CN106513287B - Enhance the radiotolerant graphite ene coatings of corrosion resistance and heat-conductive characteristic - Google Patents
Enhance the radiotolerant graphite ene coatings of corrosion resistance and heat-conductive characteristic Download PDFInfo
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- CN106513287B CN106513287B CN201610876551.3A CN201610876551A CN106513287B CN 106513287 B CN106513287 B CN 106513287B CN 201610876551 A CN201610876551 A CN 201610876551A CN 106513287 B CN106513287 B CN 106513287B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/34—Coverings or external coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
- B05D2202/15—Stainless steel
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- Life Sciences & Earth Sciences (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of radiotolerant graphite ene coatings for enhancing corrosion resistance and heat-conductive characteristic, carries out graphene coating treatment technology to high-level waste glass solidified body container containing.The graphene coating layer thickness is 1~10 μm, is coated on high-level waste glass solidified body container containing outer surface, and the high-level waste glass solidified body container containing is austenitic stainless steel material.The high-level waste glass solidified body container containing is with a thickness of 2~10mm.The radiotolerant graphite ene coatings of enhancing corrosion resistance and heat-conductive characteristic of the present invention, by the good physical and chemical performance of graphene itself, the corrosion resistance of disposal container can not only be improved, and the decay heat of high-level waste glass solidified body can also be exported in time in time, to improve performance and the service life of container containing, increase temporary library.
Description
Technical field
The present invention relates to high-level waste glass solidified body container containings to carry out graphene coating treatment technology, improves and contains
Container corrosion resistance and heat-conductive characteristic.
Background technique
High-level waste safe disposal is that current nuclear power development and nuclear technology utilize one of the outstanding problem faced, and radiation
The key points and difficulties problem of property waste management.Geological disposal is considered as the disposal method of most engineering prospect, " at geology
Set " refer to underground stablize geological structure in (hundreds of meters or deeper inside usually below earth's surface) facility in carry out solid radioactive
Property Waste disposal so that radioactive waste with biosphere is permanently effective is isolated.It is with the containing of radionuclide, is isolated into core
Intracardiac appearance, with multibarrier (including waste body, packing container, buffering backfilling material and disposition country rock) for main means, and
Year up to ten thousand the above public health and environmental protection be basic security target extremely complex system engineering." Chinese people's republicanism
State's Law on the Prevention and Control of Radioactive Pollution " clearly stipulate that China's high-level waste implements the deep geological disposal concentrated.
High-level waste includes that height puts glass solidified body, other types high-level solid waste and α solid waste.High-level waste glass
The radioactive activity highest of glass solidified body, heat release amount is maximum, toxicity is most strong, therefore high activity liquid waste glass solidified body is packed into contain and hold
Before carrying out geological disposal after device, since its initial heat release amount is about 2000W, it is therefore desirable to keep in 30~50 in temporary library
Year, so that its heat release amount is down to 700~800W.
Graphene is by carbon atom with sp2What the monoatomic layer of hydridization connection was constituted, basic structural unit is organic material
Most stable of benzene hexatomic ring, theoretic throat are only 0.35nm in material, are the most thin two-dimensional materials found at present.Graphene
It is the basic unit for constituting other graphite materials, the fullerene of zero dimension can be become with warpage, curl into one-dimensional carbon nanotube
Or it is stacked to three-dimensional graphite (see Fig. 1).This special construction has contained abundant and peculiar physical phenomenon, makes graphene table
Reveal many excellent physicochemical properties, as the intensity of graphene be in test material it is highest, reach 130GPa, be steel
More than 100 times；Its carrier mobility is up to 1.5 × 104cm2·V-1·s-1, it is the antimony with highest mobility being currently known
2 times of phosphide material, more than 10 times of commercial silicon wafer mobility, under given conditions (such as cryogenic quenching), mobility is even
Up to 2.5 × 105cm2·V-1·s-1；The thermal conductivity of graphene is up to 5 × 103W·m-1·K-1, it is 3 times of diamond；Stone
The particularity such as black alkene corrosion resistance also with super strength, room-temperature quantum Hall effect (Hall effect) and room-temperature ferromagnetic
Matter.
It to sum up analyzes, at present in conceptual design and Safety Evaluation Mode used by high-level waste geology treatment, height is put useless
The material that uses of object glass solidified body container containing design is austenitic stainless steel, and wall thickness is about 5mm, and the service life of container containing is
By the corrosion resistance and heating conduction of metal itself.Therefore graphene disposition splendid attire surface is added to as coating to be formed
Graphite ene coatings, the domestic research in this field also belong to blank.
Summary of the invention
The purpose of the present invention is to provide the radiotolerant graphene paintings of a kind of enhancing corrosion resistance and heat-conductive characteristic
Layer；The present invention carries out graphene coating treatment technology to high-level waste glass solidified body container containing, and it is resistance to improve container containing
Corrosive nature and heat-conductive characteristic.
Realize the technical solution of the object of the invention:
A kind of radiotolerant graphite ene coatings enhancing corrosion resistance and heat-conductive characteristic of the present invention, the graphite
Ene coatings are coated on high-level waste glass solidified body container containing outer surface, the high-level waste glass with a thickness of 1~10 μm
Solidified body container containing is austenitic stainless steel material.
A kind of radiotolerant graphite ene coatings enhancing corrosion resistance and heat-conductive characteristic as described above, described in
High-level waste glass solidified body container containing is with a thickness of 2~10mm.
A kind of height of the radiotolerant graphite ene coatings with enhancing corrosion resistance and heat-conductive characteristic of the present invention is put useless
Object glass solidified body container containing, which is coated with graphite ene coatings, described
Graphene coating layer thickness be 1~10 μm, the high-level waste glass solidified body container containing be austenitic stainless steel material.
A kind of height of radiotolerant graphite ene coatings with enhancing corrosion resistance and heat-conductive characteristic as described above
Put waste glass solidified body container containing, described in high-level waste glass solidified body container containing with a thickness of 2~10mm.
The preparation of the radiotolerant graphite ene coatings of any enhancing corrosion resistance and heat-conductive characteristic of the present invention
Method comprising following steps:
(a) a certain amount of graphene oxide is added in a certain amount of aqueous solution, is handled by radiation effect, make graphene
It is dispersed in water-based system and is restored partial oxidation of graphite alkene, forms graphene dispersing solution；
(b) high-level waste glass solidified body container containing outer surface is surface-treated, removes austenitic stainless steel table
The oxide layer in face；
(c) the resulting graphene oxide of step (a) is coated on and is surface-treated resulting high-level waste glass through step (b)
Solidified body container containing surface；
(d) the high-level waste glass solidified body container containing with graphite oxide ene coatings of step (c) is placed in inertia
In the environment of gas shield, heat treatment 3-5 hours is carried out at 150~250 DEG C, to remove the moisture in graphene oxide and incite somebody to action
Graphene oxide is reduced into graphene, combines graphene firmly on high-level waste glass solidified body container containing surface.
A kind of radiotolerant graphite ene coatings enhancing corrosion resistance and heat-conductive characteristic as described above, repeat to walk
Suddenly (c) applies the graphene on high-level waste glass solidified body container containing surface to step (d) by repeatedly coating and being heat-treated
The thickness of layer reaches 1~10 μm.
A kind of preparation of graphite ene coatings enhancing corrosion-resistant and heating conduction and resistance to large dosage γ irradiation as described above
Method, the processing of radiation effect described in step (a) is carries out gamma-rays irradiation, irradiation under the dosage of 500~1000Gy/h
Time is 35~70 hours.
A kind of preparation side of the radiotolerant graphite ene coatings of enhancing corrosion resistance and heat-conductive characteristic as described above
A certain amount of graphene oxide is added in a certain amount of water described in step (a) by method, the specific mass ratio of the two be 1:(5 ×
106~1 × 107)。
A kind of preparation side of the radiotolerant graphite ene coatings of enhancing corrosion resistance and heat-conductive characteristic as described above
Method, inert gas described in step (d) are argon gas.
A kind of preparation side of the radiotolerant graphite ene coatings of enhancing corrosion resistance and heat-conductive characteristic as described above
Method, surface treatment described in step (b) are polishing, sandblasting or plating.
Effect of the invention is that:
The radiotolerant graphite ene coatings of enhancing corrosion resistance and heat-conductive characteristic of the present invention, by graphene
Itself good physical and chemical performance can not only improve the corrosion resistance of disposal container, and can also in time put height useless
The decay heat of object glass solidified body exports in time, to improve performance and the service life of container containing, increases temporary library.
It is provided by the present invention to put the increased graphite ene coatings in glass solidified body container containing surface in height and mention
The corrosion resistance of high disposal container, and can also in time export the decay heat of high-level waste glass solidified body in time, thus
In performance and the service life for improving container containing, increase the temporary ability and safety of temporary library.
The container containing of containing graphene coating provided in the present invention compared with current pure metal disposal container, have with
Lower advantage:
(1) since graphene has good corrosion resistance, it can be improved the overall corrosion resistance energy of temporary container,
Reduce corrosion rate, in the case where simulating temporary environment (big irradiation dose (3MGy), high temperature (170 DEG C), around for air), graphitiferous
The austenitic stainless steel corrosion rate of ene coatings is pure metal 8% hereinafter, enhancing the corrosion resistance of disposal container, significantly
Extend the service life of disposal container；
(2) increase the heating conduction of disposal container itself, the disposal container heating conduction of containing graphene coating increases by 40%
More than, the high decay heat for putting glass solidified body can be allowed quickly to conduct into ambient enviroment；
(3) by increasing the corrosion resistance and heating conduction of container containing, increase the temporary ability and safety of temporary library
Property.
Detailed description of the invention
Fig. 1 is single-layer graphene and its derivative schematic diagram；
Fig. 2 is graphite ene coatings schematic diagram of the invention.
In figure: 1. graphite ene coatings；2. high-level waste glass solidified body container containing.
Specific embodiment
In the following with reference to the drawings and specific embodiments to a kind of enhancing corrosion resistance of the present invention and heat-conductive characteristic
Radiotolerant graphite ene coatings be further described.
Embodiment 1
A kind of radiotolerant graphite ene coatings enhancing corrosion resistance and heat-conductive characteristic of the present invention, such as Fig. 2
Shown, which is coated on high-level waste glass solidified body with a thickness of 1~10 μm (such as: 1 μm, 5 μm or 10 μm)
2 outer surface of container containing, the high-level waste glass solidified body container containing are austenitic stainless steel material.
The high-level waste glass solidified body container containing is with a thickness of 2~10mm (such as: 2mm, 6mm or 10mm).
Embodiment 2
A kind of radiotolerant graphite ene coatings with enhancing corrosion resistance and heat-conductive characteristic of the present invention
High-level waste glass solidified body container containing, 2 outer surface of high-level waste glass solidified body container containing are applied coated with graphene
Layer 1, the graphene coating layer thickness are 1~10 μm (such as: 1 μm, 5 μm or 10 μm), the high-level waste glass solidification
Body container containing is austenitic stainless steel material.
A kind of radiotolerant graphite ene coatings with enhancing corrosion resistance and heat-conductive characteristic of the present invention
High-level waste glass solidified body container containing, the high-level waste glass solidified body container containing is with a thickness of 2~10mm (example
Such as: 2mm, 6mm or 10mm).
Embodiment 3
The radiotolerant graphene of any enhancing corrosion resistance and heat-conductive characteristic described in embodiment 1 or embodiment 2 applies
The preparation method of layer comprising following steps:
(a) a certain amount of graphene oxide is added in a certain amount of aqueous solution, is handled by radiation effect, make graphene
It is dispersed in water-based system and is restored partial oxidation of graphite alkene, forms graphene dispersing solution；The radiation effect processing
To carry out gamma-rays irradiation under the dosage of 800Gy/h, irradiation time is 50 hours.Both described graphene oxide and water
Specific mass ratio is 1:8 × 106。
(b) high-level waste glass solidified body container containing outer surface is surface-treated (such as: polishing, sandblasting or electricity
Plating), remove the oxide layer of austenite stainless steel surface；
(c) the resulting graphene oxide of step (a) is coated on and is surface-treated resulting high-level waste glass through step (b)
Solidified body container containing surface；
(d) the high-level waste glass solidified body container containing with graphite oxide ene coatings of step (c) is placed in inertia
In the environment of gas (such as: argon gas) protection, heat treatment 4 hours is carried out at 190 DEG C, to remove the moisture in graphene oxide
And graphene oxide is reduced into graphene, combine graphene firmly in high-level waste glass solidified body container containing table
Face.
(e) step (c) is repeated to step (d) by repeatedly coating and being heat-treated, and contains high-level waste glass solidified body
The thickness of the graphite ene coatings of vessel surface reaches 5 μm.
Embodiment 4
The radiotolerant graphene of any enhancing corrosion resistance and heat-conductive characteristic described in embodiment 1 or embodiment 2 applies
The preparation method of layer comprising following steps:
(a) a certain amount of graphene oxide is added in a certain amount of aqueous solution, is handled by radiation effect, make graphene
It is dispersed in water-based system and is restored partial oxidation of graphite alkene, forms graphene dispersing solution；The radiation effect processing
To carry out gamma-rays irradiation under the dosage of 500Gy/h, irradiation time is 70 hours.Both described graphene oxide and water
Specific mass ratio is 1:5 × 106；
(b) high-level waste glass solidified body container containing outer surface is surface-treated (such as: polishing, sandblasting or electricity
Plating), remove the oxide layer of austenite stainless steel surface；
(c) the resulting graphene oxide of step (a) is coated on and is surface-treated resulting high-level waste glass through step (b)
Solidified body container containing surface；
(d) the high-level waste glass solidified body container containing with graphite oxide ene coatings of step (c) is placed in inertia
In the environment of gas (such as: argon gas) protection, heat treatment 5 hours is carried out at 150 DEG C, to remove the moisture in graphene oxide
And graphene oxide is reduced into graphene, combine graphene firmly in high-level waste glass solidified body container containing table
Face.
(e) step (c) is repeated to step (d) by repeatedly coating and being heat-treated, and contains high-level waste glass solidified body
The thickness of the graphite ene coatings of vessel surface reaches 1 μm.
Embodiment 5
The radiotolerant graphene of any enhancing corrosion resistance and heat-conductive characteristic described in embodiment 1 or embodiment 2 applies
The preparation method of layer comprising following steps:
(a) a certain amount of graphene oxide is added in a certain amount of aqueous solution, is handled by radiation effect, make graphene
It is dispersed in water-based system and is restored partial oxidation of graphite alkene, forms graphene dispersing solution；The radiation effect processing
To carry out gamma-rays irradiation under the dosage of 1000Gy/h, irradiation time is 35 hours.The graphene oxide and water two
The specific mass ratio of person is 1:1 × 107。
(b) high-level waste glass solidified body container containing outer surface is surface-treated (such as: polishing, sandblasting or electricity
Plating), remove the oxide layer of austenite stainless steel surface；
(c) the resulting graphene oxide of step (a) is coated on and is surface-treated resulting high-level waste glass through step (b)
Solidified body container containing surface；
(d) the high-level waste glass solidified body container containing with graphite oxide ene coatings of step (c) is placed in inertia
In the environment of gas (such as: argon gas) protection, heat treatment 3 hours is carried out at 250 DEG C, to remove the moisture in graphene oxide
And graphene oxide is reduced into graphene, combine graphene firmly in high-level waste glass solidified body container containing table
Face.
(e) step (c) is repeated to step (d) by repeatedly coating and being heat-treated, and contains high-level waste glass solidified body
The thickness of the graphite ene coatings of vessel surface reaches 10 μm.
Claims (6)
1. a kind of preparation method of the radiotolerant graphite ene coatings of enhancing corrosion resistance and heat-conductive characteristic, feature exist
In: this method comprises the following steps:
(a) a certain amount of graphene oxide is added in a certain amount of aqueous solution, is handled by radiation effect, make graphene uniform
It is scattered in water-based system and is restored partial oxidation of graphite alkene, forms graphene dispersing solution；The described radiation effect processing for
Gamma-rays irradiation is carried out under the dosage of 500~1000Gy/h, irradiation time is 35~70 hours；It is described by a certain amount of oxygen
Graphite alkene is added in a certain amount of water, and the specific mass ratio of the two is 1:(5 × 106~1 × 107)；
(b) high-level waste glass solidified body container containing outer surface is surface-treated, removal austenite stainless steel surface
Oxide layer；
(c) the resulting graphene oxide of step (a) is coated on and is surface-treated resulting high-level waste glass solidification through step (b)
Body container containing surface；
(d) the high-level waste glass solidified body container containing with graphite oxide ene coatings of step (c) is placed in inert gas
In the environment of protection, heat treatment 3-5 hours is carried out at 150~250 DEG C, to remove the moisture in graphene oxide and will aoxidize
Graphene is reduced into graphene, combines graphene firmly on high-level waste glass solidified body container containing surface.
2. the radiotolerant graphite ene coatings of a kind of enhancing corrosion resistance according to claim 1 and heat-conductive characteristic
Preparation method, it is characterised in that: the graphite ene coatings (1) are coated on high-level waste glass solidified body with a thickness of 1~10 μm
Container containing (2) outer surface, the high-level waste glass solidified body container containing are austenitic stainless steel material.
3. the radiotolerant graphite ene coatings of a kind of enhancing corrosion resistance according to claim 2 and heat-conductive characteristic
Preparation method, it is characterised in that: the high-level waste glass solidified body container containing is with a thickness of 2~10mm.
4. the radiotolerant graphite ene coatings of a kind of enhancing corrosion resistance according to claim 1 and heat-conductive characteristic
Preparation method, it is characterised in that: repeat step (c) to step (d) by repeatedly coating and being heat-treated, keep high-level waste glass solid
The thickness for changing the graphite ene coatings on body container containing surface reaches 1~10 μm.
5. the radiotolerant graphite ene coatings of a kind of enhancing corrosion resistance according to claim 1 and heat-conductive characteristic
Preparation method, it is characterised in that: inert gas described in step (d) is argon gas.
6. the radiotolerant graphite ene coatings of a kind of enhancing corrosion resistance according to claim 1 and heat-conductive characteristic
Preparation method, it is characterised in that: surface treatment described in step (b) is polishing, sandblasting or plating.
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