Radiation-proof glass as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of special glass preparation, and particularly relates to radiation-proof glass as well as a preparation method and application thereof. The radiation-proof glass is prepared from the following oxides in percentage by mass: 30 to 45 percent by weight of SiO2, 10 to 25 percent by weight of B2O3, 7 to 12 percent by weight of BaO, 1 to 5 percent by weight of ZnO, 1 to 5 percent by weight of CeO2, 15 to 24 percent by weight of La2O3, 5 to 9 percent by weight of Gd2O3, 1 to 5 percent by weight of Ga2O3, 1 to 5 percent by weight of WO3 and 1 to 4.9 percent by weight of HfO2. The radiation-proof glass has the following advantages that the radiation-proof glass does not contain any one of heavy metal oxides such as As2O3, Sb2O3, PbO, Tl2O, CdO, BeO and V2O5 harmful to the environment, the shielding rate of the glass is larger than or equal to 96%, and the radiation-proof glass is excellent in optical uniformity, chemical stability and mechanical performance and good in anti-radiation performance. The invention further provides application of the radiation-proof glass in medical treatment, nuclear power and nuclear physics experiment protection and gamma ray protection.

Description

Technical Field

[0001] The invention belongs to the technical field of special glass preparation, and particularly relates to a radiation-proof glass material and a preparation method and application thereof. Background Art

[0002] With the continuous development of nuclear science and technology in my country, its application in nuclear power plants, radioactive medical diagnosis, nuclear power facilities, industrial flaw detection, nuclear physics experiments, space exploration and other fields has become increasingly widespread. However, various radiation in the field of nuclear science and technology, such as X-rays, gamma rays and neutron radiation, are very harmful to human health, the environment and the normal operation of instruments and equipment. In particular, gamma rays are extremely penetrating and harmful, making efficient radiation protection essential. In radiation protection, alpha and beta rays are usually not the main focus because of their weak penetrating ability and easy absorption, while the high energy and strong penetrating ability of gamma rays and neutrons make them the focus of shielding material protection. Nuclear radiation shielding windows are important equipment and facilities for researchers or operators to observe the solidification of nuclear waste, purification of spent fuel, and processing of nuclear raw materials on one side of the operating room. The shielding performance and radiation protection performance of their window materials are extremely high.

[0003] Since radiation-proof glass has the advantages of a wide adjustable range of glass components, excellent chemical stability, good mechanical properties, simple preparation method, and a large absorption capacity for high-energy particles and radiation, it is used as a shielding and peep window material and is widely used in the field of radiation protection. The radiation-proof glass in the prior art generally uses lead glass with a high lead content. Since this type of lead glass achieves radiation protection by adding heavy metal elements such as lead, as my country and the world gradually pay attention to environmental protection requirements, lead as a heavy metal element will cause pollution to the environment and damage to human health. In addition, it is difficult to improve the radiation shielding range, radiation protection effect, mechanical properties and chemical resistance of lead-containing radiation-proof glass. Summary of the invention

[0004] The purpose of the present invention is to provide a radiation-proof glass which has excellent chemical resistance, mechanical properties and does not contain heavy metal elements such as lead that pollute the environment and harm human health, in view of the deficiencies in the prior art.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A radiation-proof glass is prepared by including the following oxides in accordance with mass percentage (wt.%):

[0007]

[0008] Furthermore, the radiation-proof glass is preferably prepared by including the following oxides in accordance with mass percentage (wt.%):

[0009]

[0010] The radiation-proof glass of the present invention contains substantially no alkali metal oxides. Further, the alkali metal oxides herein refer to Li 2 O、Na 2 O.K 2 O、Rb 2 O、Cs 2 O、Fr 2 Any one of O, etc.

[0011] The radiation-proof glass of the present invention does not contain any metal oxides harmful to the environment, such as As 2 O 3 , Sb 2 O 5 , PbO, Tl 2 O, CdO, BeO, V 2 O 5 Any of the above.

[0012] The present invention also provides a method for preparing the above-mentioned radiation-proof glass, comprising the following steps:

[0013] The raw materials are mixed evenly according to proportion; the mixture is melted at high temperature; the glass liquid is stirred, clarified and formed; and the radiation-proof glass is obtained after annealing.

[0014] The specific steps of melting include placing the uniformly mixed raw materials at a high temperature of 1460-1550° C. for melting for 6-12 hours.

[0015] The stirring speed during melting is 5-9r / min, and the stirring time is 4-6 hours, which promotes the clarification and homogenization of the glass liquid; the stirring is carried out in an oxygen atmosphere, and while stirring, oxygen is blown into the glass liquid at a flow rate of 0.2-0.5L / min, and the ventilation time is 2-3 hours.

[0016] The glass forming step includes cooling the forming temperature after melting to 1160-1250°C.

[0017] The annealing temperature of the glass is 600-650° C., and the annealing time is 18-36 hours.

[0018] In addition, the present invention also provides an application of the above-mentioned radiation-proof glass or the radiation-proof glass prepared by the above-mentioned preparation method in the fields of medical diagnosis, nuclear power and nuclear physics experiment protection, and gamma-ray protection. For example, it can be used as a radiation shielding window material in various instruments and equipment that require high transmittance, high precision and processing-resistant glass.

[0019] Compared with the prior art, the radiation-proof glass provided by the present invention has the following significant advantages:

[0020] (1) The present invention does not contain environmentally harmful metal oxides or heavy metal oxides such as As 2 O 3 , Sb 2 O 5 , PbO, Tl 2 O, CdO, BeO, V 2 O 5 Any one of the above, green and environmentally friendly;

[0021] (2) The radiation-proof glass provided by the present invention has good optical uniformity, chemical stability and mechanical properties. The shielding rate of the glass is ≥96%, and the transmittance is ≥90% in the visible light range of 390nm-780nm;

[0022] (3) The glass prepared by the method for preparing radiation-proof glass provided by the present invention has good radiation protection properties, high optical uniformity and melting quality, and can achieve large-scale and high-uniformity production. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the present invention clearer, the embodiments of the present invention are further described in detail below. The present invention is further described in detail below in conjunction with specific embodiments, but it is not intended to limit the present invention.

[0024] The present invention provides a radiation-proof glass, which is prepared by including the following oxides in accordance with mass percentage (wt.%):

[0025]

[0026] Preferably, the radiation-proof glass comprises the following oxides in weight percentage (wt.%):

[0027]

[0028] The radiation-proof glass provided by the present invention comprises SiO 2 It is a glass-forming oxide and an important network former of the radiation-proof glass provided by the present invention. It can improve the glass-forming ability and chemical stability of the glass. However, excessive use of SiO2 will increase the melting temperature of the glass and bring difficulties to the melting of the glass.2 The mass percentage is 30wt.%-45wt.%, preferably SiO 2 30wt.%-40wt.%, can not only obtain homogeneous glass, but also ensure reasonable glass melting temperature. If the content of this component is less than 30wt.%, the glass forming property, chemical stability, mechanical properties, etc. of the glass will be reduced, but if the content is higher than 45wt.%, the melting temperature of the glass will be increased, the viscosity will increase, and the radiation protection ability will be deteriorated.

[0029] B 2 O 3 It is a glass-forming oxide and a component of the glass network. It is also a solvent that reduces the viscosity of the glass melt and is the main component for increasing the refractive index of the glass. 3 ] and boron-oxygen tetrahedron [BO 4 ] as the structural component, under different conditions, boron may exist in the form of triangular [BO 3 ] or boron-oxygen tetrahedron [BO 4 ] exists. Under high temperature melting conditions, it is generally difficult to form boron-oxygen tetrahedrons, and can only exist in the form of trihedrons. However, at low temperatures, under certain conditions, B 3+ It has a tendency to capture free oxygen to form tetrahedrons, making the structure compact and increasing the low-temperature viscosity of the glass. However, it has the characteristics of reducing the viscosity of the glass at high temperatures and increasing the viscosity of the glass at low temperatures. 2 O 3 It also plays a role in fluxing. 2 O 3 It has a great interception effect on high-energy particle thermal neutrons and has a good ability to absorb radiation. 2 O 3 The mass percentage of B is 10wt.%-25wt.%, preferably 10wt.%-20wt.%. 2 O 3 The content of B is lower than 10wt.%, the shielding rate of the glass will be reduced, and the chemical stability of the glass will be reduced; 2 O 3 If the content is greater than 25wt.%, the mechanical properties of the glass will be reduced and the phase separation tendency of the glass will be increased.

[0030] BaO can improve the ability of glass to absorb gamma rays. The mass percentage of BaO is 7wt.%-12wt.%, preferably 7wt.%-10wt.%. If the content of BaO is less than 7wt.%, the protection ability of the glass will not be significantly improved, and the chemical stability of the glass will be reduced; if the content of BaO is greater than 12wt.%, the chemical resistance and mechanical properties of the glass will be reduced.

[0031] ZnO is a glass intermediate oxide and an important component of radiation-proof glass with excellent chemical stability. 6 ] octahedral form as a network exosome, when there is enough free oxygen in the glass, it can also exist as [ZnO 4 ] enters the network structure of the glass in the form of tetrahedron. The mass percentage of ZnO is controlled to be 1wt.%-5wt.%. When the content of ZnO is lower than 1wt.%, the chemical stability of the glass will be reduced; when the content of ZnO is higher than 5wt.%, the transmittance of the glass will be reduced and the phase separation tendency of the glass will be increased.

[0032] CeO 2 It can improve the radiation resistance of glass, and at the same time, it helps to clarify the glass and reduce the occurrence of glass defects. 2 The mass percentage is 1wt.%-5wt.%, CeO 2 When the content of CeO is less than 1wt.%, it has little effect on improving the radiation protection performance of the glass. 2 The content of Al2O3 above 5wt.% will reduce the transmittance of the glass.

[0033] La 2 O 3 It is a lanthanide rare earth oxide, La 3+ The ion radius is large and the electric field is strong, which results in a strong aggregation effect in the glass. It is a necessary component for the radiation-proof glass of the present invention to have radiation-proof ability and can improve the glass's ability to absorb gamma rays. 2 O 3 The mass percentage is 15wt.%-24wt.%, preferably 15wt.%-20wt.%, La 2 O 3 When the content is lower than 15wt.%, the radiation protection ability of the glass becomes poor and it is difficult to meet the application requirements. 2 O 3 When the content is greater than 24 wt.%, the chemical resistance of the glass will be deteriorated and the crystallization tendency of the glass will increase.

[0034] G 2 O 3 It can increase the quality of cations, increase the radiation shielding efficiency of glass, and improve the chemical stability of glass. 2 O 3 The mass percentage is 5wt.%-9wt.%, Gd 2 O 3 When the content is lower than 5wt.%, the radiation protection performance of the glass will deteriorate, but Gd 2 O 3 When the content is greater than 9 wt.%, the crystallization tendency of the glass will increase.

[0035] Ga 2 O 3 It is a glass network intermediate oxide, which can improve the glass forming properties, reduce the crystallization of glass and lower the melting temperature. 2 O 3 The mass percentage of Ga is 1wt.%-5wt.%. 2 O 3 When the content of Ga is less than 1wt.%, it cannot improve the glass forming properties. 2 O 3 A content greater than 5 wt.% will reduce the chemical stability of the glass.

[0036] WO 3 Can improve the chemical resistance of glass, WO 3 The mass percentage is 1wt.%-5wt.%, WO 3 When the content is less than 1wt.%, the chemical stability of the glass is not significantly improved, but WO 3 When the content is greater than 5 wt.%, the crystallization tendency of the glass will increase.

[0037] HkDJ 2 Can improve the chemical resistance of glass, HfO 2 The mass percentage is 1wt.%-4.9wt.%, preferably 1wt.%-3wt.%, HfO 2 The content of HfO is less than 1wt.%, which has little effect on improving the chemical resistance of glass. 2 The content of is higher than 4.9wt.%, which will increase the crystallization tendency of the glass.

[0038] The radiation-proof glass of the present invention does not contain any alkali metal oxides. The alkali metal oxides herein refer to Li 2 O、Na 2 O.K 2 O、Rb 2 O、Cs 2 O、Fr 2 Any one of O, etc.

[0039] According to the requirements of radiation protection application scenarios, especially the requirements for the properties of glass used for radiation protection equipment, shielding window materials, etc., the radiation protection glass of the present invention does not contain any heavy metal oxides such as As that are harmful to the environment. 2 O 3 , Sb 2 O 5 , PbO, Tl 2 O, CdO, BeO, V 2 O 5Any of the above, even if contained in very small amounts, is due to the other glass raw materials.

[0040] Furthermore, the radiation-proof glass provided by the present invention has good chemical stability and mechanical properties in the use environment, the shielding rate of the glass is ≥96%, and the transmittance is ≥90% in the visible light range of 390nm-780nm.

[0041] The glass prepared by the method for preparing the radiation-proof glass provided by the present invention has good radiation protection, high optical uniformity and high melting quality, and can realize large-size and high-uniformity production.

[0042] The parameters, measuring methods and instruments measured for a radiation-proof glass of the present invention are as follows. Table 1 lists in detail the glass chemical composition (wt.%) and glass properties of the embodiment.

[0043] Testing method for shielding rate of radiation-proof glass: using radiation source as 235 U, the radiation capacity is 143KeV, the detector is made of high-purity germanium crystal, the sample is 10cm away from the radiation source, and 10cm away from the detector. The radiation source is started to irradiate the sample to be tested with gamma rays, and the high-purity germanium detector is used to record the energy spectrum. The total energy peak area A of the 143KeV ray with or without the sample to be tested is analyzed. 有 and A 无 , and then calculate the shielding rate, shielding rate = (A 无 -A 有 ) / A 无 ×100%.

[0044] Test method for the transmittance of radiation-proof glass: Use UV-visible-infrared spectrophotometer for testing, and refer to the method of GB / T 2680-2021 "Determination of visible light transmittance, direct sunlight transmittance, total solar energy transmittance, ultraviolet transmittance and related window glass parameters of architectural glass".

[0045] Test method for optical uniformity of radiation-proof glass: refer to GB / T 7962.2-2010 "Test method for colorless optical glass Part 2: Optical uniformity - Fizeau plane interferometry" for testing.

[0046] Test method for elastic modulus of radiation-proof glass: refer to GB / T7962.6-2010 "Test method for colorless optical glass Part 6: Young's modulus, shear modulus and Poisson's ratio" for testing.

[0047] Test method for acid resistance stability of radiation-proof glass: refer to the method of GB / T 7962.14-2010 "Test method for colorless optical glass Part 14: Acid resistance stability" for testing.

[0048] Test method for moisture resistance stability of radiation-proof glass: refer to the method of GB / T 7962.15~2010 "Test method for colorless optical glass Part 15: Moisture resistance stability" for testing.

[0049] Table 1 Chemical composition (wt.%) and glass properties of the examples

[0050]

[0051] The present invention also provides a method for preparing radiation-proof glass. The components and amounts thereof are shown in Table 1. The following are the raw materials used in the embodiment and their requirements:

[0052] Quartz sand (high purity, 150μm sieve material less than 1%, 45μm sieve material less than 30%, Fe 2 O 3 Content less than 0.01wt.%), boric acid or boric anhydride (400μm sieve material is less than 10%, 63μm sieve material is less than 10%), barium carbonate (analytical grade), zinc oxide (analytical grade), cerium oxide (analytical grade), lanthanum oxide (analytical grade), gadolinium oxide (analytical grade), gallium oxide (analytical grade), tungsten oxide (analytical grade), hafnium oxide (analytical grade).

[0053] Example 1

[0054] First, according to the glass composition of Example 1 in Table 1, the corresponding raw materials are selected and weighed, and the alkali metal content in the glass raw materials is strictly controlled so that the ingredients meet the glass chemical composition of Example 1 in Table 1. Then, the glass batch materials are mixed evenly, and then the batch materials are added to the high temperature of 1500°C for melting for 10 hours. After the batch materials are all formed into glass liquid, they are stirred to promote the clarification and homogenization of the glass liquid. The stirring speed is 7r / min, and the stirring time is 5 hours. While stirring, oxygen is blown into the glass liquid at a flow rate of 0.4L / min, and the ventilation time is 2.5 hours. After the glass liquid is clarified and homogenized, it is cooled to 1200°C for leaking and forming. After the glass liquid is solidified and finalized, it is placed in an annealing furnace at 630°C for annealing for 24 hours. After it is naturally cooled to room temperature, a radiation-proof glass is obtained. Its test performance is shown in Example 1 in Table 1.

[0055] Example 2

[0056] According to the glass composition of Example 2 in Table 1, the corresponding raw materials are selected and weighed, and the alkali metal content in the glass raw materials is strictly controlled so that the ingredients meet the glass chemical composition of Example 2 in Table 1. Then the glass batch materials are mixed evenly, and then the batch materials are added to the high temperature of 1550°C for melting for 6 hours. After the batch materials are all formed into glass liquid, they are stirred to promote the clarification and homogenization of the glass liquid. The stirring speed is 9r / min, and the stirring time is 4 hours. While stirring, oxygen is blown into the glass liquid at a flow rate of 0.2L / min, and the ventilation time is 3 hours. After the glass liquid is clarified and homogenized, it is cooled to 1250°C for leaking and forming. After the glass liquid is solidified and finalized, it is placed in an annealing furnace at 650°C for annealing for 18 hours. After it is naturally cooled to room temperature, a radiation-proof glass is obtained. Its test performance is shown in Example 2 in Table 1.

[0057] Example 3

[0058] According to the glass composition of Example 3 in Table 1, the corresponding raw materials are selected and weighed, and the alkali metal content in the glass raw materials is strictly controlled so that the ingredients meet the glass chemical composition of Example 3 in Table 1. Then the glass batch materials are mixed evenly, and then the batch materials are added to the high temperature of 1460°C for melting for 12 hours. After the batch materials are all formed into glass liquid, they are stirred to promote the clarification and homogenization of the glass liquid. The stirring speed is 5r / min, and the stirring time is 6 hours. While stirring, oxygen is blown into the glass liquid at a flow rate of 0.5L / min, and the ventilation time is 2 hours. After the glass liquid is clarified and homogenized, it is cooled to 1160°C and leaked to form. After the glass liquid is solidified and finalized, it is placed in an annealing furnace at 600°C for annealing for 36 hours. After it is naturally cooled to room temperature, a radiation-proof glass is obtained. Its test performance is shown in Example 3 in Table 1.

[0059] Example 4

[0060] According to the glass composition of Example 4 in Table 1, the corresponding raw materials are selected and weighed, and the alkali metal content in the glass raw materials is required to be strictly controlled so that the ingredients meet the glass chemical composition of Example 4 in Table 1, and the same melting process system and test conditions as in Example 1 are used. The test performance of the sample is shown in Table 1.

[0061] Example 5

[0062] According to the glass composition of Example 5 in Table 1, the corresponding raw materials are selected and weighed, and the alkali metal content in the glass raw materials is required to be strictly controlled so that the ingredients meet the glass chemical composition of Example 5 in Table 1, and the same melting process system and test conditions as in Example 1 are used. The test performance of the sample is shown in Table 1.

[0063] From the data obtained in the examples, it can be seen that the radiation-proof glass of the present invention does not contain heavy metal oxides such as Pb that are harmful to the environment, and has the advantages of excellent chemical stability and mechanical properties, and is suitable for use in the fields of medical diagnosis, nuclear power and nuclear physics experiment protection, and gamma ray protection.

[0064] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. The protection scope of the present invention is defined by the claims. Those skilled in the art may make any modification or equivalent substitution, improvement, etc. to the present invention within the essence and protection scope of the present invention, and such modification or equivalent substitution is also deemed to fall within the protection scope of the present invention.

Claims

1. A radiation-proof glass, characterized in that: The invention comprises the following oxides prepared in accordance with mass percentage:

2. The radiation-proof glass according to claim 1, characterized in that: Preferably, the following oxides are prepared according to mass percentage:

3. The method for preparing radiation-proof glass according to claim 1 or 2, characterized in that: The following steps are involved: Mix the raw materials uniformly according to the proportion; melt the mixture at high temperature; The glass liquid is then stirred, clarified and formed; The radiation-proof glass is obtained after annealing.

4. The method for preparing radiation-proof glass according to claim 3, characterized in that: The specific melting step includes placing the uniformly mixed raw materials at a high temperature of 1460-1550° C. for melting for 6-12 hours.

5. The method for preparing radiation-proof glass according to claim 3, characterized in that: During the melting, the stirring speed is 5-9 r / min, and the stirring time is 4-6 hours; and while stirring, oxygen is blown into the glass liquid at a flow rate of 0.2-0.5 L / min, and the ventilation time is 2-3 hours.

6. The method for preparing radiation-proof glass according to claim 3, characterized in that: The forming temperature after melting is 1160-1250°C.

7. The method for preparing radiation-proof glass according to claim 3, characterized in that: The annealing temperature of the glass is 600-650° C., and the annealing time is 18-36 hours.

8. The radiation-proof glass according to claim 1 or 2, characterized in that: The radiation-proof glass does not substantially contain any metal oxides harmful to the environment, such as As2O3, Sb2O5, PbO, Tl2O, CdO, BeO, V2O5, etc.; and does not substantially contain any alkali metal oxides, where the alkali metal oxides refer to any one of Li2O, Na2O, K2O, Rb2O, Cs2O, Fr2O, etc.

9. The radiation-proof glass according to claim 1 or 2, characterized in that: The radiation-proof glass has good optical uniformity, chemical stability and mechanical properties. The shielding rate of the glass is ≥96%, and the transmittance is ≥90% in the visible light range of 390nm-780nm.

10. An application of the radiation protection glass according to claim 1 or 2, characterized in that: The radiation-proof glass can be applied to the fields of medical diagnosis, nuclear power and nuclear physics experiment protection, and gamma-ray protection.

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