation may also be used to prepare the graphene fluoride/titanium dioxide composite anticorrosive filler, with specific reference to table 1, and the steps for preparing the graphene fluoride/titanium dioxide composite anticorrosive filler of examples 5 to 20 are the same as those of examples 1 to 4, except that specific parameters in each step are selected.
TABLE 1 reaction conditions Table for examples 5-20
Structural characterization and performance testing:
please refer to fig. 2, which is an SEM image of the fluorinated graphene/titanium dioxide composite anticorrosive filler prepared in example 2, wherein the left image is magnified 10000 times and the right image is magnified 30000 times. As shown in fig. 2, the titanium dioxide is white round particles, the fluorinated graphene is gray massive solid, the titanium dioxide grows on the fluorinated graphene in situ, and the distribution is uniform. In addition, it can be seen from the SEM image at 30000 x magnification: the sample has a multi-layer structure, each layer has white particles distributed on the sample, and the prepared fluorinated graphene/titanium dioxide composite anti-corrosion filler has an interlayer punctiform filling structure.
Referring to FIG. 3, there is shown an FTIR spectrum of a fluorinated graphene/titanium dioxide composite anticorrosive filler prepared in each example, 1215cm from the chart -1 The C-F bond present and 652cm -1 The stretching vibration peak of Ti-O-Ti can show that the fluorinated graphene/titanium dioxide composite anti-corrosion filler has been successfully prepared.
Comparing the fluorine content of the fluorinated graphene/titanium dioxide composite anticorrosive filler prepared by the invention with that of the fluorinated graphene reported in other documents, it can be found that: the fluorination rate of the invention is larger than or similar to the values reported in the literature only when the reaction time is 6 h. Compared with the existing preparation method of the fluorinated graphene, the preparation method of the fluorinated graphene is simple in preparation process and short in preparation time.
Table 2 fluorine content of fluorinated graphene reported in literature
The salt spray test is one of the important tests for evaluating the protective performance of the coating. The graphene fluoride/titanium dioxide composite anticorrosive filler prepared in example 2 is added into epoxy resin (accounting for 0.5% of the total mass of the coating) according to a certain proportion, and is coated on a metal substrate, the thickness is controlled to be 50-70 mu m, a pure epoxy coating without the graphene fluoride/titanium dioxide composite anticorrosive filler is prepared according to the same method, diagonal lines are drawn on the two coatings by a knife, the epoxy coating containing example 2 and the pure epoxy coating are placed into a salt spray box, and a neutral salt spray test is carried out according to the GB/T10125-2012 standard.
Referring to fig. 4, fig. 4a is a surface view of a pure epoxy coating 0h, and fig. 4b is a surface view of a pure epoxy coating after 144h salt spray test; fig. 4c is a surface view of an epoxy coating 0h containing the fluorinated graphene/titanium dioxide composite anti-corrosion filler prepared in example 2, and fig. 4d is a surface view of an epoxy coating 144h salt spray tested containing the fluorinated graphene/titanium dioxide composite anti-corrosion filler prepared in example 2. From the graph, after 144h of salt spray test, the epoxy coating containing the fluorinated graphene/titanium dioxide composite anti-corrosion filler of example 2 only has one corrosion at the scratch, two bubbles are formed outside the scratch, the degree is slight, and the pure epoxy coating has multiple corrosion at the scratch and has serious degree. The test results show that the protective performance of the original coating is greatly improved after the embodiment is added, and the special structure of the fluorinated graphene/titanium dioxide composite anti-corrosion filler plays an important role in preventing corrosive medium from penetrating.
In summary, graphene oxide, fluotitanate and boric acid are used as raw materials, and the fluorinated graphene/titanium dioxide composite anti-corrosion filler is prepared by a hydrothermal method, wherein titanium dioxide grows on the fluorinated graphene in situ and alternates with the fluorinated graphene, so that an interlayer punctiform filling structure is formed. The in-situ growth of the titanium dioxide effectively prevents aggregation between the fluorinated graphene layers, so that the fluorinated graphene with a large-area planar structure is widely distributed, and the excellent barrier property of the fluorinated graphene is fully utilized. The interlayer punctiform filling structure formed by the staggered fluorinated graphene with excellent barrier property and the low-chemical-activity titanium dioxide improves the difficulty of penetration and damage of the corrosive medium to the structure. In addition, the low conductivity of the fluorinated graphene and the titanium dioxide is not beneficial to electron transmission between interlayer punctiform filling structures, so that the electrochemical corrosion process is inhibited. Therefore, the fluorinated graphene/titanium dioxide composite anticorrosive filler has excellent barrier property and excellent anticorrosive effect.
The invention is not limited to the use of the description and embodiments listed, which can be applied to various fields suitable for the invention, and further modifications and variations can be easily realized by those skilled in the art without departing from the spirit and the essence of the invention, but these corresponding modifications and variations shall fall within the scope of protection claimed by the invention.
The above description is only a few examples of the present invention and is not intended to limit the embodiments and the protection scope of the present invention, and it should be appreciated by those skilled in the art that equivalent substitutions and obvious changes made by the content of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a fluorinated graphene/titanium dioxide composite anticorrosive filler is characterized by comprising the following steps: the method comprises the following steps:
s1: dispersing graphene oxide in distilled water, and performing ultrasonic treatment;
s2: adding a fluorotitanate solution and a boric acid solution into the solution obtained in the step S1, and uniformly stirring; the mass concentration of the fluorotitanate solution is 0.0125-0.1 g/mL, and the mass concentration of the boric acid solution is 0.0125-0.1 g/mL; the weight ratio of graphene oxide to fluorotitanate to boric acid in the mixed solution is 1 (2.5-20): 2.5-20; the fluotitanate is one or more of ammonium fluotitanate, sodium fluotitanate and potassium fluotitanate;
s3: transferring the mixed solution obtained in the step S2 into a polytetrafluoroethylene lining in a hydrothermal kettle for hydrothermal reaction; the temperature of the hydrothermal reaction is 160-200 ℃, and the hydrothermal reaction time is 4-12 h;
s4: and (3) washing the product after the reaction in the step (S3) with distilled water for 5-10 times, and then drying for 2 hours at the temperature of 100 ℃ to obtain the fluorinated graphene/titanium dioxide composite anti-corrosion filler.
2. The method for preparing the fluorinated graphene/titanium dioxide composite anticorrosive filler according to claim 1, characterized in that: in the step S1, the dosage ratio of the graphene oxide to the distilled water is 100 mg/60 mL.
3. The method for preparing the fluorinated graphene/titanium dioxide composite anticorrosive filler according to claim 1, characterized in that: in step S1, the ultrasonic treatment time is 1h.
4. The fluorinated graphene/titanium dioxide composite anticorrosive filler is characterized in that: the preparation method of the fluorinated graphene/titanium dioxide composite anticorrosive filler is characterized in that the fluorinated graphene/titanium dioxide composite anticorrosive filler is prepared by adopting the preparation method of the fluorinated graphene/titanium dioxide composite anticorrosive filler.
5. The fluorinated graphene/titanium dioxide composite anticorrosive filler according to claim 4, characterized in that: the fluorinated graphene/titanium dioxide composite anticorrosive filler has a multilayer structure, and titanium dioxide grows on the fluorinated graphene in situ and is uniformly distributed.
6. Use of the fluorinated graphene/titanium dioxide composite anticorrosive filler according to claim 4 or 5 in epoxy coatings.
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| CN102728337A (en) * | 2012-06-08 | 2012-10-17 | 华北电力大学 | Graphite / titanium dioxide composite material and preparation method thereof |
| CN106824065A (en) * | 2016-12-29 | 2017-06-13 | 贵州科学院 | The graphene-based TiO of humic acid in a kind of removal rural potable water2Nano composite material and preparation method thereof |
| CN110305559A (en) * | 2019-07-10 | 2019-10-08 | 四川轻化工大学 | A kind of corrosion resistant heat-conductive coating and preparation method thereof |
| CN110776805A (en) * | 2019-10-14 | 2020-02-11 | 广州盛门新材料科技有限公司 | Water-based fluorinated graphene coating and preparation method and application thereof |
| CN111244406A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Fluorinated graphene modified titanium dioxide material, and preparation and application thereof |
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Patent Citations (5)
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| CN102728337A (en) * | 2012-06-08 | 2012-10-17 | 华北电力大学 | Graphite / titanium dioxide composite material and preparation method thereof |
| CN106824065A (en) * | 2016-12-29 | 2017-06-13 | 贵州科学院 | The graphene-based TiO of humic acid in a kind of removal rural potable water2Nano composite material and preparation method thereof |
| CN111244406A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Fluorinated graphene modified titanium dioxide material, and preparation and application thereof |
| CN110305559A (en) * | 2019-07-10 | 2019-10-08 | 四川轻化工大学 | A kind of corrosion resistant heat-conductive coating and preparation method thereof |
| CN110776805A (en) * | 2019-10-14 | 2020-02-11 | 广州盛门新材料科技有限公司 | Water-based fluorinated graphene coating and preparation method and application thereof |
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