For making polarization3Glass of He gas container and manufacturing method thereof
阅读说明：本技术 一种用于制作极化3He气体容器的玻璃及其制作方法 (For making polarization3Glass of He gas container and manufacturing method thereof ) 是由 王欣 吴骏军 吴海平 吴嘉琪 皮耕尉 于 2021-03-07 设计创作，主要内容包括：本发明提供一种用于制作极化～3He气体容器的玻璃及其制作方法,所述玻璃由以下摩尔百分比的组分制成：SiO-250-75mol％；Al-2O-35-20mol％；MO 15-45mol％；M为Mg、Ca、Sr、Ba、Pb、Zn中的一种或多种；其中50mol％＜(SiO-2+Al-2O-3-BaO-CaO-PbO-SrO)＜70mol％；同时65mol％＜(SiO-2+Al-2O-3+MgO+ZnO-BaO-CaO-PbO-SrO)。本发明的技术路线是综合考虑极化～3He容器玻璃的可加工性、退极化以及氦气透过率进行的配方设计,从而得到综合性能优良的极化～3He容器玻璃,使得极化～3He气体的产生、储运以及应用过程更为稳定。(The invention provides a method for making polarization 3 The glass of the He gas container and the manufacturing method thereof are characterized in that the glass is prepared from the following components in percentage by mole: SiO 2 2 50‑75mol％；Al 2 O 3 5-20 mol%; MO 15-45 mol%; m is one or more of Mg, Ca, Sr, Ba, Pb and Zn; wherein 50 mol% < (SiO) 2 +Al 2 O 3 -BaO-CaO-PbO-SrO) < 70 mol%; while 65 mol% < (SiO) 2 +Al 2 O 3 + MgO + ZnO-BaO-CaO-PbO-SrO). The technical route of the invention is healdTaking into account polarization 3 Formulation of processability, depolarization, and helium permeability of He vessel glass to achieve superior combinations of polarization properties 3 He vessel glass to polarize 3 The generation, storage and transportation and application processes of the He gas are more stable.)
1. For making polarization3The glass of the He gas container is characterized in that: the glass is prepared from the following components in percentage by mole: SiO 22 50-75mol％；Al2O35-20 mol%; MO 15-45 mol%; m is one or more of Mg, Ca, Sr, Ba, Pb and Zn.
2. A method for making a polarization according to claim 13The glass of the He gas container is characterized in that: 50 mol% < (SiO)2+Al2O3-BaO-CaO-PbO-SrO)＜70mol％。
3. A method for making a polarization according to claim 13The glass of the He gas container is characterized in that: 65 mol% < (SiO)2+Al2O3+MgO+ZnO-BaO-CaO-PbO-SrO)。
4. A method for making a polarization according to claim 13The glass of the He gas container is characterized in that: the density of the glass is more than 2.7g/cm3。
5. A method for making a polarization according to claim 13The glass of the He gas container is characterized in that: the glass has an atomic packing coefficient of not less than 0.48.
6. A method for making a polarization according to claim 13The glass of the He gas container is characterized in that: the helium permeation rate of the glass is more than 10000 times lower than that of quartz glass at the temperature of 100 ℃.
7. A method for making a polarization according to claim 13The glass of the He gas container is characterized in that: the coefficient of thermal expansion of the glass is less than 50 x 10-7/K。
8. Polarization3The manufacturing method of He gas container glass is characterized in that: firstly, 50-75 mol% of SiO2(ii) a 5-20 mol% of Al2O3(ii) a Mixing 15-45 mol% of MO, wherein M is one or more of Mg, Ca, Sr, Ba, Pb and Zn; then, uniformly mixing the mixed materials, placing the mixed materials in a crucible (platinum), placing the crucible containing the mixed materials in a melting furnace at 1600 ℃, and stirring the glass liquid after the mixed materials are melted; and after 10 hours, pouring the glass liquid into a mold, and after the glass liquid is shaped, placing the glass liquid into an annealing furnace at 650 ℃ for annealing to obtain a finished product.
Technical Field
The invention relates to the technical field of special glass, in particular to a method for manufacturing polarization3Glass for He gas container and its manufacturing method are provided.
Background
Polarised3He gas has been confirmed to be applicable to various fields. In middle and high energy nuclear physics experiments, polarization3He can act as an ideal, effectively polarized neutron target, producing polarized neutrons. Polarization in the field of life science3He also plays an important role, and research shows that polarization is performed3He is applied to magnetic resonance imaging to obtain organ images with higher quality, and the corresponding technology gradually becomes a new image totality in clinical diagnosis. In addition, polarization3He gas has important application in surface physics, basic symmetry inspection, quantum gyroscope and other aspects. Polarization is currently obtained3He is mainly spin-exchange optical pumping method, filled with3He、N2And an alkali metal polarization chamber is placed in a magnetic field, heated to a high temperature of about 200 ℃ by hot air to obtain saturated alkali metal vapor, and irradiated with laser light to obtain a high-polarization-degree3He gas.
Polarization of glass container3He gas plays an important role in the processes of generation, storage, transportation and application. Are currently used for3He gas glass vessels are often made of borosilicate glass as well as quartz glass. However, the quartz glass has low density and high helium permeability, and is not beneficial to the storage of 3He gas; polarization of3He gas has a high depolarization rate in borosilicate glass, which is not favorable3Polarization of He gas is maintained. Other more common silicate glasses (e.g., window glass) have a high coefficient of expansion, which is detrimental to the thermal processing of glass containers
Therefore, in view of the shortcomings of the prior art, it is necessary to design a method for making polarization3Glass for He gas container and its manufacturing method are provided to solve the above problems.
Disclosure of Invention
To overcome the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a method for making a polarizer3Glass for He gas container having low depolarization rate of polarized 3He gas, low thermal expansion coefficient and low thermal expansion coefficient, and method for producing sameHelium permeability.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: for making polarization3He gas container glass, the glass being made from the following components in mole percent: SiO 22 50-75mol％；Al2O35-20 mol%; MO 15-45 mol%; m is one or more of Mg, Ca, Sr, Ba, Pb and Zn.
The preferable technical scheme is as follows: 50 mol% < (SiO)2+Al2O3-BaO-CaO-PbO-SrO)＜70mol％。
The preferable technical scheme is as follows: 65 mol% < (SiO)2+Al2O3+MgO+ZnO-BaO-CaO-PbO-SrO)。
The preferable technical scheme is as follows: the density of the glass is more than 2.7g/cm3。
The preferable technical scheme is as follows: the glass has an atomic packing coefficient of not less than 0.48.
The preferable technical scheme is as follows: the helium permeation rate of the glass is more than 10000 times lower than that of quartz glass at the temperature of 100 ℃.
The preferable technical scheme is as follows: the coefficient of thermal expansion of the glass is less than 50 x 10-7/K。
Polarization3The He gas container glass is produced by mixing 50-75 mol% SiO2(ii) a 5-20 mol% of Al2O3(ii) a Mixing 15-45 mol% of MO, wherein M is one or more of Mg, Ca, Sr, Ba, Pb and Zn; then, uniformly mixing the mixed materials, placing the mixed materials in a crucible (platinum), placing the crucible containing the mixed materials in a melting furnace at 1600 ℃, and stirring the glass liquid after the mixed materials are melted; and after 10 hours, pouring the glass liquid into a mold, and after the glass liquid is shaped, placing the glass liquid into an annealing furnace at 650 ℃ for annealing to obtain a finished product.
Due to the application of the technical scheme, the invention has the beneficial effects that:
the technical route of the invention is to comprehensively consider polarization3Formulation of processability, depolarization, and helium permeability of He vessel glasses to achieve a combination of propertiesExcellent polarization3He vessel glass to polarize3The generation, storage and transportation and application processes of the He gas are more stable.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Polarization of3The He glass container is manufactured by adopting a blowing mode, and the processability of the glass refers to whether the glass is suitable for blowing. The blowing process generally involves heating the glass to a temperature above the softening temperature, controlling the deformation of the glass by changes in air pressure, and then cooling. Since a rapid cooling and heating process from a softening temperature to a room temperature is designed in the blowing process, the glass is required to have a small thermal expansion coefficient. The invention controls the expansion coefficient of the glass by designing the components of the glass, and does not add alkali metal elements which can cause the expansion coefficient to be increased.
3Depolarization of He gas is also called polarization relaxation, and longer polarization relaxation time indicates that polarization performance is better maintained. Influence of3Factors of He polarization relaxation time mainly include other factors3Collisions of He atoms, spatial gradients of the magnetic field, collisions and magnetic interactions with the inner wall of the polarized gas vessel, etc. The content of the invention is that the glass does not contain magnetic ions such as transition metal ions and the like, and polarization is avoided3Magnetic interaction of He gas with the glass. In addition, the generation of microcracks in the glass is avoided as much as possible to reduce3He gas has an effective area with the glass. The Al element in the glass exists in two forms of six coordination and four coordination, the stress of the tip of the generated crack corresponding to the glass microstructure area is about 1Gpa in the glass crack generation process, and if the Al element exists in the glass, part of the stress can be released through the change of the coordination number of the Al element, so that the generation of cracks is avoided. Therefore, the present invention relates to Al in glass2O3The content is more than 5mol percent, so that the probability of generating cracks can be reduced.
Studies have shown that helium permeability is related to the content of formers in the glass and to the atomic packing density of the glass, and that generally the lower the content of formers in the glass, the higher the density of the glass and the atomic packing coefficient, the lower the helium permeability. If the formula of the glass can be represented as MxOy, the glass atom packing coefficient V can be expressed as:
where ρ is the density, N0In terms of the Avogastrol constant, M is the molecular weight of the glass, and r is the ionic radius. For example, the density of the silica glass is 2.3g/cm3The atomic stacking factor was 0.45. The density of the glass related to the invention is more than 2.6g/cm by considering the helium permeability of the glass3The atomic packing coefficient is greater than 0.48.
He gas permeation rate K of the glass container can be expressed as:
wherein Q is the permeation quantity of He gas, delta p is the pressure difference of the He gas on two sides of the glass, A is the area of the glass, d is the thickness of the glass, and t is time.
Comprehensive polarization3The performance and process requirements of He container glass, the glass composition components of the invention comprise the following components in percentage by mole: SiO 22 50-75mol％；Al2O35-20 mol%; MO 15-45 mol%, wherein M is one or more of Mg, Ca, Sr, Ba, Pb and Zn;
wherein 50 mol% < (SiO)2+Al2O3-BaO-CaO-PbO-SrO)＜70mol％；
Meanwhile, 65 mol% < (SiO)2+Al2O3+MgO+ZnO-BaO-CaO-PbO-SrO)。
Specific examples (1-8) of the present invention are shown in Table 1. Table 1 shows the composition (mole percent) of the glass, the glass transition temperature Tg (. degree. C.), and the expansion coefficient (10 ℃ C.) in the range of 30 to 300 ℃-7(K); density (g/cm)3) And atomic packing coefficient.
Table 1:
example 1
Example 2
Example 3
Example 4
Example 5
Example 6
Example 7
Example 8
SiO2
72.5
65
50
50
50
70
60
50
Al2O3
10.1
8
12
12
20
5
5
17
MgO
15
20
10
15
10
CaO
8.4
5
8
8
SrO
0.3
8
BaO
8.7
5
5
5
ZnO
10
20
15
10
20
20
PbO
7
5
SiO2+Al2O3-BaO-CaO-PbO-SrO
65.2
61
62
62
70
70
60
54
SiO2+Al2O3+MgO+ZnO-BaO-CaO-PbO-SrO
65.2
76
84
84
100
90
80
74
Tg(℃)
740
746
713
770
756
Expansion coefficient (10) in the range of 30-300 DEG C-7/K)
45
46
45
45
37
44
49
49
Density (g/cm)3)
2.77
2.95
2.76
3.02
2.83
2.77
3.33
3.14
Atomic packing coefficient
0.49
0.49
0.50
0.51
0.50
0.48
0.50
0.49
Log10K*
-16.6
-18.2
-16.5
-18.8
-17.1
-16.6
-21.5
-19.8
Log10(K/KSiO2)
-4.5
-6.0
-4.4
-6.7
-5.0
-4.5
-9.4
-7.7
Wherein, Log10K is used for representing the permeation condition of helium at 100 ℃, K is the permeation rate,q is He gas permeability in cm3(ii) a Δ p is the pressure difference of He gas on both sides of the glass, expressed in cmHg; a is the area of the glass in cm2(ii) a d is the glass thickness in mm; t is time in units of s.
The invention also provides a method for manufacturing polarized 3He gas container glass, firstly, 50-75 mol% of SiO2(ii) a 5-20 mol% of Al2O3(ii) a Mixing 15-45 mol% of MO, wherein M is one or more of Mg, Ca, Sr, Ba, Pb and Zn; then, uniformly mixing the mixed materials, placing the mixed materials in a crucible (platinum), placing the crucible containing the mixed materials in a melting furnace at 1600 ℃, and stirring the glass liquid after the mixed materials are melted; after 10 hours, pouring the glass liquid into a mold, and after the glass liquid is shaped, placing the glass liquid into an annealing furnace at 650 ℃ for annealing to obtain the glassAnd (5) obtaining a finished product.
Therefore, the invention has the following advantages:
the technical route of the invention is to comprehensively consider polarization3Formulation of processability, depolarization, and helium permeability of He vessel glass to achieve superior combinations of polarization properties3He vessel glass to polarize3The generation, storage and transportation and application processes of the He gas are more stable.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
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