CN102690579B - Reparation method of self-embrittled radioactive decontamination coating - Google Patents
Reparation method of self-embrittled radioactive decontamination coating Download PDFInfo
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- CN102690579B CN102690579B CN201210201015.5A CN201210201015A CN102690579B CN 102690579 B CN102690579 B CN 102690579B CN 201210201015 A CN201210201015 A CN 201210201015A CN 102690579 B CN102690579 B CN 102690579B
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Abstract
The invention discloses a preparation method of a self-embrittled radioactive decontamination coating. The self-embrittled radioactive decontamination coating is prepared by performing copolymerization on a methacrylic acid monomer and a methyl methacrylate monomer through emulsion. Crosslinking agent is added into the prepared polymer emulsion so as to realize complexing and crosslinking of polymer molecular chain sections in the emulsion, and the emulsion can be self-embrittled and stripped off after being painted, molded and solidified, thus being separated from a contaminated object; and a certain amount of complexing agent is added into the polymer emulsion to perform a complexing adsorption action on radioactive nuclide particles, thus fulfilling the aim of clearing radioactive nuclide. The self-embrittled coating can be applied to radioactive decontamination in general occasions and on the surface of complicated structural parts; and brittle sheets produced by decontamination can be collected mechanically, so that the radiation amount to an operator can be reduced.
Description
Technical field
The present invention relates to nuclear pollution decontamination technology field, in particular a kind of preparation method from crisp type radioactive decontamination coating.
Background technology
In the retired and various nuclear emergency incident response of core, removing radionuclide contamination is all key issue.Decontamination refers to removes or alleviates surperficial alpha-contamination process, and the object of decontamination is the radioactive activity in order to reduce facility and environment, continues safe handling or carries out place and open to realize facility.The essence of decontamination process is that radioactive pollutant is transferred to secondary refuse from the surface of decontamination object.Decontamination technology major part is transplanted and is come from other technologies field, is then improved development according to the work characteristics of radioactive decontamination (as high in the decontamination factor of radiation hazradial bundle problem, pollution problem again, requirement) again.The actual decontamination process using can be divided into two large classes substantially now: physical technology of removing pollution and chemical subtraction.Traditional physical technology of removing pollution method has wiping, top layer to peel off etc., and chemical subtraction is for cleaning Polluted area, facility etc. with chemical solvents (organic solvent, acid solution, complex solution, salts solution etc.).These decontamination methods have been obtained certain effect and have been solved some practical problemss; But exist clean effect undesirable or produce a lot of new problems such as refuse, waste liquid.At present, the physics and chemistry means of various modern have been applied in nuclear installation decontamination, and as ultrasonic, plasma body, laser, supercritical technology, electrochemical method etc., with regard to current various decontamination technologies, various technology all have some limitations.The body material of Contaminated Parts, pollutant kind, decontamination object etc., all have restrictive function to the selection of decontamination technology.Thereby in actual nuclear installation operation or retired process, decontamination is the integrated application of multiple technologies often.
Peelable film decontamination technology is a kind of decontamination method that newly-developed gets up, it refers to develops a kind of type material of peeling off dirt-removing functions that has, it is before coating, be generally liquid-type coating, coating contaminated facility, after equipment surface, through natural air drying after a while, form thin film body on facility surface, with general coating difference be, this coating thin-film body forming can pass through machinery or manual operation again, by its peel-off device surface, simultaneously because coating experiences a series of chemistry and physical action and original equipment surface pollutent rejected or part is removed in equipment surface, finally through once or several times operations, finally reach contaminated equipment surface decontamination object.Peelable decontamination coating in general sense, be one or more high molecular polymers that contain functional group be matrix (all kinds of rubber, polystyrene, polyvinyl chloride, chlorinated polyvinyl chloride etc.), if and functional type auxiliary agent in adding in the mixture of itself and solvent, this comprises: film coalescence aid, emulsification function auxiliary agent, treating compound, dispersion agent, functional type coagent, dirt-removing functions auxiliary agent etc.This kind of decontamination technology easy construction, safety, non-secondary pollution, produce the compressible burning of refuse, particularly suitable additive method is difficult to the occasion of construction, as huge nuclear reactor shell, main equipment, surface decontamination can conveniently be carried out by the method for spraying in working hall etc.The limitation of this method is that it is poor to the coarse object of porousness, complex components clean effect, can produce certain irradiation dose to operator in the process of stripping simultaneously.
Summary of the invention
The present invention is intended to prepare a kind of radioactive decontamination coating, is being coated on after contaminated object surface, and after its film-forming, embrittlement is peeled off voluntarily, reaches the object of decontamination simultaneously.This novel decontamination coating can be used for the coarse object of porousness, complex components surface decontamination, and the refuse (crisp) of simultaneously its generation can mechanical collection, reduces operator's the irradiation dose that is subject to.
Technical scheme of the present invention is as follows:
From a preparation method for crisp type radioactive decontamination coating, measure polymer emulsion, regulating pH value with NaOH solution is 7.5～9.0, stirs 15～30 minutes, adds polymeric crosslinker, stirs 15～30 minutes, sealing and standing 12 hours, obtains decontamination coating; Wherein the volume of polymeric crosslinker is 15～25% of polymer emulsion volume.
Described preparation method, the preparation method of described polymer emulsion is, taking the polymer emulsion total mass of synthesizing as 100 parts:
A: prepare monomer pre-emulsification thing: Sodium dodecylbenzene sulfonate (SDBS) and fatty alcohol-polyoxyethylene ether (AEO-7) are added in beaker, add again deionized water, after stirring is dissolved Sodium dodecylbenzene sulfonate and fatty alcohol-polyoxyethylene ether completely, add methyl methacrylate (MMA) and methacrylic acid (MAA), and strong stirring forms stable monomer pre-emulsification thing; Monomer 1 is methyl methacrylate (MMA) consumption: 5～7.5 parts; Monomer 2 is methacrylic acid (MAA) consumption: 2.5～7.5 parts; Monomer 1 is with monomer 2 mass ratioes at 1: 1 to 3: 1, and both total mass umbers are at 10～15 parts; Sodium dodecylbenzene sulfonate (SDBS): 0.02～0.06 part, consumption is 0.2～0.4% of monomer total mass; Fatty alcohol-polyoxyethylene ether (AEO-7): 0.08～0.24 part, consumption is 0.8～1.6% of monomer total mass; Deionized water: 4～7.5 parts, consumption is 40～50% of monomer total mass;
B: prepare initiator solution: by Potassium Persulphate (K
2s
2o
8) add in beaker, then add deionized water and stirring that it is dissolved completely, form initiator solution; Initiator amount: 0.05～0.15 part, initiator amount is 0.5～1.0% of monomer total mass; Deionized water consumption is 90～100 times of initiator quality;
C: the preparation of polymer emulsion: add 61.8～81.2 parts of deionized waters and 0.06～0.18 part (consumption be monomer total mass 0.6～1.8%) Sodium dodecylbenzene sulfonate (SDBS) in reactor, stirring is warming up to after 75～85 DEG C, the monomer pre-emulsification thing that adds 1/3 volume steps A to prepare, stir the initiator solution that adds the step B of 2/3 volume to prepare after 15～30 minutes, after stirring reaction 15～30 minutes, drip remaining initiator solution and monomer pre-emulsion, time for adding was controlled at about 15～100 minutes simultaneously again.Be added dropwise to complete rear insulation reaction 3～4 hours, cooling rear discharging.
For the weak point of peelable decontamination technology, the present invention carries out the development from crisp type radioactive decontamination coating.From the concept of crisp type coating be after coating is coated the object surface film-forming of getting dirty voluntarily embrittlement peel off, reach the effect of decontamination simultaneously.This coating is formed through emulsion copolymerization by two kinds of monomers.Adopt methacrylic acid as " soft " monomer in emulsion polymeric product, give the film forming properties that emulsion is certain; Adopting methyl methacrylate is " firmly " monomer in emulsion polymeric product, makes to have certain fragility after emulsion drying and forming-film.In the polymer emulsion of preparation, add linking agent make emulsion in the complexing of polymer molecule segment, crosslinked after, spraying film forming after solidifying voluntarily embrittlement peel off, reach the object separating with the object of getting dirty; Meanwhile, add certain complexing agent at the polymer emulsion of preparation, radionuclide particle is had to complexing adsorption, thereby reach the object of removing radionuclide.Copolymer emulsion decontamination coating prepared by the present invention can be applicable in the surperficial radioactive decontamination of relevant departments, and provides reference for follow-up work.
Brief description of the drawings
Fig. 1 is the technology of the present invention route map;
Fig. 2 is process flow sheet of the present invention;
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
One, polymer emulsion is synthetic
The preparation of 1.1 monomer pre-emulsification things
5.5g Sodium dodecylbenzene sulfonate (SDBS) and 21.5g fatty alcohol-polyoxyethylene ether (AEO-7) are added in beaker, add again 870g deionized water, after stirring is dissolved Sodium dodecylbenzene sulfonate and fatty alcohol-polyoxyethylene ether completely, add 1500g methyl methacrylate (MMA) and 500g methacrylic acid (MAA), and strong stirring forms stable monomer pre-emulsification thing.
The preparation of 1.2 initiator solutions
By 15.2g Potassium Persulphate (K
2s
2o
8) add in beaker, then add 1170g deionized water and stirring that it is dissolved completely, form initiator solution.
Synthesizing of 1.3 polymer emulsions
Add 15.1kg deionized water and 20.5g Sodium dodecylbenzene sulfonate (SDBS) at 30L reactor, stirring is warming up to (stirring velocity: 500r/min) after 82 DEG C, get the monomer pre-emulsification thing of preparation in 1.1, add 1/3 volume monomer pre-emulsification thing, stir after 30 minutes, get the initiator solution of preparation in 1.2, add the initiator solution of 2/3 volume, after stirring reaction 30 minutes, drip remaining initiator solution and monomer pre-emulsion, time for adding was controlled at about 100 minutes simultaneously again.Be added dropwise to complete rear insulation reaction 4 hours, cooling rear discharging, needs to filter if any insolubles.
Two, the preparation of decontamination coating
The preparation of 2.1 polymeric crosslinker
Get zinc chloride 750g and disodium ethylene diamine tetraacetate (disodium ethylene diamine tetraacetate (EDTA-Na
2) for nucleic complexing agent) 300g puts into large beaker, adds deionized water 3600mL and stirs, and after clarifying, adds strong aqua 1700mL, stirs, dissolve, sealing, cooling, obtain polymeric crosslinker for subsequent use.
The preparation of 2.2 decontamination coating
Measure polymer emulsion 10L, regulating pH value with NaOH solution is 8.0, stirs 15min (rotating speed 250～400r/min), add polymeric crosslinker 1950mL, stir 30 minutes (rotating speed 500-900r/min), sealing and standing 12 hours, obtains decontamination coating.
The viscosity adjustment of 2.3 decontamination coating
After decontamination coating preparation, sealing and standing, after 12 hours, is surveyed its viscosity (being generally greater than 1000mPas), is progressively diluted to target viscosities value (200～800mPas), sealed storage with deionized water.
Three, embrittlement and clean effect evaluation
Choose the unlike material surfaces such as metal, lacquer painting plank, glass, marble, mark 20cm × 20cm region, the coating of preparation is coated on to dielectric surface, coating thickness 2mm, at room temperature places in 36 hours film forming embrittlement occurs, and its crisp chip size is 2～6cm.
Carry out the clean effect evaluation experimental of coating by the test method of No. 48, safe book series of GB/T14057-93, IAEA.Choose the unlike material surfaces such as metal, lacquer painting plank, glass, marble, mark each 2～3 of 5cm × 5cm region.Use CoMo170 surface radiocontamination instrument to carry out background measurement.The active fall-out that lays different radioactive surface activity in the region of delimiting at dielectric surface (is mixed radioactivity in the horizontal soil powder of natural background
32p) and surface measurements be infected with level.Spray decontamination coating at Polluted area, certainly peel off surface measurements radioactivity residual level after decontamination, result shows, the decontamination coating once-used decontaminating rate > 84% that adopts the present invention to prepare.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (1)
1. from a preparation method for crisp type radioactive decontamination coating, it is characterized in that, measure polymer emulsion, regulating pH value with NaOH solution is 7.5～9.0, stirs 15-30 minute, adds polymeric crosslinker, stir 15-30 minute, sealing and standing 12 hours, obtains decontamination coating; Wherein the volume of polymeric crosslinker is 15～25% of polymer emulsion volume; The preparation of polymeric crosslinker: get zinc chloride 750g and disodium ethylene diamine tetraacetate 300g puts into large beaker, add deionized water 3600mL and stir, after clarifying, add strong aqua 1700mL, stir, dissolve, sealing, cooling, obtain polymeric crosslinker for subsequent use; The preparation method of described polymer emulsion is, taking the polymer emulsion total mass of synthesizing as 100 parts:
A: prepare monomer pre-emulsification thing: Sodium dodecylbenzene sulfonate and fatty alcohol-polyoxyethylene ether are added in beaker, add again deionized water, after stirring is dissolved Sodium dodecylbenzene sulfonate and fatty alcohol-polyoxyethylene ether completely, add methyl methacrylate and methacrylic acid, and strong stirring forms stable monomer pre-emulsification thing; Monomer 1 is methyl methacrylate consumption: 5～7.5 parts; Monomer 2 is methacrylic acid consumption: 2.5～7.5 parts; Monomer 1 is with monomer 2 mass ratioes at 1: 1 to 3: 1, and both total mass umbers are at 10～15 parts; Sodium dodecylbenzene sulfonate: 0.02～0.06 part, consumption is 0.2～0.4% of monomer total mass; Fatty alcohol-polyoxyethylene ether: 0.08～0.24 part, consumption is 0.8～1.6% of monomer total mass; Deionized water: 4～7.5 parts, consumption is 40～50% of monomer total mass;
B: prepare initiator solution: Potassium Persulphate is added in beaker, then add deionized water and stirring that it is dissolved completely, form initiator solution; Initiator amount: 0.05～0.15 part, initiator amount is 0.5～1.0% of monomer total mass; Deionized water consumption is 90～100 times of initiator quality;
C: the preparation of polymer emulsion: add 61.8～81.2 parts of deionized waters and 0.06～0.18 part of Sodium dodecylbenzene sulfonate in reactor, stirring is warming up to after 75～85 DEG C, the monomer pre-emulsification thing that adds 1/3 volume steps A to prepare, stir the initiator solution that adds the step B of 2/3 volume to prepare after 15～30 minutes, after stirring reaction 15～30 minutes, drip remaining initiator solution and monomer pre-emulsion, time for adding is controlled at 15～100 minutes simultaneously again; Be added dropwise to complete rear insulation reaction 3～4 hours, cooling rear discharging.
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| CN106317998A (en) * | 2016-08-22 | 2017-01-11 | 王利萍 | Waterborne strippable decontamination paint preparation method |
| CN107779031B (en) * | 2017-10-16 | 2020-07-31 | 广州大学 | Low-adhesion antifouling smooth coating prepared by emulsion system without any organic solvent |
| CN107779032B (en) * | 2017-10-16 | 2020-07-31 | 广州大学 | Crude oil low-adhesion antifouling coating and preparation method thereof |
| CN110277182B (en) * | 2019-06-18 | 2021-05-18 | 西南科技大学 | Preparation method of corrosive self-brittle radioactive detergent for iron-based material surface |
| CN111978810A (en) * | 2020-08-31 | 2020-11-24 | 北京国原新技术有限公司 | Method for producing coating material and coating material |
| CN112552753B (en) * | 2020-12-09 | 2021-12-17 | 中国科学院过程工程研究所 | Strippable decontamination coating and preparation method and application thereof |
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| CN1111666A (en) * | 1995-04-07 | 1995-11-15 | 清华大学 | Paint capable of removing radioactive pollution by stripping |
| CN101245215A (en) * | 2008-02-02 | 2008-08-20 | 广州秀珀化工有限公司 | Radioresistant paint for nuclear power plant and manufacture method thereof |
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