CN1073263C - Mixed lanthanide contg. Shield composite material for medical X-ray protection - Google Patents
Mixed lanthanide contg. Shield composite material for medical X-ray protection Download PDFInfo
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- CN1073263C CN1073263C CN 96106434 CN96106434A CN1073263C CN 1073263 C CN1073263 C CN 1073263C CN 96106434 CN96106434 CN 96106434 CN 96106434 A CN96106434 A CN 96106434A CN 1073263 C CN1073263 C CN 1073263C
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Abstract
The present invention relates to a compound shielding material which contains mixing lanthanide and is used for medical X-ray protection. Finely-granular ray absorbing matter and a vector material are uniformly kneaded, and then, heat pressing is carried out to form the compound shielding material. The present invention is characterized in that the mixing lanthanide is used as a main component in the absorbing matter, and simultaneously, and simultaneously, the mixing lanthanide contains a small amount of Pb and /or W; the present invention has the advantages of strong absorbing capacity of rays, low cost and light weight. Under the condition of the same ray absorbing capacity, the weight of the compound shielding material of the present invention is 27 to 37% lighter than that of a simple Pb shielding material and is 5 to 15% lighter than that of a compound shielding material of the prior art.
Description
The invention belongs to medical X-ray protection material field, relate in particular to a kind of lanthanide series composite shielding material that is used for mixing containing of medical X-ray protection.
Mixing lanthanum (La) series elements among the present invention is meant by extracting in the natural crystal, the potpourri of being made up of element La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
As everyone knows, in medical X-ray is checked, especially in interventional radiology programs such as angiocardiography, angioplasty and delicate procedure, medical radiology worker must expose to the open air for a long time in the X ray field and work, in order to prevent the radiation damage of X ray, they must wear the personal protective equipment that band is made by radiation shielding material for a long time.Existing shielding material is generally lead (Pb) shielding material, because its weight is heavier, quality is harder, often makes medical radiology worker back, waist muscle very tired, even sustains damage.Carried out the research of composite shielding material in recent years abroad in succession for this reason.The seventies, the Edward W.Webster of the U.S. has worked out the composite shielding material (United States Patent (USP) of being made up of radiation absorption materials such as I, Sn, Sb, Ba, Pb, 3514607, now stop), Paul H.Murphy of Canadian Martin J.Yaffe in 1991, the U.S. in 1993 etc. has carried out research to the composite shielding material of being made up of Pb and Ba, W, Sn, Yb, Cu etc.Though above-mentioned composite shielding material is lighter than conventional P b shielding material, and the physical property of its ray absorption properties and material also has bigger improvement, but this composite shielding material weight is still heavier, and cost is higher, therefore also be not in optimum condition, also need further to improve.
The object of the present invention is to provide the composite shielding material that is used for medical X-ray protection that a kind of barrier propterty is good, in light weight, cost is low.
Shielding material is by contained absorbing material in the material absorption of ionising radiation to be finished to the shielding action of ionising radiation.Material carries out with following dual mode substantially to the absorption of ray, and promptly energy absorbs and the particle absorption.Energy absorption is carried out with ray and material particle generation elasticity and inelastic scattering mode, as Compton scattering.4 powers of the size of energy absorption and absorbing material atomic number are proportional.Making the time spent energy absorption when material and high-energy ray occupies an leading position.Atom or atomic nucleus generation interaction mode that particle absorbs with ray particle and material carry out, as photoelectric effect.The principal element of decision material particle receptivity is that the K layer of this material atom is inhaled position, limit (Kabsorptionedge), in other words, depends on that the K layer of material absorbs energy or the power spectrum that whether covers ray.To low energy X ray, the L layer of material absorbs also plays a role.Do the time spent when material and middle energy and low energy X ray, particle absorbs and occupies critical role.
Traditional medical Pb shielding material, its contained absorbing material is Pb, its atomic number is 82 to have the excellent energy absorption characteristic, so Pb is a kind of ideal material in order to the shielding high-energy ionization radiation.From the particle absorption characteristic, the K layer absorption edge of Pb is 88.0keV again, and promptly it has good particle receptivity to the photon that energy is equal to and greater than 88.0keV; The L layer absorption edge of Pb is 13.0keV, this means that the L layer absorption peak of Pb is 13.0keV, and along with the rising of ray energy, its L layer receptivity weakens gradually, and when ray energy increased to 40keV, its L layer receptivity was very faint.The above results shows, the Pb shielding material is higher than 88.0keV and between the ionising radiation between the 13.0keV to 40keV good receptivity is arranged energy, but the ionising radiation between 40k eV to 88.0keV exists the zone (hereinafter to be referred as " the weak uptake zone " of Pb) of a particle receptivity weakness to energy, as shown in Figure 1.Special needs to be pointed out is, usually most photons of the medical diagnosis X radial that produces by the following tube voltage of 130kVp, its energy is lower than 88.0keV, and the power spectrum peak of X ray is in the energy area of 40keV to 88.0keV, therefore energy and low energy X ray are main diagnosis X radial in Pb being used for shielding as the made shielding material of unique absorbing material, and its defective is conspicuous.In order to remedy the deficiency that Pb absorbs diagnosis X radial, the logical practice is to choose some atomic number to be lower than Pb, and in the element adding shielding material of its K layer absorption edge between 40keV to 88.0keV, replaces part Pb, makes composite shielding material.Because the middle energy and the low energy X ray receptivity of institute's addition element are better than Pb, and its weight is lighter, so the composite shielding material of making has than the independent advantage (referring to Fig. 2,3,4) of, better protecting effect lighter as the shielding material weight that absorbing material constitutes by Pb.This occurs being replaced gradually by composite shielding material the reason place of Pb shielding material trend just in radiation shielding material evolution.
But in the prior art, element Cu, Sn, Sb, I, Ba and the Yb that uses as main absorbing material is not in order to remedy the optimal material of uptake zone a little less than the Pb.The K layer absorption edge of element Cu, Sn, Sb and I is respectively 9.0keV, 29.2keV, 30.5keV and 33.1keV, and be far away apart from the lower limit of weak uptake zone, all can not play the effect that remedies the weak uptake zone of Pb well.The K layer absorption edge of element Yb is 61.3keV, though have the superperformance that remedies the weak uptake zone of Pb, it costs an arm and a leg, and should not use from economic angle.Element B a chemical property is active, can not can only be used for composite shielding material with compound form with simple substance.In the compound of Ba, the shared percentage by weight of Ba element is the highest among the first-elected BaO, but BaO alkalescence is strong, chemical toxicity is bigger, and price is more expensive, has reduced use value.If use BaSO
4Though, can overcome the chemical toxicity of Ba, strengthen chemical stability, Ba element shared percentage by weight in this compound low excessively (59%) is unfavorable for alleviating of shielding material weight.
The present invention adopts mixing La series elements to replace above-mentioned element, is the desirable absorbing material that remedies the weak uptake zone of Pb, the reasons are as follows.1. the minimum La of atomic number is an example in the La series elements to mix, and its K layer absorption edge is 38.9keV, is in the ideal position that remedies the weak uptake zone of Pb.Mix simultaneous other element in the La series elements, its K layer absorption edge raises gradually with the increase of atomic number, promptly rises to the 63.3keV of Lu gradually from the 38.9keV of La, just in time is in the ideal position of the weak uptake zone of comprehensive covering Pb.2. because to mix its K layer absorption edge of different elements that comprises in the La series elements inequality, make the particle absorptive character of these elements can be complementary, its result makes and mixes the La series elements and more attain perfect to the absorption of diagnosis X radial.What use in the composite shielding material 3. of the present invention is the potpourri of La series elements and do not need single La series elements, thereby has avoided the Chemical Decomposition program between difficult La series elements, has saved expensive separation cost, thereby has greatly reduced production cost.The chemical condition of the mixing La series elements that uses in the composite shielding material 4. of the present invention is generally oxide, and its chemical property is stable, and chemical toxicity is little, and the weight percentage height (average out to 85%) of wherein contained mixing La series elements, helps using.According to above-mentioned analysis, by ray absorption properties to employed main radiation absorption material, price, chemical toxicity, indexs such as chemical stability are carried out comprehensive judgement as can be seen, the mixing La series elements that uses in the composite shielding material of the present invention obviously is better than the Cu that uses in the prior art, Sn, Sb, I, Ba, elements such as Yb, because this feature, composite shielding material of the present invention is compared with domestic and international existing shielding material, not only have outstanding substantive distinguishing features, and it is good to have ray absorption properties, in light weight, price is low, marked improvements such as stable chemical performance.
Mix the La series elements except that using in the composite shielding material of the present invention, also partly used Pb, in order to absorb below the 40keV and the photon of the above energy of 88.0keV.Should illustrate because the consumption of Pb in composite shielding material of the present invention be less than mixing the La series elements, so its in this composite shielding material only the identity with less important absorbing material work.
The K layer absorption edge of considering element W in addition is 69.5keV, can effectively remedy the absorption of 69.5keV to 88.0keV energy section photon in the weak uptake zone of Pb, and the effect that can replace Pb absorbs the photon of the above energy of 88.0keV, therefore in composite shielding material of the present invention, the situation of using part W is arranged also as required sometimes.It is limited that but W remedies the effect of the weak uptake zone of Pb, that is it can not remedy the absorption of 40keV to 69.5keV energy section photon, so it can not replace the effect that mixes the La series elements, can only replenishing as the latter.In addition, because the price of W and Pb or mix La series elements oxide and compare relative more expensively, from economic angle, the present invention has also only used a small amount of W in improved supershielded material.
Below in conjunction with accompanying drawing principle of the present invention is described further.
Fig. 1 to Fig. 4 represents that in the improved various composite shielding materials of the present invention 3 kinds weaken the comparison of ability with simple Pb shielding material to diagnosis X radial.For ease of comparing, the gross mass thickness of the contained radiation absorption material of various shielding materials is all unified to be 5.65kg/m
2, list in table 1 concrete the composition.
Table 1
| Shielding material | Absorbing material is formed, kg/m 2 | |||
| Pb | W | Ln 2O 3 | Add up to | |
| The common I type of Pb shielding material composite shielding material high-quality of the present invention I type high-quality II type | 5.65 - 1.88 1.35 | - 2.04 1.88 - | - 3.61 1.89 4.30 | 5.65 5.65 5.65 5.65 |
* Ln
2O
3Expression mixes La series elements oxide
Curve b represents the typical power spectrum (left coordinate) by the X ray of 100kvp tube voltage generation among Fig. 1; Curve a represents the X ray quality attenuation coefficient (Mass attenuation coefficient) (right coordinate) of 0.5mmPb shielding material, and the dotted line below is that pb is to diagnosis X radial receptivity weakness zone; Curve c is the X-ray energy spectrum (right coordinate) that passes behind the Pb shielding material.
Among Fig. 2, Fig. 3 and Fig. 4, curve b and Fig. 1 illustrate that curve a represents high-quality I type of the present invention, high-quality II type and the common I type composite shielding material quality attenuation coefficient (right coordinate) to diagnosis X radial respectively together; Curve c represents to pass the X-ray energy spectrum (left coordinate) behind the above-mentioned composite shielding material respectively.
Comparison diagram 1 to Fig. 4 can draw the following conclusions: the quantity of the x-ray photon after weighing respectively incident X-rays and pass shielding material with the integral area of X-ray energy spectrum, according to the material particle absorption characteristic, can calculate the unified 5.65kg/m of being of gross mass thickness of absorbing material2The time, diagnosis X radial passes the penetrance of Pb shielding material and the improved high-quality I of this patent type, high-quality II type and common I type composite shielding material, and they are respectively 15.7%, 9.9%, 11.0% and 11.5%. Can also further calculate above-mentioned shielding material to the heavy attenuation coefficient of the matter of X ray according to above data, they are respectively 6.4,10.1,9.1 and 8.7 (m2/ kg). The above results shows that when the mass thickness of shielding material equated, the X ray of composite shielding material of the present invention weakened ability apparently higher than the Pb shielding material. This means that if use mix La series elements composite shielding material of the present invention containing, its weight will be than using simple Pb shielding material obviously to alleviate in order to satisfy given other requirement of shelter of level, the amplitude of alleviating is 37%～27%.
The chemical form of the concrete absorbing material that uses in the composite shielding material of the present invention can be determined according to chemical stability and some special requirement of above-mentioned element simple substance: if the element simple substance stable chemical nature then can use the simple substance (metal) of this element; If the unstable chemcial property of element simple substance or because of special requirement can use the compound of these elements. Main operating position is listed in table 2.
Table 2
| Element | Spendable chemical form |
| Mix the La series elements | Oxide, hydroxide, cyanide, chloride, sulfide, sulfate nitrate, carbonate, oxalates |
| Pb | Metal, oxide |
| W | Metal |
The size that the composite shielding material ray weakens ability not only depends on the kind (absorbing the element kind) of used radiation absorption material, also depend on the weight rate between the various absorbing materials, depend in other words various absorbing materials relation between the shared percentage by weight in shielding material. In order to make composite shielding material in specific X ray field, reach best shield effectiveness, various absorbing materials shared percentage by weight in shielding material should be determined according to energy or the power spectrum of shielding ray, in other words according to producing the employed tube voltage of X ray and filtering the employed filter thickness of ray and determine. The various absorbing materials that adopt in the composite shielding material of the present invention in this material shared percentage by weight just according to above-mentioned factor and taken into account that consideration economically determines.
In order to make the shielding material of making have enough pliabilities and mechanical strength, in order to further be made into the protective articles such as protective garment, do not use the metallic plate of pb plate, W plate or mixing La series elements in the composite shielding material of the present invention, but use the fine grained of they or they compound, by above-mentioned fine material and carrier material plastics or rubber evenly are blended together, and adopt plastics or rubber processing method with its hot forming, make certain thickness soft board. Plastics comprise polyethylene, polyvinyl chloride, polypropylene, Polyurethane etc., and rubber comprises natural rubber and artificial rubber. In order to alleviate to greatest extent the weight of shielding material, the consumption of carrier material should be controlled at and can keep shielding material to have minimum amount under the desired physical properties prerequisite.
The object of the present invention is achieved like this. A kind of for mixing La series elements composite shielding material containing of medical X-ray protection, consisted of by radiation absorption material and carrier material, it is characterized in that in the absorbing material except comprise Pb and (or) the W, mainly comprises and mix the La series elements, and the weight percentage of its various components is as follows:
Mix La series elements 25～75%;
Pb 0～45％；
W 0～40；
Carrier material 15～20%.The mass thickness of this composite shielding material is 4.5～5.5kg/m
2, by 130kV
pBe equivalent to 0.5mmPb in the X ray field that following tube voltage produces.
According to above-mentioned overall compound design, at different service conditions, composite shielding material of the present invention can specifically be divided into following three kinds again.
(1) by mixing the La high-quality I type composite shielding material that series elements+the W+ carrier material constitutes, wherein the weight percent of each component is composed as follows:
Mix La series elements 30～75%;
W 10～40％；
Carrier material 15～20%.The mass thickness of this composite shielding material is 4.5～4.8kg/m
2, by 100kV
pBe equivalent to 0.5mmPb in the X ray field that following tube voltage produces.
Cost is higher relatively because this composite shielding material ray absorption properties is good, in light weight (because of the higher institute of W price to), so be applicable to economic condition better, the contact medical institutions that the X ray time is long, intensity is big use, and are especially suitable by 100kV
pUse under the X ray condition that following tube voltage produces.
The optimum formula (percentage by weight) of producing this composite shielding material is as follows:
Mix La series elements oxide 58%;
W 27％；
Tygon 15%; The mass thickness of this shielding material is 4.5kg/m
2
(2) by mixing the La high-quality II type composite shielding material that series elements+the Pb+W+ carrier material constitutes, wherein the weight percent of various components is composed as follows:
Mix La series elements 25～50%;
Pb 20～40％；
W 6～30％；
Carrier material 15～20%.The mass thickness of this composite shielding material is 4.5～4.8kg/m
2, by 100～130kV
pBe equivalent to 0.5mmPb in the X ray field that tube voltage produces.
, contact X ray time long, intensity big medical institutions use better at economic condition that this composite shielding material is suitable for especially is fit to by 100～130kV
pUse under the X ray condition that tube voltage produces.
The optimum formula (weight percentage) of producing this composite shielding material is as follows:
Mix La series elements oxide 33%;
W 25％；
Pb 25％；
PEF 17%.The mass thickness of this composite shielding material is 4.5kg/m
2
(3) by mixing the La plain edition composite shielding material that series elements+the Pb+ carrier material constitutes, wherein the weight percent of various components is composed as follows:
Mix La series elements 30～75%;
Carrier material 15～20%.The mass thickness of this composite shielding material is 4.8～5.5kg/m
2, by 100kV
pBe equivalent to 0.5mmPb in the X ray field that tube voltage produces.
Because this composite shielding material production cost is low, but weight is heavier relatively, therefore be suitable for medical institutions' use relatively poor at economic condition but that the contact X ray time is short, intensity is lower.
The optimum formula (weight percentage) of producing this composite shielding material is as follows:
Mix La series elements oxide 64%;
Pb 21％；
PEF 15%.The mass thickness of this shielding material is 4.8kg/m
2
In order to realize the present invention better, enumerate following examples again.
1 one kinds of composite shielding materials of embodiment, wherein the weight percentage of each component is as follows:
Mix La series elements oxide 73%;
W 11％；
Polyvinylchloride 16%.The mass thickness of this composite shielding material is 4.8kg/m
2, by 100kV
pBe equivalent to 0.5mmPb in the X ray field that following tube voltage produces.
Embodiment 2
A kind of composite shielding material, the weight percentage of each component is as follows:
Mix La series elements oxide 48%;
W 35％；
PEF 17%.The mass thickness of this composite shielding material is 4.8kg/m
2, by 100kV
pBe equivalent to 0.5mmPb in the X ray field that tube voltage produces.
Embodiment 3
A kind of composite shielding material, wherein the weight percentage of each component is as follows:
Mix La series elements oxide 45%;
W 6％；
Pb 32％；
Polyvinyl chloride 17%.The mass thickness of this composite shielding material is 4.8kg/m
2, by 100～130KV
pBe equivalent to 0.5mmPb in the X ray field that tube voltage produces.
Embodiment 4
A kind of composite shielding material, wherein the weight percentage of each component is as follows:
Mix La series elements sulfide 50%;
PbO 33％；
Natural rubber 17%.The mass thickness of this shielding material is 5.5kg/m
2, by 100kV
pBe equivalent to 0.5mmPb in the X ray field that tube voltage produces.
Embodiment 5
A kind of composite shielding material, wherein the weight percentage of each component is as follows:
Mix La series elements oxyhydroxide 70%;
Pb 14％；
Polyvinyl chloride 16%.The mass thickness of this shielding material is 5.5kg/m
2, by 100kV
pBe equivalent to 0.5mmPb in the X ray field that tube voltage produces.
In sum, the present invention has broken away from and has often used some individual element as the pattern that remedies the weak uptake zone of Pb absorbing material in the prior art, take the lead in having used the potpourri of forming by the very close La series elements of number of chemical character, i.e. alleged mixing La series elements in this patent.Do the Chemical Decomposition between the La series elements of not only having avoided difficult like this, thereby reduced production cost significantly, and because its K layer absorption edge of each element in the La series elements all is distributed in the weak uptake zone of Pb, all can play the effect that remedies the weak uptake zone of Pb, therefore each element in them all is fully used, the more important thing is, because the K layer absorption edge of these elements arranged gradually, when it unites use, the energy areal coverage of its radiation absorption is greatly expanded, and makes its absorption to low energy and middle energy X ray more become perfect.Therefore, selecting mixing La series elements is major technique feature of the present invention as the main radiation absorption material of composite shielding material, also be to be directed at the basic reason that composite shielding material of the present invention has superperformances such as ray absorption properties is good, in light weight, cost is low, make the present invention have remarkable social benefit and economic benefit.
Claims (5)
1, a kind ofly is used for mixing containing of medical X-ray protection La series elements composite shielding material, constitute by radiation absorption material and carrier material, it is characterized in that absorbing material mainly comprises mixing La series elements, the use chemical form of La series elements can be one of oxide, oxyhydroxide, and the weight percentage of various components is as follows in the shielding material:
Mix La series elements 25～75%;
Pb 0～32％；
W 0～40％；
Carrier material 15～20%.
2, according to claim 1 being used for mixed La series elements composite shielding material containing of medical X-ray protection, it is characterized in that the weight percent content of its various components is:
Mix La series elements oxide 73%;
W 11％；
Polyvinylchloride 16%.
3, according to claim 1 being used for mixed La series elements composite shielding material containing of medical X-ray protection, it is characterized in that the weight percent content of its various components is:
Mix La series elements oxide 48%;
W 35％；
Polyvinylchloride 17%.
4, according to claim 1 being used for mixed La series elements composite shielding material containing of medical X-ray protection, it is characterized in that the weight percent content of its various components is:
Mix La series elements oxide 45%;
Pb 32％；
W 6％；
Polyvinylchloride 17%.
5, according to claim 1 being used for mixed La series elements composite shielding material containing of medical X-ray protection, it is characterized in that the weight percent content of its various components is:
Mix La series elements oxyhydroxide 70%;
Pb 14％；
Polyvinylchloride 16%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96106434 CN1073263C (en) | 1996-08-13 | 1996-08-13 | Mixed lanthanide contg. Shield composite material for medical X-ray protection |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96106434 CN1073263C (en) | 1996-08-13 | 1996-08-13 | Mixed lanthanide contg. Shield composite material for medical X-ray protection |
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|---|---|
| CN1153389A CN1153389A (en) | 1997-07-02 |
| CN1073263C true CN1073263C (en) | 2001-10-17 |
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| CN101137285B (en) * | 2007-10-12 | 2010-08-25 | 魏宗源 | Composite shielding material for medical X-ray protection |
| CN101572129B (en) * | 2009-06-15 | 2011-08-31 | 北京化工大学 | Overall lead-free X-ray shielding plastic compound material |
| CN102995389B (en) * | 2012-12-11 | 2014-10-22 | 武汉纺织大学 | Method for acquiring neutron protective fabric by doping rare earth element |
| CN109501425B (en) * | 2018-11-14 | 2019-10-29 | 山东大学 | A kind of medical X-ray-preventing composite material and preparation method |
| CN110774512A (en) * | 2019-10-10 | 2020-02-11 | 中广核研究院有限公司 | Forming method of tungsten boron crosslinked polyethylene composite shield with high tungsten content |
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