CN102250268A - Poly unsaturated olefinic acid metal salt radiation shielding material and preparation method thereof - Google Patents
Poly unsaturated olefinic acid metal salt radiation shielding material and preparation method thereof Download PDFInfo
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- CN102250268A CN102250268A CN2011101053731A CN201110105373A CN102250268A CN 102250268 A CN102250268 A CN 102250268A CN 2011101053731 A CN2011101053731 A CN 2011101053731A CN 201110105373 A CN201110105373 A CN 201110105373A CN 102250268 A CN102250268 A CN 102250268A
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Abstract
The invention discloses a poly unsaturated olefinic acid metal salt radiation shielding material used for nuclear leak emergency and a preparation method thereof. The shielding material is prepared by the following steps of: polymerizing unsaturated olefinic acid metal salt into poly unsaturated olefinic acid metal salt; and performing a molding process. Through structural characterization and performance tests, the shielding material has the characteristics of simple preparation process, low cost, light weight, no toxicity and outstanding performance. The shielding material has the function of shielding a neutron, electron and photon hybrid field, is suitable for radiation protection in nuclear power station maintenance or emergency, and is also suitable for medical radiotherapy accelerators, protective doors for X-ray computed tomography, mobile nuclear facilities and electronic component packaging materials in the field of aerospace.
Description
Technical field
The present invention relates to a kind of poly-ethylenic unsaturation acid metal salt radiation shielding material and preparation method who is used for the nuclear leakage emergency episode.
Background technology
The generation of nuclear leakage accident of Japan impels people to examine problems in the Application of Nuclear Technology again closely.Undeniable, the widespread use of nuclear technique has brought huge economic benefit to the mankind, but has brought potential danger also for environmental safety and social life, if mishandling, even can become and jeopardize the healthy and life security " stealthy killer " of people.When Nuclear power plants generation nuclear leakage accident, the technician who carries out emergent management need carry out radio-protective, not only require this moment shielding material to have the ability of multiple rays such as protection neutron, electronics and photon, and require shielding material to have easy-formation, easy mobile, nontoxic and resistance and high temperature resistance property.Present radiation shielding material on the market, multiaspect is to medical field, such as medical protection gloves, protective clothing, protective baffle plate.After the Fukushima, Japan nuclear power plant accident takes place, do not have the suitable radiation protection material that is used under the Nuclear power plants emergency episode situation, the operator who carries out cooling operations can't cause the reactor core cooling to be obstructed near the operating area because radiation is crossed by force.The present situation of enough protection in emergency circumstances can't be provided at present Nuclear power plants protective clothing, the present invention has developed a kind of poly-ethylenic unsaturation acid metal salt shielding barrier material, can be used as the inner lining material of various fire-fighting vehicles, also can be used as the structured material of removable shielding unit.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of light weight, the radiation shielding material that is used for the nuclear leakage emergency episode that inexpensive, performance is outstanding are provided.
Another object of the present invention provides a kind of preparation method of above-mentioned matrix material.
The object of the present invention is achieved like this: by 100 parts of lead or rare-earth compounds, 50 ~ 100 parts of compositions of unsaturated diluted acid salt are in weight part; Described lead or rare-earth compound are a kind of or any two or more mixture of lead or the inorganic solubility hydrochlorate of rare earth oxide, lead or rare earth; Described unsaturated olefin(e) acid is vinylformic acid, methacrylic acid, any one in butenoic acid, the methylcrotonic acid or any two or more mixture.
The method for preparing material of the present invention is made up of following steps successively:
(a) lead or rare-earth compound are added in the ethylenic unsaturation aqueous acid;
(b) system constant temperature being stirred to solid matter for 80 ℃ no longer dissolves;
(c) filtered while hot (rare earth compound needs crystallisation by cooling several times, to remove impurity wherein) is got filtrate and is added the azo two different initiated polymerizations of fixing one's eyes upon;
(d) get polymerization after solid in thermostat container, be dried to constant weight;
(e) get dry back solid ball milling 10h in ball mill;
(f) get powder 150-200 ℃ of compression moldings in plasticator behind the ball milling.
It can also carry out step (f) acquisition finished product at the two or more ethylenic unsaturation lead plumbates behind the ball milling that step (e) obtains or rare-earth salts polymkeric substance by after waiting mass ratio to mix.
The chemical formula and the reaction formula of each material are as follows:
On behalf of lead oxides and vinylformic acid reaction, equation (A) generate the propylene lead plumbate; (B) represent the reaction of Erbium trichloride and vinylformic acid to generate the vinylformic acid erbium; (C) represent the acrylate polymerization to generate polyacrylate.Wherein a kind of just.
The invention has the beneficial effects as follows that it is nontoxic, with low cost and be easy to the characteristics of moulding that poly-ethylenic unsaturation acid metal salt radiation shielding material has a light weight.The amount of the protection element lead/erbium of shielding material can reach very high concentration, has good shield effectiveness.With the polypropylene lead plumbate is example, and content plumbous in the polypropylene lead plumbate reaches 59.4%, and protective value reaches 0.284mmPb(2.1cm, 1.33MeV), has good photon shield effectiveness.Theoretical Calculation shows that the polypropylene lead plumbate is better than aluminium to the shield effectiveness of electronics.By content plumbous in the reasonable combination material, erbium, can make material have neutron, electronics and photon composite shielding function.
Description of drawings
The FTIR phenogram of Fig. 1 material of the present invention;
Fig. 2 is material section SEM illness that has not attacked the vital organs of the human body figure of the present invention;
Fig. 3 material photon of the present invention dosage depth theory calculated curve;
Fig. 4 material electronics dosage of the present invention depth theory calculated curve.
Embodiment
Mode below by embodiment is elaborated to technical solution of the present invention, but protection scope of the present invention is not limited to described embodiment.
A kind of poly-ethylenic unsaturation acid metal salt radiation shielding material is characterized in that: in weight part, by 100 parts of lead or rare-earth compounds, 50 ~ 100 parts of compositions of unsaturated diluted acid salt; Described lead or rare-earth compound are one or more mixing of lead or rare earth oxide or inorganic solubility hydrochlorate; Described unsaturated olefin(e) acid is vinylformic acid, methacrylic acid, any one in butenoic acid, the methylcrotonic acid or multiple mixing.Lead or rare-earth compound are added in the ethylenic unsaturation aqueous acid, maintenance system constant temperature is stirred to solid matter for 80 ℃ and no longer dissolves, filtered while hot (rare earth compound needs crystallisation by cooling several times, to remove impurity wherein) is got filtrate and is added the azo two different initiated polymerizations of fixing one's eyes upon.Solid is dried to constant weight after getting polymerization in thermostat container, with the ball milling 10h in ball mill of solid after the drying, again with the compression molding in plasticator of the powder behind the ball milling.
Polypropylene lead plumbate radiation shielding material preparation process is as follows:
(a) 50 parts of plumbous oxide are added in 100 parts of acrylic acid aqueous solutions;
(b) system constant temperature being stirred to solid matter for 80 ℃ no longer dissolves;
(c) filtered while hot is got filtrate and is added 1～2 part of azo two different fixing one's eyes upon, 80 ℃ of initiated polymerizations of constant temperature;
(d) the polypropylene lead plumbate after the polymerization is dried to constant weight in thermostat container;
(e) with dried polypropylene lead plumbate ball milling 10h in ball mill;
(f) with 150-200 ℃ of compression moldings in plasticator of the powder behind the ball milling.
Reaction equation is as follows:
Polymethyl acrylic acid erbium radiation shielding material preparation process is as follows:
(a) 100 parts of erbium hydroxides are added in 100 parts of butenoic acid aqueous solution;
(b) system constant temperature being stirred to solid matter for 80 ℃ no longer dissolves;
(c) after the filtered while hot, underpressure distillation crystallization 2 times, get filtrate and add 1～2 part of azo two different fixing one's eyes upon, 80 ℃ of initiated polymerizations of constant temperature; (d) the polymethyl acrylic acid erbium after the polymerization is dried to constant weight in thermostat container;
(e) with dried polymethyl acrylic acid erbium ball milling 10h in ball mill;
(f) with 150-200 ℃ of compression moldings in plasticator of the powder behind the ball milling.
Reaction equation is as follows:
Embodiment 4
Polyacrylic acid cerium radiation shielding material preparation process is as follows:
(a) 50 parts of cerium oxide are added in 100 parts of acrylic acid aqueous solutions;
(b) system constant temperature being stirred to solid matter for 80 ℃ no longer dissolves;
(c) filtered while hot is got filtrate and is added 1～2 part of azo two different fixing one's eyes upon, 80 ℃ of initiated polymerizations of constant temperature;
(d) the polyacrylic acid cerium after the polymerization is dried to constant weight in thermostat container;
(e) with dried polyacrylic acid cerium ball milling 10h in ball mill;
(f) with 150-200 ℃ of compression moldings in plasticator of the powder behind the ball milling.
Polyacrylic acid alkene lead/methacrylic acid erbium/vinylformic acid cerium radiation shielding material preparation process is as follows:
(a) obtain polyacrylic acid lead powder end behind the ball milling with the method for embodiment 2;
(b) obtain polymethyl acrylic acid erbium powder behind the ball milling with the method for embodiment 3;
(c) obtain polyacrylic acid cerium powder behind the ball milling with the method for embodiment 4
(c) three kinds of powder are mixed according to the mass ratio such as grade
(d) with mixed powder 100-200 ℃ of compression moldings in plasticator.
The FTIR phenogram of Fig. 1 material of the present invention; With polypropylene lead plumbate (cerium) is example: wherein (A) is the FT-IR spectrum of propylene lead plumbate, (B) be that the FT-IR spectrum (C) of the polypropylene lead plumbate FT-IR during for polyacrylic acid composes.Figure (A) acrylic acid as can be seen two characteristic peak: 1705cm
-1Place's carbonyl (C=O), 930cm
-1(O-H COOH) disappears acrylate (COO to hydroxyl
-) two symmetries and antisymmetric stretching vibration peak appear at 1425cm
-1, 1549cm
-1Show the generation salt-forming reaction of vinylformic acid and plumbous oxide success, generate the propylene lead plumbate.Figure (B) shows the unsaturated absorption peak (1643cm of C=C of propylene lead plumbate
-1) by C=O(1705cm
-1) replace, show propylene lead plumbate generation self-polymeric reaction, and 930cm
-1(OH, characteristic peak COOH) does not occur hydroxyl, shows that lead ion does not come off from carboxyl in the polymerization process.Figure (C) each peak position of polyacrylic acid cerium as can be seen overlaps in figure (B) is basic, thereby can draw and scheme (B) similarly conclusion.More than the explanation: acrylic acid two functional groups all participate in the reaction, successful preparation polypropylene lead plumbate radiation protection material.
Fig. 2 is material section SEM illness that has not attacked the vital organs of the human body figure of the present invention.As can be seen from the figure powder particle is evenly and fine and close being superimposed tangible fusion do not take place reinvent phenomenon after the compression moulding.The space is less between the particle, can effectively avoid the penetrating radiation that causes because of the material vacancy.By certain compression-molding process, can make material evenly fine and close more, can further improve the shielding properties of material.
Fig. 3 material photon of the present invention dosage depth theory calculated curve; As can be seen from the figure, (0.662MeV, 1.17MeV 1.33MeV), have very high dosage deposition at material internal, at the boundary dosage of material and air a tangible drop are arranged for the photon of different projectile energies.With propylene lead plumbate (cerium) is example: thickness is that the propylene lead plumbate of 2.1cm reaches 0.28mmPb in the protective value under the 1.33MeV, is issued to 0.324mmPb at 0.662MeV; Thickness is the shielding rate 11.8% of vinylformic acid cerium under 1.17MeV of 1.1cm, is issued to 19.3% at 0.662MeV.Show that more than material has good shield effectiveness to high-energy photon.
Fig. 4 material electronics dosage of the present invention depth theory calculated curve.As can be seen from the figure, the absorption curve of the fluence distribution curve of electronics and electronic standard cartridge aluminium is quite similar.With propylene lead plumbate (cerium) is example: energy is 3,6, the linear range of electronics in the propylene lead plumbate of 9MeV is 0.5,1.0 respectively, 1.5cm, can calculate the estimation equation of the linear range of propylene lead plumbate electronics:
（1）
Obtain the estimation equation of the linear range of electronics of vinylformic acid cerium with quadrat method:
The calculation formula of known aluminium is:
Wherein
Be the energy of electronics, unit is MeV,
Be range, unit is mm, and visible institute prepared material is better than aluminium to the assimilation effect of electronics.
Claims (6)
1. poly-ethylenic unsaturation acid metal salt radiation shielding material is characterized in that: be made of a kind of ethylenic unsaturation lead plumbate or rare-earth salts polymkeric substance, or two or more ethylenic unsaturation lead plumbate or rare-earth salts polymkeric substance are composited.
2. a kind of poly-ethylenic unsaturation acid metal salt radiation shielding material according to claim 1, it is characterized in that: in parts by weight: described ethylenic unsaturation lead plumbate or rare-earth salts polymkeric substance are that lead or 100 parts of rare-earth compounds and unsaturated diluted acid are polymerized for 50 ~ 100 parts, and wherein to be that azo two is different decide 1 ~ 2 part of nitrile with initiator.
3. poly-ethylenic unsaturation acid metal salt radiation shielding material according to claim 2, it is characterized in that: described unsaturated olefin(e) acid is vinylformic acid, methacrylic acid, any one in butenoic acid, the methylcrotonic acid or any two or more mixture.
4. poly-ethylenic unsaturation acid metal salt radiation shielding material according to claim 2 is characterized in that: described lead or rare-earth compound are a kind of or any two or more mixture of lead or the inorganic solubility hydrochlorate of rare earth oxide, lead or rare earth.
5. the preparation method of a poly-ethylenic unsaturation acid metal salt radiation shielding material is characterized in that pressing step and realizes, counts by weight:
(a) lead or rare-earth compound are added in 50 ~ 100 parts of aqueous solution of unsaturated olefin(e) acid for 100 parts;
(b) system constant temperature being stirred to solid matter for 80 ℃ no longer dissolves;
(c) filtered while hot is got filtrate and is added that 1～2 part of azo two is different decides nitrile, 80 ℃ of initiated polymerizations of constant temperature;
(d) get polymerization after solid in thermostat container, be dried to constant weight;
(e) get dry back solid ball milling 10h in ball mill;
(f) get powder 150-200 ℃ of compression moldings in plasticator behind the ball milling.
6. according to the preparation method of claim 5 a poly-ethylenic unsaturation acid metal salt radiation shielding material, it is characterized in that two or more ethylenic unsaturation lead plumbates behind the ball milling that its step (e) obtains or rare-earth salts polymkeric substance by after waiting mass ratio to mix, carry out step (f) acquisition finished product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277173A (en) * | 2014-10-30 | 2015-01-14 | 东南大学 | Polyacrylic acid metal salt/boron oxide material as well as preparation method and application thereof |
| CN107129736A (en) * | 2017-04-17 | 2017-09-05 | 中国人民解放军61489部队 | A kind of radioactive contamination control with radiation shielding capability is with removing material |
| CN115926074A (en) * | 2022-12-22 | 2023-04-07 | 南京航空航天大学 | Preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693760A (en) * | 2009-10-16 | 2010-04-14 | 南京航空航天大学 | Polyacrylic acid lead base epoxy resin radiation protection composite material and preparation method thereof |
-
2011
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693760A (en) * | 2009-10-16 | 2010-04-14 | 南京航空航天大学 | Polyacrylic acid lead base epoxy resin radiation protection composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 孙孝红: "聚合物/铅辐射防护材料的制备及其辐射屏蔽性能研究", 《中国优秀硕士学位论文全文数据库 基础科学辑》 * |
| 张瑜等: "聚丙烯酸铅辐射防护材料的制备及性能研究", 《物理学报》 * |
| 李江苏等: "聚丙烯酸钐/环氧树脂辐射防护材料的制备工艺及性能", 《原子能科学技术》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277173A (en) * | 2014-10-30 | 2015-01-14 | 东南大学 | Polyacrylic acid metal salt/boron oxide material as well as preparation method and application thereof |
| CN104277173B (en) * | 2014-10-30 | 2016-06-15 | 东南大学 | Polyacrylic acid metal salt/boron oxide material and its preparation method and application |
| CN107129736A (en) * | 2017-04-17 | 2017-09-05 | 中国人民解放军61489部队 | A kind of radioactive contamination control with radiation shielding capability is with removing material |
| CN115926074A (en) * | 2022-12-22 | 2023-04-07 | 南京航空航天大学 | Preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler |
| CN115926074B (en) * | 2022-12-22 | 2023-12-29 | 南京航空航天大学 | Preparation method of lead acrylate-boron nitride organic-inorganic hybrid radiation shielding functional filler |
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Application publication date: 20111123 |