CN108623146A - Environmentally friendly special type protection glass - Google Patents
Environmentally friendly special type protection glass Download PDFInfo
- Publication number
- CN108623146A CN108623146A CN201810672491.2A CN201810672491A CN108623146A CN 108623146 A CN108623146 A CN 108623146A CN 201810672491 A CN201810672491 A CN 201810672491A CN 108623146 A CN108623146 A CN 108623146A
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- China
- Prior art keywords
- glass
- special type
- environmentally friendly
- type protection
- protection glass
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
Abstract
The invention discloses a kind of environmentally friendly special type protection glass, contain following components in percentage by weight：SiO20.5 40.0%, Gd2O30.5 50.0%, B2O31.0 40.0%, BaO0.5 60.0%, Bi2O30.5 50.0%, MO0.1 40.0%, Al2O30.5 20.0%, TiO20.1 20.0%, W2O30 30.0%, La2O30 30.0%, CeO20 10.0%, Ta2O50 50.0%.The present invention is by the optimization to glass ingredient, without PbO, As2O3、Cr2O3In the case of causing the component seriously polluted to environment, the environmentally friendly special type protection glass that there can be good absorption ability to gamma-rays and X-ray is obtained.
Description
Technical field
The present invention relates to a kind of special type protection glass, and in particular to a kind of for the environmentally friendly of gamma-rays and X-ray
Special type protection glass.
Background technology
Special type protection glass, the i.e. glass with radiation protection and radiation hardness function, it can play X-ray, gamma-rays
Iris action, be widely used in nuclear energy research pry through and protective window, nuclear power station hagioscope, nuclear radiation environment under optical instrument panel
With camera lens, interplanetary probe protection face board, nuclear medicine protection etc. a variety of nuclear radiation environments, play an important role in core application field,
It is a kind of indispensable optical glass material.
Non-browning glass is mainly the glass for having to gamma-rays and X-ray larger absorbability.When gamma-rays or X-ray into
When entering protective glass, since inside glass generates photoelectric effect, generation electron-positron pair, while excitation state and free state electricity are generated
Son makes the gamma-rays of injection or X-ray energy reduce, and penetration power declines, and plays protective action.When the density of non-browning glass
When increase, screening ability also accordingly increases.
Addition PbO, As are generally required in current special type protection glass2O3、Cr2O3Equal toxic heavy metals, to improve to X
Ray, gamma-ray shield effectiveness, but with the improvement of people ' s living standards and the enhancing of environmental protection consciousness, gradually in glass
Give up PbO, As in production2O3、Cr2O3Deng the component for causing seriously to pollute to environment.
Invention content
The technical problem to be solved in the present invention is to provide a kind of environment that can have good absorption ability to gamma-rays and X-ray
Friendly special type protection glass.
There is provided a kind of environmentally friendly special type protections for technical solution used by the present invention solves above-mentioned technical problem
Glass contains following components in percentage by weight：SiO2：0.5-40.0%, Gd2O3：0.5-50.0%, B2O3：1.0-
40.0%, BaO：0.5-60.0%, Bi2O3：0.5-50.0%, MO：0.1-40.0%, Al2O3：0.5-20.0%, TiO2：0.1-
20.0%, W2O3：0-30.0%, La2O3：0-30.0%, CeO2：0-10.0%, Ta2O5：0-50.0%；Wherein, M Mg, Ca,
At least one of Sr, Zn；SiO2、B2O3And Al2O3The sum of weight percent be 2.0-60.0%, SiO2And Al2O3Weight hundred
Divide the sum of ratio and B2O3The ratio between weight percent is 0.2-1.2；As 1.0%≤BaO<When 40.0%, Bi2O3、Gd2O3、W2O3With
Ta2O5The sum of weight percent is 30.0-70.0%；As 40.0≤BaO≤60.0%, Bi2O3、Gd2O3、W2O3And Ta2O5Weight
It is 1.0-40.0% to measure the sum of percentage；SiO2And B2O3The sum of weight percent and TiO2The ratio between weight percent is 10-30.
Further, in environmentally friendly special type protection glass described above, also contain the group of following weight percent
Point：Y2O3：0-20.0%, ZrO2：0-10.0%, Sb2O3：0-5.0%, R2O：0-10.0%；Wherein, R Li, Na, K, Rb, Cs
At least one of.
Preferably, in environmentally friendly special type protection glass described above, SiO2：0.5-30.0%.
Preferably, in environmentally friendly special type protection glass described above, Gd2O3：0.5-45.0%.
Preferably, in environmentally friendly special type protection glass described above, B2O3：2.0-40.0%.
Preferably, in environmentally friendly special type protection glass described above, BaO：0.5-55.0%.
Preferably, in environmentally friendly special type protection glass described above, Bi2O3：1.0-45.0%.
Preferably, in environmentally friendly special type protection glass described above, MO：0.1-30.0%.
Preferably, in environmentally friendly special type protection glass described above, Al2O3：0.5-15.0%.
Preferably, in environmentally friendly special type protection glass described above, TiO2：0.1-10.0%.
Preferably, in environmentally friendly special type protection glass described above, W2O3：0.1-20.0%.
Preferably, in environmentally friendly special type protection glass described above, La2O3：0.1-20.0%.
Preferably, in environmentally friendly special type protection glass described above, CeO2：0-5.0%.
Preferably, in environmentally friendly special type protection glass described above, Ta2O5：0-20.0%.
Preferably, in environmentally friendly special type protection glass described above, Y2O3：0-10.0%.
Preferably, in environmentally friendly special type protection glass described above, ZrO2：0-5.0%.
Preferably, in environmentally friendly special type protection glass described above, Sb2O3：0-1.0%.
Preferably, in environmentally friendly special type protection glass described above, R2O：0-5.0%.
Wherein, environmentally friendly special type protection glass described above, nd 1.5-2.0.
Wherein, environmentally friendly special type protection glass described above, lead equivalent are not less than 0.03mmPb/mm.
Wherein, environmentally friendly special type protection glass described above, density 3.5-5.5g/cm3。
Wherein, environmentally friendly special type protection glass described above, coefficient of expansion α (20~300) DEG C<80×10-7/
℃。
Wherein, environmentally friendly special type protection glass described above, 1mm thickness special type protection glass are saturating in 550nm wavelength
Cross rate >=80%.
The beneficial effects of the invention are as follows：
The present invention makes the nd of special type protection glass reach 1.5-2.0 by the optimization to glass ingredient, and lead equivalent is not less than
0.03mmPb/mm, density 3.5-5.5g/cm3, 1mm thickness special type protection glass is in 550nm wavelength transmitance >=80%, expansion
Factor alpha (20~300) DEG C<80×10-7/ DEG C, without PbO, As2O3、Cr2O3Deng the component feelings for causing seriously to pollute to environment
Under condition, a kind of environmentally friendly special type protection glass is obtained.
Specific implementation mode
Specifically, environmentally friendly special type protection glass, contains following components in percentage by weight：SiO2：0.5-
40.0%, Gd2O3：0.5-50.0%, B2O3：1.0-40.0%, BaO：0.5-60.0%, Bi2O3：0.5-50.0%, MO：0.1-
40.0%, Al2O3：0.5-20.0%, TiO2：0.1-20.0%, W2O3：0-30.0%, La2O3：0-30.0%, CeO2：0-
10.0%, Ta2O5：0-50.0%；Wherein, at least one of M Mg, Ca, Sr, Zn；SiO2、B2O3And Al2O3Weight hundred
It is 2.0-60.0%, SiO to divide the sum of ratio2And Al2O3The sum of weight percent and B2O3The ratio between weight percent is 0.2-1.2；When
1.0%≤BaO<When 40.0%, Bi2O3、Gd2O3、W2O3And Ta2O5The sum of weight percent is 30.0-70.0%；When 40.0≤
When BaO≤60.0%, Gd2O3、W2O3And Ta2O5The sum of weight percent is 1.0-40.0%；SiO2And B2O3Weight percent it
With with TiO2The ratio between weight percent is 10-30.
SiO2The generation body best as glass is the skeleton that glass is formed, can increase the viscosity of glass, reduce its crystallization
Tendency, improves chemical stability, thermal stability, mechanical strength and the transparency of glass, but if its content is excessive, then can increase
The fusing difficulty of glass, reduces the barrier propterty of glass；Therefore, SiO2Weight content is 0.5-40.0%；Preferably 0.5-
30.0%.
B2O3Body is generated as glass, is filled in SiO2Between network, the compactness of glass network is improved, reaches raising glass
Glass density is to improve glass to gamma-rays and X-ray protection ability, B2O3Can also improve glass at glass properties, inhibit
Devitrification of glass, but if its content is excessive, then chemical stability and barrier propterty can all reduce；Therefore, B2O3Weight content is
1.0-40.0%；Preferably 2.0-40.0%；
Gd2O3With larger quality, it is steady to the protective capacities of gamma-rays and X-ray and chemistry to can effectively improve glass
Qualitatively effect, weight content 0.5-50.0%；Preferably 0.5-45.0%.
Al2O3As network intermediate, the stability of network can be increased, increase glass density and to gamma-rays and X-ray
Protective capacities, devitrification of glass can also be inhibited, but if its content is excessive, then can increase the fusing difficulty of glass, reduce glass
The density of glass is to reduce the barrier propterty of glass；Therefore Al2O3Weight content is 0.5-20.0%；Preferably 0.5-15.0%.
W2O3The density of glass can be improved and to gamma-rays and X-ray protection ability, but if its content is excessive, then glass
The transmitance of glass declines；Therefore, W2O3Weight content is 0-30.0%；Preferably 0.1-20.0%.
BaO can increase the chemical stability of glass, while BaO can also effectively reduce glass viscosity so that glass itself
Activity increase, make glass be easy to melt, clarification, BaO be used as heavy metallic oxide, still ideal ray absorbent material, but
If content is excessive, glass is easy devitrification；Therefore, BaO weight contents are 0.5-60.0%；Preferably 0.5-55.0%.
Bi2O3The density of glass can be significantly improved and to gamma-rays and X-ray protection ability, but if its content is excessive,
The transmitance of glass can be then caused to decline；Therefore, Bi2O3Weight content is 0.5-50.0%；Preferably 1.0-45.0%.
CaO can increase chemical durability of glass, mechanical strength, shortening strip as network outer body, and excessive introduce is easy
Crystallization, glass embrittlement, molding difficulty increase；For ZnO as network intermediate, being suitably introduced into reduces glass expansion coefficient, raisingization
Stability and thermostability are learned, glass surface smoothness is improved, if the amount introduced is excessive, glass surface tension becomes larger, and bubble is difficult
To overflow, devitrification of glass is also resulted in；MgO can reduce high temperature viscosity, tendency towards devitrification and the crystallization of glass as network outer body
Speed improves mechanical strength, chemical stability and thermal stability, and frit is made to lengthen, but if content is excessive, glass it is steady
Qualitative reduction is easy devitrification；SrO can reduce the fusion temperature of glass as network modifying oxide, and it is steady to increase glass chemistry
It is qualitative, ray can also be absorbed；It is 0.1-40.0% that the present invention, which controls MO weight contents,；Preferably 0.1-30.0%；Wherein, M
For at least one of Mg, Ca, Sr, Zn.
La2O3To improving the density of glass and being beneficial to gamma-rays and X-ray protection ability, but if its content mistake
More, then glass is easy crystallization devitrification；Therefore, La2O3Weight content is 0-30.0%；Preferably 0.1-20.0%.
CeO2To improving the density of glass and being beneficial or good clarification to gamma-rays and X-ray protection ability
Agent contributes to bubble to eliminate, and also has good radiation resistance, prevents glass devitrification under radiation environment, but its content mistake
More, glass transmitance declines apparent；Therefore, CeO2Weight content is 0-10.0%；Preferably 0-5.0%.
TiO2As network intermediate, the extent of polymerization of network can be improved, improves the density of glass and to gamma-rays and X
Radiation protection ability can also improve chemical durability of glass, TiO2The radiation resistance that glass can also be improved, prevents glass
The devitrification under high-energy irradiation, but if its content is excessive, then glass is easy crystallization devitrification, and chemical stability reduces；Therefore, TiO2
Weight content is 0.1-20.0%；Preferably 0.1-10.0%.
Ta2O5The density of glass can be improved and to gamma-rays and X-ray protection ability, but since it is expensive, so
If it is too high that its content crosses at most glass cost；Therefore, Ta2O5Weight content is 0-50.0%；Preferably 0-20.0%.
In order to advanced optimize environmentally friendly special type protection glass properties, on the basis of the above, in special type protection glass
Also contain following components in percentage by weight：Y2O3：0-20.0%, ZrO2：0-10.0%, Sb2O3：0-5.0%, R2O：0-
10.0%；Wherein, at least one of R Li, Na, K, Rb, Cs.
Y2O3The devitrification resistance property of glass can be improved, but if its content is excessive, then chemical stability reduces, and glass holds
Easy devitrification；Therefore, Y2O3Weight content is 0-20.0%；Preferably 0-10.0%.
ZrO2As intermediate oxide, the hardness, elasticity and chemical stability of glass can be improved, the heat of glass is reduced
The effect of the coefficient of expansion is beneficial to gamma-rays and X-ray protection ability, but if its content is excessive, then glass melting is tired
Difficulty is easy crystallization devitrification；Therefore, ZrO2Weight content is 0-10.0%；Preferably 0-5.0%.
Sb2O3It is a kind of good fining agent, is conducive to the spilling of gas in glass；Therefore, Sb2O3Weight content is 0-
5.0%；Preferably 0.1-1.0%.
R2O can reduce the viscosity of glass, and glass is made to be easy to melt, and can reduce the crystallization tendency of glass, increase glass
Transparency and gloss, but if its content is excessive, then the density of glass reduces, and barrier propterty is substantially reduced；Therefore, R2O weights
Amount content is 0-10.0%；Preferably 0-5.0%.
The present invention passes through SiO2、B2O3And Al2O3Combination keep glass finer and close, then add BaO, Bi2O3、Gd2O3、W2O3
And Ta2O5The protection of glass is improved etc. the density that can significantly improve glass and to the component of gamma-rays and X-ray protection ability
Ability, then pass through CeO2And/or TiO2Introducing reach radiation-resistant function.
The present invention makes the nd of special type protection glass reach 1.5-2.0 by the optimization to glass ingredient, and lead equivalent is not less than
0.03mmPb/mm, density 3.5-5.5g/cm3, 1mm thickness special type protection glass is in 550nm wavelength transmitance >=80%, expansion
Factor alpha (20~300) DEG C<80×10-7/ DEG C, without PbO, As2O3、Cr2O3Deng the component feelings for causing seriously to pollute to environment
Under condition, a kind of environmentally friendly special type protection glass is obtained.
Below by embodiment, invention is further described in detail, but does not therefore limit the scope of the present invention
Among the embodiment described range.
The optical glass that the embodiment of the present invention 1~10 is provided is prepared as follows：
Raw material corresponding to the component of glass in Examples 1 to 10 is weighed in proportion, platinum earthenware is added after being sufficiently mixed
It in crucible, melts at 1200~1500 DEG C, clarify, cool down after homogenizing；Melten glass is poured at 1100~1300 DEG C or so
Metal die after preheating；The melten glass of metal die after injection is preheated is put into togerther Xu in annealing furnace with metal die
It is cold, environmentally friendly special type protection glass, the relevant parameter of test environment friendly special type protection glass are obtained after annealing.
The component and performance test methods of the environmentally friendly special type protection glass of Examples 1 to 10 are as follows：
Refractive index (nd) GB/T903-87 colouless optical glasses refractive index and chromatic dispersion test method are tested, density GB/
T7962 colouless optical glass density measurement methods are tested, and Tg, Ts, α are with GB/T7962 colouless optical glasses linear expansion coefficient and turn
Temperature test method is tested, and 550nm transmitances are tested with GB/T7962 colouless optical glass spectrum internal transmittance test methods,
Lead equivalent is tested with the GB/T7962 colouless optical glasses performance test methods of resistance to X-ray, and lead equivalent is indicated per mm of thickness glass
It is equivalent to the protective capacities of how many mm of thickness stereotypes.
The component and performance of the environmentally friendly special type protection glass of Examples 1 to 10 are as described in Table 1：
1 Examples 1 to 10 special type protection glass of table
As shown in Table 1, the present invention makes special type protection glass have the lower coefficient of expansion by the optimization to glass ingredient
With higher Ts, glass is avoided to be deformed in gradient of temperature, lead equivalent is not less than 0.03mmPb/mm, is penetrated to gamma-rays and X
Line has good protective capacities, and is free of PbO, As2O3、Cr2O3Deng the component for causing seriously to pollute to environment, safer environmental protection.
Claims (9)
1. environmentally friendly special type protection glass, it is characterised in that：Contain following components in percentage by weight：SiO2：0.5-
40.0%, Gd2O3：0.5-50.0%, B2O3：1.0-40.0%, BaO：0.5-60.0%, Bi2O3：0.5-50.0%, MO：0.1-
40.0%, Al2O3：0.5-20.0%, TiO2：0.1-20.0%, W2O3：0-30.0%, La2O3：0-30.0%, CeO2：0-
10.0%, Ta2O5：0-50.0%；Wherein, at least one of M Mg, Ca, Sr, Zn；SiO2、B2O3And Al2O3Weight hundred
It is 2.0-60.0%, SiO to divide the sum of ratio2And Al2O3The sum of weight percent and B2O3The ratio between weight percent is 0.2-1.2；When
1.0%≤BaO<When 40.0%, Bi2O3、Gd2O3、W2O3And Ta2O5The sum of weight percent is 30.0-70.0%；When 40.0≤
When BaO≤60.0%, Gd2O3、W2O3And Ta2O5The sum of weight percent is 1.0-40.0%；SiO2And B2O3Weight percent it
With with TiO2The ratio between weight percent is 10-30.
2. environmentally friendly special type protection glass according to claim 1, it is characterised in that：Also contain following weight percent
The component of ratio：Y2O3：0-20.0%, ZrO2：0-10.0%, Sb2O3：0-5.0%, R2O：0-10.0%；Wherein, R Li, Na,
K, at least one of Rb, Cs.
3. environmentally friendly special type protection glass according to claim 1 or 2, it is characterised in that：At least meet following
One：
Preferably, SiO2：0.5-30.0%；
Preferably, Gd2O3：0.5-45.0%；
Preferably, B2O3：2.0-40.0%；
Preferably, BaO：0.5-55.0%；
Preferably, Bi2O3：1.0-45.0%；
Preferably, MO：0.1-30.0%；
Preferably, Al2O3：0.5-15.0%；
Preferably, TiO2：0.1-10.0%；
Preferably, W2O3：0.1-20.0%；
Preferably, La2O3：0.1-20.0%；
Preferably, CeO2：0-5.0%；
Preferably, Ta2O5：0-20.0%.
4. environmentally friendly special type protection glass according to claim 2, it is characterised in that：At least meet following one
：
Preferably, Y2O3：0-10.0%；
Preferably, ZrO2：0-5.0%；
Preferably, Sb2O3：0-1.0%；
Preferably, R2O：0-5.0%.
5. according to the environmentally friendly special type protection glass of Claims 1 to 4 any one of them, it is characterised in that：The special type
The nd of protective glass is 1.5-2.0.
6. according to the environmentally friendly special type protection glass of Claims 1 to 4 any one of them, it is characterised in that：The special type
The lead equivalent of protective glass is not less than 0.03mmPb/mm.
7. according to the environmentally friendly special type protection glass of Claims 1 to 4 any one of them, it is characterised in that：The special type
The density of protective glass is 3.5-5.5g/cm3。
8. according to the environmentally friendly special type protection glass of Claims 1 to 4 any one of them, it is characterised in that：The special type
20~300 DEG C of coefficient of expansion α of protective glass<80×10-7/℃。
9. according to the environmentally friendly special type protection glass of Claims 1 to 4 any one of them, it is characterised in that：1mm is thick extraordinary
Protective glass is in 550nm wavelength transmitance >=80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810672491.2A CN108623146A (en) | 2018-06-26 | 2018-06-26 | Environmentally friendly special type protection glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810672491.2A CN108623146A (en) | 2018-06-26 | 2018-06-26 | Environmentally friendly special type protection glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108623146A true CN108623146A (en) | 2018-10-09 |
Family
ID=63688394
Family Applications (1)
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| CN201810672491.2A Pending CN108623146A (en) | 2018-06-26 | 2018-06-26 | Environmentally friendly special type protection glass |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205067A (en) * | 2020-01-15 | 2020-05-29 | 武汉科技大学 | Glass-ceramic material for cooperative protection of neutrons and gamma rays and preparation method thereof |
| CN114222721A (en) * | 2019-09-30 | 2022-03-22 | 住田光学玻璃公司 | X-ray shielding glass and glass member |
| CN115611513A (en) * | 2022-10-28 | 2023-01-17 | 南京玻璃纤维研究设计院有限公司 | Radiation-resistant glass material and preparation method and application thereof |
| CN116750966A (en) * | 2023-06-20 | 2023-09-15 | 成都光明光电有限责任公司 | Radiation-resistant glass |
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| CN1785864A (en) * | 2005-11-02 | 2006-06-14 | 河南安彩高科股份有限公司 | Leadless silicate glass composition and pipe cone glass for cathode ray tube |
| WO2007043280A1 (en) * | 2005-10-13 | 2007-04-19 | Ohara Inc. | Radiation shielding glass |
| CN104926120A (en) * | 2015-06-11 | 2015-09-23 | 成都光明光电有限责任公司 | Special protective glass |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007043280A1 (en) * | 2005-10-13 | 2007-04-19 | Ohara Inc. | Radiation shielding glass |
| CN1785864A (en) * | 2005-11-02 | 2006-06-14 | 河南安彩高科股份有限公司 | Leadless silicate glass composition and pipe cone glass for cathode ray tube |
| CN104926120A (en) * | 2015-06-11 | 2015-09-23 | 成都光明光电有限责任公司 | Special protective glass |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114222721A (en) * | 2019-09-30 | 2022-03-22 | 住田光学玻璃公司 | X-ray shielding glass and glass member |
| CN111205067A (en) * | 2020-01-15 | 2020-05-29 | 武汉科技大学 | Glass-ceramic material for cooperative protection of neutrons and gamma rays and preparation method thereof |
| CN111205067B (en) * | 2020-01-15 | 2022-04-01 | 武汉科技大学 | Glass-ceramic material for cooperative protection of neutrons and gamma rays and preparation method thereof |
| CN115611513A (en) * | 2022-10-28 | 2023-01-17 | 南京玻璃纤维研究设计院有限公司 | Radiation-resistant glass material and preparation method and application thereof |
| CN116750966A (en) * | 2023-06-20 | 2023-09-15 | 成都光明光电有限责任公司 | Radiation-resistant glass |
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Application publication date: 20181009 |