阅读说明：本技术 一种铋基辐射屏蔽材料及制品 (Bismuth-based radiation shielding material and product ) 是由 夏纪勇 王军 唐谟堂 赵异梅 丁志平 李果 李娟娟 于 2021-08-10 设计创作，主要内容包括：本发明涉及一种铋基辐射屏蔽材料及制品,将铋基功能性粉体,加入液态高分子聚合物中进行真空搅拌,成型固化后,即为无铅X射线和γ射线辐射屏蔽防护材料—铋基辐射屏蔽材料或者制品,适合固定或者移动人在其内活动的处所的射线屏蔽防护。其显著特点是通过三种不同铋源(金属铋粉和二种不同晶型的氧化铋)的配方组合,与硫酸钡组合使用,具有材料成本低,制品安全无毒、屏蔽效能高,易于稳定量产等优势。(The bismuth-base radiation shielding material or product is prepared by adding bismuth-base functional powder into liquid high-molecular polymer, vacuum stirring, molding and curing, and is a lead-free X-ray and gamma-ray radiation shielding and protecting material, i.e. bismuth-base radiation shielding material or product, which is suitable for radiation shielding and protecting places where people move or fix. The bismuth powder shielding material is characterized in that three different bismuth sources (metal bismuth powder and two different crystal forms of bismuth oxide) are combined according to a formula and are combined with barium sulfate for use, and the bismuth powder shielding material has the advantages of low material cost, safety and no toxicity of products, high shielding efficiency, easiness in stable mass production and the like.)

1. A bismuth-based radiation shielding material and a product thereof are formed by molding and curing a shielding rubber material body; the shielding colloid body is formed by vacuum stirring and mixing functional shielding powder, resin and other additives; the liquid high molecular polymer is epoxy resin, phenolic resin, liquid polyurethane, liquid silica gel and/or other liquid resins; the functional shielding powder is formed by mixing bismuth-based shielding powder and other shielding element powder, wherein the other shielding element powder is mainly barium sulfate and the like; the mass ratio of the liquid high molecular polymer to the functional shielding powder is 1 (1-10); the method is characterized in that: the bismuth-based shielding powder is prepared by mixing metal bismuth powder and bismuth oxides with different crystal forms: the fineness of the metal bismuth powder is-100 meshes or more and 95 percent to-200 meshes or more and 95 percent, the mass percentage of the metal bismuth powder in the bismuth-based shielding powder is 0-100 percent (the preferred proportion is 20-80 percent), and the rest is bismuth oxide powder with different crystal forms; the bismuth oxide powder is prepared from beta-Bi₂O₃Powder and alpha-Bi₂O₃Mixing the powder: beta-Bi₂O₃And alpha-Bi₂O₃The average grain diameter of the powder is 1-5 microns and 2-80 microns respectively, beta-Bi₂O₃The weight percentage of the bismuth oxide powder is 0-100% (the preferred proportion is 25% -75%), and the rest is alpha-Bi₂O₃And (3) powder.

2. The bismuth-based radiation shield and article of claim 1, wherein: the product is a shielding brick, which consists of an upper plate 1 and a lower plate 2, wherein the upper plate 1 is a square plate or a rectangular plate with equal thickness, the side lengths of the side edges 1-1, 1-2, 1-3 and 1-4 are equal, or the side edges 1-1 and 1-3 are equal in length, and the side edges 1-2 and 1-4 are equal in length; the lower plate 2 is a square plate or a rectangular plate with equal thickness, four corners are cut off, the side lengths of the sides 2-1, 2-3, 2-5 and 2-7 are equal, or the sides 2-1 and 2-5 are equal, and the sides 2-3 and 2-7 are equal; the lower layer plate and the upper layer plate are provided with laps with uniform width, the lower layer plate is provided with an equilateral right-angled triangle at two adjacent sides, the length of the straight side of the triangle is half of the width of the laps, and four symmetrical corner cutting edges of 2-2, 2-4, 2-6 and 2-8 are formed.

3. The bismuth-based radiation shield and article of claim 1, wherein: the product is a shielding brick, which consists of an upper plate 1 and a lower plate 2, wherein the upper plate 1 is a square plate or a rectangular plate with equal thickness, the side lengths of the side edges 1-1, 1-2, 1-3 and 1-4 are equal, or the side edges 1-1 and 1-3 are as long as each other, and the side edges 1-2 and 1-4 are as long as each other; the lower plate 2 is a square plate or a rectangular plate with the same thickness, the side lengths of the side edges 2-1, 2-2, 2-3 and 2-4 are equal, or the side edges 2-1 and 2-3 are equal, and the side edges 2-2 and 2-4 are equal; the lower layer plate and the upper layer plate are square or rectangular plates with the same shape and size, and are uniformly distributed and staggered, so that uniform overlap edges are formed around the upper layer and the lower layer.

4. The bismuth-based radiation shield and article of claim 1, wherein: the product is a shielding brick, which consists of an upper plate 1 and a lower plate 2, wherein the upper plate 1 is a square plate or a rectangular plate with equal thickness, the side edges 1-1, 1-2, 1-3 and 1-4 are equal in length, or the side edges 1-1 and 1-3 are equal in length, and the side edges 1-2 and 1-4 are equal in length; the lower plate 2 is a square plate or a rectangular plate with the same thickness, the side edges 2-1, 2-2, 2-3 and 2-4 are equal in length, or the side edges 2-1 and 2-3 are equal in length, and the side edges 2-2 and 2-4 are equal in length; the adjacent two sides 1-1 and 1-2 of the upper layer plate are aligned with the corresponding positions of the adjacent straight edges 2-1 and 2-2 of the lower layer plate; the other adjacent straight edges 1-3 and 1-4 of the upper plate are staggered with the straight edges 2-3 and 2-4 of the corresponding positions of the lower plate to form lap edges with the same width.

Technical Field

The application relates to a radiation shielding material for X rays and gamma rays and a product, in particular to a bismuth-based radiation shielding material and a product, belonging to the field of functional materials.

Background

At present, the material is mainly used for shielding and protecting materials of X-ray and gamma-ray radiation at home and abroad, mainly comprises materials of lead, tungsten, antimony, rare earth, rare metal, barium and the like, and is also beneficial to the technical scheme of preparing the shielding material by using industrial waste residues. Because lead is toxic and has outstanding environmental protection problems, materials such as tungsten, rare earth, rare metal and the like have high preparation cost. Research is being conducted to find lead-free protective materials for shielding and protecting against X-ray and gamma-ray radiation, which are required to be low in cost, safe and nontoxic.

CN110105743A patent application discloses a lead-free X, gamma ray radiation shielding protective material and its preparation method. Uniformly mixing erbium-source solid powder, tungsten-source solid powder, bismuth-source solid powder and a coupling agent to obtain a first mixture; adding a polyurethane emulsion into the first mixture and mixing to prepare a second mixture; and curing the second mixture to obtain the X-ray and gamma-ray radiation shielding and protecting material. The lead-free X-ray and gamma-ray radiation shielding and protecting material provided by the invention takes an erbium source, a tungsten source and a bismuth source as ray shields, fully utilizes the complementary effect of absorption boundaries of K layers of Er, W and Bi and realizes effective shielding of X-rays and gamma-rays. However, the erbium source and the tungsten source used in the patent application are very expensive materials, and tungsten is a rare strategic resource regulated by the state; due to restrictions of policy, economy and the like, the patented technology has no general applicability.

CN110828019A discloses a silica gel-based flexible shielding material for gamma ray shielding and a preparation method thereof, the material is prepared from silica gel A, silica gel B and tungsten powder, and the preparation comprises the following steps: 1) weighing silica gel A, silica gel B and tungsten powder, and mixing and stirring the silica gel A and the silica gel B uniformly to obtain a mixture; 2) grinding tungsten powder, pouring the ground tungsten powder into the mixture obtained in the step 1), and uniformly stirring to obtain a mixture of silica gel and tungsten powder; 3) the mixture of silica gel and tungsten powder is poured into a mold, then placed in a vacuum tank, vacuumized, cooled after bubbles disappear, and the flexible silica gel-based shielding material for gamma ray shielding is obtained, can effectively block gamma rays, is green and environment-friendly, cannot cause harm to human bodies, and is simple in preparation method.

CN106543643B discloses an organic composite high-energy ray shielding material, which is prepared from the following components in percentage by mass: 20-50% of epoxy resin; 20-60% of tungsten source powder; 0-1% of coupling agent; 10-30% of curing agent. The invention also discloses a preparation method of the shielding material. The shielding material is light and convenient, has high shielding efficiency, particularly has higher shielding rate on X rays, gamma rays and neutrons, and has good mechanical property. In addition, the shielding material has the advantages of easily available raw materials, low cost, no toxicity, simple production process, capability of being formed at room temperature and energy conservation.

In order to overcome the problems of high cost, difficult mass production and the like of the traditional lead-free X-ray and gamma-ray radiation shielding material, bismuth-based functional powder is added into a liquid high molecular polymer for vacuum stirring, and after molding and curing, the bismuth-based radiation shielding material or the bismuth-based radiation shielding material serving as a lead-free X-ray and gamma-ray radiation shielding protective material is obtained and is suitable for fixing or moving the radiation shielding protection of places where people move.

The bismuth powder shielding material is characterized in that three different bismuth sources (metal bismuth powder and two kinds of bismuth oxide with different crystal forms and particle sizes) are combined according to a formula and are combined with barium sulfate for use, and the bismuth powder shielding material has the advantages of low material cost, safety and no toxicity of products, high shielding efficiency, easiness in stable mass production and the like.

Disclosure of Invention

The lead-free X-ray and gamma-ray radiation shielding and protecting material is prepared by placing bismuth-based functional powder and liquid high molecular polymer into a vacuum stirrer, uniformly stirring, placing into a mold cavity or injecting into the mold cavity under pressure, placing for a certain time in an environment at normal temperature or a certain temperature, curing, demolding, and obtaining the radiation shielding and protecting material or product.

The technical scheme of the application is as follows:

the radiation shielding and protecting material or the product is formed by molding and curing a shielding rubber material body. The shielding colloid body is formed by vacuum stirring and mixing functional shielding powder, resin and other additives. The curing temperature is generally 50-120 ℃, the surface curing time is generally 20-120min, and the complete curing time is generally 12-24 h.

The functional powder is formed by mixing bismuth-based shielding powder and other shielding powder in a compatible manner, and the other shielding powder is mainly non-lead materials such as barium sulfate and the like with low price and large quantity. The weight percentage of the bismuth-based shielding powder is generally 70-100%, and the balance is other shielding powder.

The bismuth-based shielding powder is prepared by mixing metal bismuth powder and bismuth oxides with different crystal forms: the fineness of the metal bismuth powder is-100 meshes or more and 95 percent to-200 meshes or more and 95 percent, the mass percentage of the metal bismuth powder in the bismuth-based shielding powder is 0 to 100 percent (the preferred proportion is 20 to 80 percent), and the rest is bismuth oxide powder with different crystal forms. The bismuth oxide powder is prepared from beta-Bi₂O₃Powder and alpha-Bi₂O₃Mixing the powder: beta-Bi₂O₃And alpha-Bi₂O₃The average grain diameter of the powder is 1-5 microns and 2-80 microns respectively, beta-Bi₂O₃The weight percentage of the bismuth oxide powder is 0-100% (the preferred proportion is 25% -75%), and the rest is alpha-Bi₂O₃And (3) powder.

The liquid high molecular polymer is epoxy resin, phenolic resin, liquid polyurethane, liquid silica gel and/or other liquid resins.

The mass ratio of the liquid high molecular polymer to the functional powder is 1:1-10 (the preferable ratio is 1: 3-6), namely: 1 part of liquid high molecular polymer and 1-10 parts (the preferred proportion is 3-6) of functional powder.

The radiation shielding and protecting material can be made into radiation shielding and protecting building materials (bricks), single-sided or double-sided composite cloth (or composite fiber fabric made of specified materials), radiation shielding and protecting profiles with middle fiber reinforced layers, and other radiation shielding and protecting materials with specific shapes and special requirements.

The application discloses a radiation shielding protective product-shielding brick is through special design and mould shaping. After construction according to the specified requirements, no shielding leakage dead angle can be ensured. The invention will be further described with reference to the following description of the drawings.

Drawings

FIG. 1 is a schematic structural diagram of a shielding brick with a double-layer structure, a large lower layer, a small upper layer, a lap edge around the shielding brick and four corner cuts.

Fig. 2 is a splicing effect diagram of four shielding bricks with the structure shown in fig. 1.

FIG. 3 is a schematic structural diagram of a shielding brick with a double-layer structure, wherein the upper layer and the lower layer are consistent in size and are arranged in a staggered manner, and a lap is left on the periphery of the shielding brick.

FIG. 4 is a schematic structural view of a shielding brick with a double-layer structure, a large lower layer, a small upper layer, two adjacent edges with overlap edges, and two other edges being flush.

The shielding brick shown in fig. 1 comprises an upper plate 1 and a lower plate 2, wherein the upper plate 1 is a square plate or a rectangular plate with equal thickness, the side lengths of the side edges 1-1, 1-2, 1-3 and 1-4 are equal, or the side edges 1-1 and 1-3 are equal in length, and the side edges 1-2 and 1-4 are equal in length; the lower plate 2 is a square plate or a rectangular plate with equal thickness, four corners are cut off, the side lengths of the sides 2-1, 2-3, 2-5 and 2-7 are equal, or the sides 2-1 and 2-5 are equal, and the sides 2-3 and 2-7 are equal; the peripheries of the lower layer plate and the upper layer plate form a lap edge with uniform width, the width of the lap edge is 3-15 mm, the lap edge is too narrow to be convenient for construction, and the lap edge is too wide to waste materials; the lower layer plate is cut off an equilateral right-angled triangle at two adjacent side edges, the length of the right side of the triangle is half of the width of the lap, and four symmetrical corner cutting edges of 2-2, 2-4, 2-6 and 2-8 are formed. The upper plate and the lower plate can be manufactured respectively and then bonded into a whole; the resin added with the shielding material can also be directly pressed by a combined die for mold pressing and curing molding. The formed whole body is combined with the turned edge for use, seamless connection can be achieved at the joint, and radiation leakage is prevented.

Fig. 2 shows a small shielding unit consisting of four shielding bricks shown in fig. 1, wherein two shielding bricks I are placed with their large faces facing upwards (upper left and lower right in the figure), and the other two shielding bricks I are placed with their large faces facing downwards (lower left and upper right in the figure, with purple lines). As can be seen from fig. 2, there is no leakage point at the joints and at the center of the joints of the four shielding bricks.

The shielding brick shown in fig. 3 is composed of an upper plate 1 and a lower plate 2, wherein the upper plate 1 is a square plate or a rectangular plate with equal thickness, the side lengths of the side edges 1-1, 1-2, 1-3 and 1-4 are equal, or the side edges 1-1 and 1-3 are equal, and the side edges 1-2 and 1-4 are equal. The lower plate 2 is a square plate or a rectangular plate with the same thickness, the side lengths of the side edges 2-1, 2-2, 2-3 and 2-4 are equal, or the side edges 2-1 and 2-3 are equal, and the side edges 2-2 and 2-4 are equal. The lower layer plate and the upper layer plate are square or rectangular plates with the same shape and size, and are uniformly distributed and staggered, so that uniform overlap edges are formed around the upper layer and the lower layer, the width of the overlap edges is 3-15 mm, the lower layer plate is too narrow to be convenient for construction, and the wider layer plate wastes materials. The upper plate and the lower plate can be manufactured respectively and then bonded into a whole; the resin added with the shielding material can also be directly pressed by a combined die for mold pressing and curing molding. The formed whole can be combined for use, seamless connection is achieved at the joint, and radiation leakage is prevented.

The shielding bricks shown in fig. 4 are generally used to shield edge positions of walls or faces. The laminated plate consists of an upper plate 1 and a lower plate 2, wherein the upper plate 1 is a square plate or a rectangular plate with equal thickness, the side edges 1-1, 1-2, 1-3 and 1-4 are equal in length, or the side edges 1-1 and 1-3 are equal in length, and the side edges 1-2 and 1-4 are equal in length. The lower plate 2 is a square plate or a rectangular plate with the same thickness, the side edges 2-1, 2-2, 2-3 and 2-4 are equal in length, or the side edges 2-1 and 2-3 are equal in length, and the side edges 2-2 and 2-4 are equal in length. The adjacent two sides 1-1 and 1-2 of the upper plate are aligned with the adjacent straight sides 2-1 and 2-2 of the lower plate correspondingly. The other adjacent straight edges 1-3 and 1-4 of the upper layer plate and the straight edges 2-3 and 2-4 at the corresponding positions of the lower layer plate are staggered to form overlap edges with the same width, the width of the overlap edge is 3-15 mm, the overlap edge is too narrow to be convenient for construction, and the overlap edge is too wide to waste materials. In special cases, unequal-width laps may also be provided. The upper plate and the lower plate can be manufactured respectively and then bonded into a whole; the resin added with the shielding material can also be directly pressed by a combined die for mold pressing and curing molding. The formed whole can be combined for use, seamless connection is achieved at the joint, and radiation leakage is prevented.

Detailed description of the preferred embodiments

The following examples further illustrate the implementation of the technical solutions of the present application.

Examples

Example 1

Will: epoxy E44,170 g; curing agent T31, 70 g; 240 g of barium sulfate; 1860 g of bismuth oxide (beta-Bi with an average particle size of 1.5 μm)₂O₃1000g of powder; alpha-Bi having an average particle diameter of 5 μm₂O₃860g) of the powder is put into a vacuum stirring device for fully stirring to generateAnd (3) pressing the glue into a glue inlet below the die cavity by using a glue pressing device, and exhausting air from an air outlet above the die cavity. After being formed in a combined die cavity, the product is placed in an environment with the temperature of 60 ℃ for curing for 2 hours, the surface of the product is cured, and then the product is placed at normal temperature for 24 hours, so that the X-ray and gamma-ray radiation shielding protective product which is equivalent to 3.0mmPb is obtained, the weight of the product is 2340 g, the shape of the product is the square shielding brick shown in the attached figure 1, the size of an upper layer plate is 180mm multiplied by 180mm, the thickness of the upper layer plate is 6mm, the size of a lower layer plate is 200mm multiplied by 200mm, the thickness of the lower layer plate is 6mm, the lap width is 10mm, and the straight edges of the peripheral cutting corners are right-angle equilateral triangles with the thickness of 5 mm.

Example 2

Will: 240 g of phenolic resin and curing agent; 260 g of barium sulfate; 2070 g of bismuth oxide (wherein: the average particle diameter is 1.5 μm. beta. -Bi)₂O₃1000g of powder; alpha-Bi having an average particle diameter of 75 μm₂O₃1070g) of powder is put into a vacuum stirring device for fully stirring to generate a glue compound, the glue compound is pressed into a die cavity between flat vulcanizing machines by a glue pressing device, the formed product is heated to 80 ℃ for curing for 1.5 hours after being formed under pressure, the surface of the product is cured, the product is placed at normal temperature for 24 hours, a radiation shielding brick with radiation shielding effectiveness equivalent to 3.0mm lead equivalent, namely X rays and gamma rays which are the same as those in the attached figure 3 is obtained, and the sizes of the upper layer and the lower layer are all 200mm long

200mm in thickness and 6mm in width, 8mm in width of the dislocation edge and 2570 g in weight.

Example 3

Will: 220 g of high molecular polymer liquid polyurethane resin, curing agent and modifier; 250 g of barium sulfate; 450 g of metal bismuth powder and 1400 g of bismuth oxide (wherein, the average grain diameter is 2 mu m beta-Bi)₂O₃700g of powder; alpha-Bi having an average particle diameter of 43 μm₂O₃700g of powder) is put into a vacuum stirring device to be fully stirred to generate a glue compound, the glue compound is pressed into a die cavity between flat vulcanizing machines by a glue pressing device, the pressure is formed, the temperature is increased to 80 ℃ to be cured for 1.5 hours, the surface of a product is cured, the product is placed at normal temperature for 24 hours, and an X-ray and gamma-ray shielding brick with the radiation shielding effectiveness equivalent to 3.0mm lead equivalent and the strength and the elasticity meeting the specified requirements is obtained, the weight of the product is 2320 g, and the shape of the product is shown in the attached figure4, the size of the upper layer plate is 190mm multiplied by 180mm, the thickness is 6mm, the size of the lower layer plate is 200mm multiplied by 190mm, the thickness is 6mm, and the lap width is 10 mm.