CN-121975257-A - Radiation protection tough gel based on multi-metal carbonate nano particles, and preparation method and application thereof

CN121975257ACN 121975257 ACN121975257 ACN 121975257ACN-121975257-A

Abstract

The invention discloses a radiation protection tough gel based on multi-metal carbonate nano particles, a preparation method and application thereof, wherein the radiation protection tough gel comprises a gel matrix and multi-metal carbonate nano particles uniformly dispersed in the gel matrix, the gel matrix is a polyvinyl alcohol three-dimensional network densified and physically crosslinked through carbonate ion salting-out, the multi-metal carbonate nano particles are carbonate composite nano particles containing at least two metal elements of tungsten, bismuth and gadolinium, and the mass of the multi-metal carbonate nano particles accounts for 8% -18% of the total mass of the radiation protection tough gel. According to the invention, the tungsten, bismuth and gadolinium multi-metal carbonate nano particles are used as functional cores, and the salting-out enhancement technology is combined to prepare the gel material with the advantages of high shielding efficiency, excellent mechanical property, flexible adaptation and the like, so that the integration of function giving and matrix enhancement is realized, and the gel material is suitable for wearable protection, medical radiation protection and special equipment flexible shielding scenes.

Inventors

CHEN SILEI
MA WENJIE
CHENG XIAJU
YAN YAN
WU SHUWANG
JIANG YUJIAO
LIU YIFAN

Assignees

苏州大学

Dates

Publication Date: 20260505
Application Date: 20260228

Claims (10)

1. The radiation protection tough gel based on the multi-metal carbonate nano particles is characterized by comprising a gel matrix and the multi-metal carbonate nano particles uniformly dispersed in the gel matrix; the gel matrix is a polyvinyl alcohol three-dimensional network densified and physically crosslinked through carbonate ion salting-out; The multi-metal carbonate nano particles are carbonate composite nano particles containing at least two metal elements of tungsten, bismuth and gadolinium, and the particle size of the nano particles is 80-300nm; the mass of the multi-metal carbonate nano particles accounts for 8% -18% of the total mass of the radiation protection tough gel.
2. The radiation protection tough gel based on the multi-metal carbonate nano-particles according to claim 1, wherein the molar ratio of the metal elements of tungsten, bismuth and gadolinium in the multi-metal carbonate nano-particles is (1-3): 1-2): 0.5-1.
3. The radiation protection tough gel based on the multi-metal carbonate nano-particles according to claim 1, further comprising a dispersing agent, wherein the dispersing agent is at least one of sodium dodecyl benzene sulfonate, polyethylene glycol 400 and tween 80, and the mass ratio of the dispersing agent to the multi-metal carbonate nano-particles is (0.02-0.08): 1.
4. A method for preparing the radiation protection tough gel based on multi-metal carbonate nanoparticles as claimed in any one of claims 1 to 3, comprising the steps of: step 1) preparation of multi-metal carbonate nanoparticles: Dissolving tungsten salt, bismuth salt and gadolinium salt in deionized water according to the molar ratio of (1-3) to (1-2) to (0.5-1) to prepare a mixed metal salt solution, then dropwise adding a carbonate solution serving as a precipitant into the mixed metal salt solution to react at 50-75 ℃ under the stirring condition, and centrifuging, washing and drying after the reaction to obtain multi-metal carbonate nano particles with the particle size of 80-300 nm; step 2) preparing a multi-metal carbonate nanoparticle dispersion liquid: adding the multi-metal carbonate nano particles and the dispersing agent prepared in the step 1 into deionized water, and dispersing the multi-metal carbonate nano particles in the deionized water again through ultrasonic dispersion to form uniform multi-metal carbonate nano particle dispersion liquid; Step 3) preparing polyvinyl alcohol composite sol: Firstly, dissolving polyvinyl alcohol in deionized water, heating and stirring to prepare a polyvinyl alcohol solution with the mass fraction of 12% -25%, then slowly adding the multi-metal carbonate nanoparticle dispersion liquid prepared in the step 2, and stirring and mixing uniformly to obtain composite sol; step 4) salting out to induce gelation and enhancement: Placing the composite sol into a mould, immersing the composite sol into carbonate aqueous solution with the concentration of 0.8-1.5mol/L for salting out treatment, wherein the treatment temperature is 30-50 ℃, and the treatment time is 1-2.5h, so that polyvinyl alcohol molecular chains in the composite sol are dehydrated, aggregated and form a physically crosslinked three-dimensional network through Hofmeister special effect of carbonate ions, and meanwhile, multi-metal carbonate nano particles in the composite sol are limited in the three-dimensional network to form tough gel; Step 5) post-treatment: and (3) taking out the tough gel obtained in the step (4), washing and drying to obtain the radiation protection tough gel based on the multi-metal carbonate nano particles.
5. The method of claim 4, wherein in step 1, the molar ratio of the metal elements of the tungsten salt, the bismuth salt and the gadolinium salt is 2:1.5:0.8, the concentration of the carbonate solution is 1.0mol/L, the reaction temperature of the carbonate solution and the mixed metal salt solution is 55 ℃, the continuous stirring rotation speed is 300rpm, the continuous stirring reaction time is 1.5h, the centrifugation rotation speed is 8000rpm, the centrifugation time is 15min, the drying temperature is 60 ℃, and the drying time is 6h.
6. The method according to claim 4, wherein in the step 2, the dispersing agent is sodium dodecyl benzene sulfonate, the mass ratio of the multi-metal carbonate nano particles, deionized water and the dispersing agent is 220:2000:11, the ultrasonic dispersing power is 500W, and the ultrasonic dispersing time is 30min.
7. The method according to claim 4, wherein in the step 3, the mass ratio of the polyvinyl alcohol to the deionized water is 4:25, the temperature of heating and stirring the polyvinyl alcohol and the deionized water is 95 ℃, the stirring time is 3 hours, the mass fraction of the formed polyvinyl alcohol solution is 13.8%, the reaction temperature of the poly metal carbonate nanoparticle dispersion liquid and the polyvinyl alcohol solution is 60 ℃, and the reaction stirring time is 1 hour.
8. The method according to claim 4, wherein in the step 4, the aqueous solution of carbonic acid salt is aqueous solution of sodium bicarbonate with concentration of 1.2mol/L, and the salting-out treatment of the composite sol in the aqueous solution of carbonic acid salt is carried out at 40 ℃ for 1.5 hours.
9. The method of claim 4, wherein in step 5, the method of washing the tough gel is washing 3 times with deionized water to remove residual salt ions, and the method of drying the tough gel is air-drying at 45 ℃ to constant weight.
10. Use of a radiation protective tough gel based on multi-metal carbonate nanoparticles according to any one of claims 1 to 3 and/or a radiation protective tough gel based on multi-metal carbonate nanoparticles as prepared by the preparation method according to any one of claims 4 to 9 for the preparation of wearable radiation protective equipment, medical radiation protective articles or special equipment flexible shields.

Description

Radiation protection tough gel based on multi-metal carbonate nano particles, and preparation method and application thereof Technical Field The invention belongs to the technical field of radiation protection materials, and particularly relates to radiation protection tough gel based on multi-metal carbonate nano particles, and a preparation method and application thereof. Background With the wide application of nuclear technology in the fields of medical treatment, energy sources, industrial detection and the like, the comprehensive requirements of high-efficiency shielding, excellent mechanical properties and flexible adaptation of radiation protection materials are increasingly urgent. Conventional radiation protection materials are largely classified into conventional rigid materials such as lead plates, lead-containing rubbers, and flexible gel-based materials. However, the two existing materials have the bottleneck that the functions and the performances are difficult to be compatible, and the two existing materials have the following two main defects: 1) Although traditional rigid materials such as lead plates, lead-containing rubber and the like rely on metals with high atomic numbers to realize high-efficiency shielding, the lead plates are high in density and poor in flexibility, cannot be attached to the surfaces of human bodies or complex equipment, and the toxicity and pollution of lead are not in accordance with the green development trend, so that the application scene is limited; 2) The flexible gel-based material solves the problem of rigidity, but has double bottlenecks that firstly, the shielding efficiency is insufficient, the absorption energy spectrum of a single metal filler is narrow, the attenuation capability is limited due to low-content doping, and secondly, the mechanical property is weak, the traditional gel network is loose, the tensile strength is often lower than 1MPa, the elongation at break is less than 100%, and the gel is easy to break in use. Although there is an optimization scheme for the two core defects, the effect is limited, for example, some patents improve the shielding performance through nanoparticle doping, but the problems of agglomeration and mechanical enhancement are not solved, for example, some resin matrixes are adopted to improve the strength, and the advantage of flexibility of gel is lost. At present, the multi-metal carbonate nano particles have potential in the fields of catalysis and adsorption because of stable crystal structure, abundant metal active sites and good dispersibility, but the research of applying the multi-metal carbonate nano particles as a radiation protection function filler to gel materials has not been reported yet. Meanwhile, the Hofmeister special effect should be used as a classical mechanism for regulating and controlling a polymer aggregation state structure, and the Hofmeister special effect by utilizing carbonate ions should synchronously realize the integrated design of protection and toughness of the gel with radiation protection function and mechanical property enhancement, and the related technology has not been disclosed yet. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides radiation protection tough gel based on multi-metal carbonate nano particles, a preparation method and application thereof, wherein the multi-metal carbonate nano particles of tungsten, bismuth and gadolinium are taken as functional cores, and a salting-out enhancement technology is combined to prepare a gel material with the advantages of high shielding efficiency, excellent mechanical property, flexible adaptation and the like, so that the radiation protection tough gel is suitable for wearable protection, medical radiation protection and special equipment flexible shielding scenes. In order to solve the technical problems and achieve the technical effects, the invention is realized by the following technical scheme: a radiation protection tough gel based on multi-metal carbonate nano-particles comprises a gel matrix and multi-metal carbonate nano-particles uniformly dispersed in the gel matrix; the gel matrix is a polyvinyl alcohol three-dimensional network densified and physically crosslinked through carbonate ion salting-out; the multi-metal carbonate nano particles are carbonate composite nano particles containing at least two metal elements of tungsten (W), bismuth (Bi) and gadolinium (Gd), and the particle size of the nano particles is 80-300nm; the mass of the multi-metal carbonate nano particles accounts for 8% -18% of the total mass of the radiation protection tough gel. Further, in the multi-metal carbonate nano-particles, the molar ratio of the metal elements of tungsten (W), bismuth (Bi) and gadolinium (Gd) is (1-3): 1-2): 0.5-1. Further, the radiation protection tough gel comprises a dispersing agent, wherein the dispersing agent is at least one of sodium dodecyl benzene sulfonate, p