CN1092613C - 吸收紫外辐射的棕色玻璃 - Google Patents
吸收紫外辐射的棕色玻璃 Download PDFInfo
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
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- 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
- C03C4/02—Compositions for glass with special properties for coloured glass
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- 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
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
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Abstract
本发明涉及吸收紫外辐射的棕色玻璃，其特征在于它们具有以下组分(以氧化物的重量%表示)：SiO2 59-78；Al2O3 2-6；B2O3 0-3；Na2O 7-16；K2O 2-9；CaO 0-7；BaO 0-12；ZnO 0-12；ZrO2 0-6；TiO2 0-6；MnO2 0.25-6；V2O5 1-3；Fe2O3 0-1.5；NiO 0-0.5；CoO 0-0.1；Sb2O30-0.7；As2O3 0-0.7；F 0.05-1.0；其中MnO2+Fe2O3+V2O5＞1.5；Al2O3+SiO2≥65。该玻璃可用以制造太阳眼镜。
Description
本发明涉及吸收紫外辐射的棕色玻璃。
棕色的太阳眼镜在市上销售已有很多年。近年来，人们普遍注意更好地保护自己避免受到紫外辐射。这特别表现在对于提高太阳眼镜过滤紫外辐射能力的关切。市售的满足这功能的眼镜已经存在，它们基本上是以处在被氧化形式(即在三价铁形式)的氧化铁吸收紫外辐射的能力为基础的。
但是，工业上制造含有氧化铁并且其中的铁是处于Fe3+形式的棕色玻璃是比较复杂的，因为在制造玻璃过程中要保持氧化条件。
而且，含有氧化铁作为UV吸收体的玻璃，其紫外吸收特性并不完全令人满意，特别是在吸收的波长范围方面。
因此，需要有紫外吸收性能更好而制造方法较简单的棕色玻璃。本发明的目的就是满足这种需求。
更具体地，本发明涉及吸收紫外辐射的棕色玻璃，其特征在于它们具有以下的组分(以氧化物的重量％表示)：
宽范围 较佳范围
SiO2 59-78 61-68
Al2O3 2-6 3-5
B2O3 0-3 0-1.5
Na2O 7-16 10-15
K2O 2-9 2-5
CaO 0-7 5-7
BaO 0-12 0-10
ZnO 0-12 0-10
ZrO2 0-6 0-2
TiO2 0-6 0-3
MnO2 0.25-6 1-3.5
V2O5 1-3 1-2.5
Fe2O3 0-1.5 0-1
NiO 0-0.5 0.1-0.4
CoO 0-0.1 0.0050-0.0500
Sb2O3 0-0.7 0-0.5
As2O3 0-0.7 0-0.5
F 0.05-1.0 0.1-0.75
其中MnO2+Fe2O3+V2O5 ＞1.5 ＞2.0
Al2O3+SiO2 ≥65 ≥65
附图表示本发明玻璃的色度坐标x和y，它显示限定本发明玻璃的色度坐标区域的色度多边形(box)。
本发明的2毫米厚的玻璃，在其较好的实例中，实际上吸收波长高至380毫微米甚至400毫微米的全部紫外辐射。
本发明玻璃的颜色，可通过在基本着色氧化物Fe2O3和MnO2以外，合理地添加NiO，CoO等常规的着色氧化物而非常精确地调节。特别是，可以制得在2毫米厚度下，对可见光的百分透射率小于22％的玻璃，这是用以制造太阳眼镜时所要求的，而且该玻璃的色度位于色度图上多边形ABCDA的内部，该多边形由以下色度坐标确定：
x y
A 0.4000 0.3600
B 0.4650 0.3850
C 0.4650 0.4300
D 0.4000 0.4100
在附图中，色度坐标x位于水平轴，坐标y位于垂直轴。附图中多边形ABCDA围绕能给出本发明可接受的色彩的坐标组合。
此外，其可见光透射光谱可满足道路信号识别标准。
本发明的玻璃还对化学侵蚀具有良好的抗御能力，而且可适应目前用以提高其机械性能的化学时效工艺。
在本发明的玻璃中，存在的铝必须大于2％，以保证其化学耐久性。由于同样的原因，Al2O3+SiO2之和必须超过65％。
碱金属氧化物在高温下可降低玻璃的黏度而促进其熔融。而且它们可使玻璃得以进行化学时效处理，以使它们在设想的应用中具有足够的机械强度。但是，过量加入碱金属氧化物会使玻璃的化学耐久性变差。我们发现，Na2O和K2O在玻璃中的浓度分别保持在16％和9％以下，就可能得到良好的化学时效处理能力与适当的化学耐久性相结合。
在组合物中可以存在氧化锌，因为它可促进玻璃的化学时效处理。其含量较好低于12％，以限制对应的原材料的成本。
所述玻璃的光学特性由以下各元素决定。UV-A的吸收主要由氧化钒赋予，其含量至少为1％。可见波段的透射率和玻璃的颜色是用锰、钒、铁的氧化物调节，它们各自的浓度分别不超过6、3、和1.5％，而它们的总和大于1.5％。
也可以添加常规的着色氧化物，如NiO、CoO等，以使颜色优化。氧化钴和氧化镍的含量一般分别保持在0.1和0.5％以下，以使玻璃保持足够的透射水平。
如果需要调节玻璃的折射率，可按常规的方式各别或结合地使用锆、钛或钡的氧化物。BaO的用量不超过12％，以使其密度可适应于设想的用途。ZrO2的用量应小于6％，以避免产生玻璃熔化或析晶方面的问题。
如果需要，可用氧化砷、氧化锑和/或氟来进行玻璃的澄清。但是，较好的澄清剂是氟，因为在澄清作用以外，它也可防止熔融开始时玻璃浴不合时地产生泡沫。我们发现本发明的玻璃对这种发泡现象非常敏感，在原料中加入一定比例的氟化合物，使组合物含有至少0.05％F，最好至少0.1％F，可完全消除这种现象。应当注意在原料中加入的氟的比例一般应高于这些数值，因为熔融时会产生损耗。依赖于各种条件，所加入的氟的数量可以是最终玻璃中分析量的一倍。但氟的浓度必须保持低于1％，超过该阈值，将会观察到对玻璃成形工具的过分腐蚀。
在它们的澄清作用以外，也可以为了另外的原因而使用氧化锑和/或氧化砷，即用作使铁和锰的氧化—还原态稳定的缓冲剂，从而调节玻璃在可见波段的透射率及其颜色。
在表I中，实施例1和3是本发明的玻璃。实施例2是本发明范围以外的。这些玻璃是按照以下的步骤在实验室内熔融制得的：
——精确称量玻璃制造工艺领域内常规的原料，并将其混合形成均匀的可玻璃化的混合物。例如，可用碳酸盐作为氧化钠和氧化钾的来源。
——在铂坩埚中进行熔融，在接近于1450℃的温度下进行3小时。
——然后将玻璃注入模具中形成棒状，在580℃退火一小时，以使熔融后快速冷却过程中产生的应力松弛。
——在玻璃完全冷却后，将其加工成2毫米厚的样品，由这些样品测量其性质。
虽然这方法是实验室方法，本领域的熟练技术人员清楚地知道，也可在工业条件下熔融更多数量的玻璃。
在表I中列出的光学性质是：可见光透射率(Y％)，色度坐标(x和y)，透射率等于1％处的波长(UV)，满足道路信号识别标准的能力(TSR；例如ANSI Z80.3-1986标准)，以及折射率(nd)。
实施例1和3说明了本发明组合物所能得到的性能。这两个实施例特别显示出以下特征：在可见光范围的透射率足够低，从而可用以制作太阳眼镜；三原色坐标位于前面所述的极限范围内；对紫外辐射的完全吸收；和符合信号识别标准。实施例2虽然满足所有以上性质，但它是使用半工业装置，炉中的组合物不含氟时，研究过程中遇到发泡现象的代表性产物。这种发泡意味着熔融困难，在大多数时间内导致玻璃中存在各种比例的气泡，使产品在商业上是不能接受的。因此，实施例2是在本发明的组合物范围之外的(本发明需要有最低的氟含量)
表I
| 1 | 2 | 3 | |
| SiO2 | 63.8 | 62.3 | 61.8 |
| B2O3 | - | - | - |
| Al2O3 | 5 | 5 | 5 |
| Na2O | 14.3 | 8 | 8 |
| K2O | 3.1 | 8.8 | 8.8 |
| CaO | 6.1 | - | - |
| BaO | - | 10 | 10 |
| ZnO | 3.5 | - | - |
| TiO2 | 0.3 | - | - |
| ZrO2 | - | - | - |
| V2O5 | 1.4 | 2.7 | 2.7 |
| MnO2 | 1.5 | 3.1 | 3.1 |
| Fe2O3 | 0.3 | - | - |
| NiO | 0.17 | 0.1 | 0.1 |
| CoO | 0.0160 | 0.0077 | 0.0077 |
| F | 0.5 | - | 0.5 |
| Y％ | 20.6 | 16.2 | 10.2 |
| x | 0.4047 | 0.4286 | 0.4623 |
| y | 0.3988 | 0.3953 | 0.3850 |
| UV(nm) | 386 | 402 | 402 |
| TSR | 是 | 是 | 是 |
| nd | - | 1.524 | 1.523 |
| 发泡 | 无 | 很广泛 | 无 |
Claims (5)
1.吸收紫外辐射的棕色玻璃，其特征在于它们具有下列以重量％表示的组分：
SiO2 59-78
Al2O3 2-6
B2O3 0-3
Na2O 7-16
K2O 2-9
CaO 0-7
BaO 0-12
ZnO 0-12
ZrO2 0-6
TiO2 0-6
MnO2 0.25-6
V2O5 1-3
Fe2O3 0-1.5
NiO 0-0.5
CoO 0-0.1
Sb2O3 0-0.7
As2O3 0-0.7
F 0.05-1.0
其中MnO2+Fe2O3+V2O5 ＞1.5
Al2O3+SiO2 ≥65。
2.如权利要求1所述的玻璃，其特征在于它们具有下列以重量％表示的组分：
SiO2 61-68
Al2O3 3-5
B2O3 0-1.5
Na2O 10-15
K2O 2-5
CaO 5-7
BaO 0-10
ZnO 0-10
ZrO2 0-2
TiO2 0-3
MnO2 1-3.5
V2O5 1-2.5
Fe2O3 0-1
NiO 0.1-0.4
CoO 0.0050-0.0500
Sb2O3 0-0.5
As2O3 0-0.5
F 0.1-0.75
其中MnO2+Fe2O3+V2O5＞2.0
Al2O3+SiO2 ≥65。
3.如权利要求1或2所述的玻璃，其特征在于该玻璃的色度坐标位于多边形ABCDA的内部，该多边形由以下的色度坐标确定：
x y
A 0.4000 0.3600
B 0.4650 0.3850
C 0.4650 0.4300
D 0.4000 0.4100
4.如权利要求1-2中任一项所述的玻璃，其特征在于当厚度为2毫米时，其可见光透射率低于22％。
5.如权利要求3所述的玻璃，其特征在于在2mm的厚度下其可见光透射率小于22％。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR95/15277 | 1995-12-21 | ||
| FR9515277A FR2742745B1 (fr) | 1995-12-21 | 1995-12-21 | Verre brun absorbant les rayons ultraviolets |
| US1485496P | 1996-04-04 | 1996-04-04 | |
| US60/014,854 | 1996-04-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1204306A CN1204306A (zh) | 1999-01-06 |
| CN1092613C true CN1092613C (zh) | 2002-10-16 |
Family
ID=26232399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96199034A Expired - Fee Related CN1092613C (zh) | 1995-12-21 | 1996-12-11 | 吸收紫外辐射的棕色玻璃 |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0869925B1 (zh) |
| JP (1) | JP2000506483A (zh) |
| CN (1) | CN1092613C (zh) |
| BR (1) | BR9612134A (zh) |
| CA (1) | CA2239363A1 (zh) |
| DE (1) | DE69611938T2 (zh) |
| WO (1) | WO1997023422A1 (zh) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851940A (en) * | 1997-07-11 | 1998-12-22 | Ford Motor Company | Blue glass with improved UV and IR absorption |
| US5807417A (en) * | 1997-07-11 | 1998-09-15 | Ford Motor Company | Nitrate-free method for manufacturing a blue glass composition |
| FR2804949B1 (fr) * | 2000-02-11 | 2002-09-06 | Saint Gobain Vitrage | Compositions de verre gris de type silico-sodo-calcique |
| CN1318338C (zh) * | 2004-01-17 | 2007-05-30 | 德州振华装饰玻璃有限公司 | 颜色玻璃棕色着色剂制备工艺 |
| JP6386236B2 (ja) * | 2014-02-25 | 2018-09-05 | 日本山村硝子株式会社 | 黒色系ガラス容器 |
| CN105948490A (zh) * | 2016-05-10 | 2016-09-21 | 刘康宁 | 一种教学用试剂瓶玻璃及其制备方法 |
| CN106125339A (zh) * | 2016-08-30 | 2016-11-16 | 东兴华鸿光学科技有限公司 | 茶色玻璃镜片 |
| CN106199776A (zh) * | 2016-08-30 | 2016-12-07 | 东兴华鸿光学科技有限公司 | 绿色玻璃镜片 |
| CN106154580A (zh) * | 2016-08-30 | 2016-11-23 | 东兴华鸿光学科技有限公司 | 蓝色玻璃镜片 |
| CN106348585A (zh) * | 2016-10-20 | 2017-01-25 | 南通向阳光学元件有限公司 | 一种蓝色光学玻璃 |
| FR3132656A1 (fr) * | 2022-01-29 | 2023-08-18 | Fabian Guhl | Procédé de frittage de précision pour injecter de masses à faible viscosité contenant de la poudre de verre ou de métal dans des matrices d’injection permanente modulaires en barbotine minérale |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4566987A (en) * | 1982-06-16 | 1986-01-28 | Schott-Glaswerke | Scintillation glass |
| US5403789A (en) * | 1994-02-28 | 1995-04-04 | Corning Incorporated | Ultraviolet absorbing, fixed tint brown sunglass |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL288521A (zh) * | 1963-01-30 | |||
| BE729345A (zh) * | 1969-03-04 | 1969-09-04 | ||
| US5324691A (en) * | 1990-04-10 | 1994-06-28 | Isuzu Glass Co., Ltd. | Glass composition |
| EP0456351A3 (en) * | 1990-04-10 | 1992-04-01 | Isuzu Glass Co., Ltd. | Glass compositions |
| DE4311180C1 (de) * | 1993-04-06 | 1995-01-12 | Flachglas Ag | Bronzefarbenes oder graufarbenes Kalknatron-Silikatglas |
| JP3368953B2 (ja) * | 1993-11-12 | 2003-01-20 | 旭硝子株式会社 | 紫外線吸収着色ガラス |
| US5405811A (en) * | 1994-02-28 | 1995-04-11 | Corning Incorporated | Ultraviolet absorbing, fixed tint green sunglass |
-
1996
- 1996-12-11 CN CN96199034A patent/CN1092613C/zh not_active Expired - Fee Related
- 1996-12-11 WO PCT/US1996/019723 patent/WO1997023422A1/en active IP Right Grant
- 1996-12-11 JP JP09523696A patent/JP2000506483A/ja active Pending
- 1996-12-11 DE DE69611938T patent/DE69611938T2/de not_active Expired - Fee Related
- 1996-12-11 EP EP96943693A patent/EP0869925B1/en not_active Expired - Lifetime
- 1996-12-11 CA CA 2239363 patent/CA2239363A1/en not_active Abandoned
- 1996-12-11 BR BR9612134A patent/BR9612134A/pt not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4566987A (en) * | 1982-06-16 | 1986-01-28 | Schott-Glaswerke | Scintillation glass |
| US5403789A (en) * | 1994-02-28 | 1995-04-04 | Corning Incorporated | Ultraviolet absorbing, fixed tint brown sunglass |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997023422A1 (en) | 1997-07-03 |
| EP0869925A4 (en) | 1999-03-03 |
| JP2000506483A (ja) | 2000-05-30 |
| EP0869925A1 (en) | 1998-10-14 |
| CA2239363A1 (en) | 1997-07-03 |
| CN1204306A (zh) | 1999-01-06 |
| BR9612134A (pt) | 1999-07-13 |
| DE69611938D1 (de) | 2001-04-05 |
| EP0869925B1 (en) | 2001-02-28 |
| DE69611938T2 (de) | 2001-06-13 |
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