CN1040095C - 中性的低透射率玻璃 - Google Patents
中性的低透射率玻璃 Download PDFInfo
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- C03C4/00—Compositions for glass with special properties
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Abstract
一种加入下列着色剂组分(以重量%)使太阳能透过率降低的中性、灰绿色、一般透过率低的苏打-石灰-氧化硅玻璃(不超过25%的透射率)：Fe2O3(总铁)1.3-2；NiO 0.01-0.05；CoO 0.02-0.04；Se 0.0002-0.003。此玻璃具有亚铁值为18-30。
Description
本发明涉及一种具有低可见光透射率，特别是低紫外辐射透射率和太阳能低总透过率的深色中性有色玻璃。虽然不限于特定的用途，该玻璃显示一种多方面性能的结合，使其高度适用于例如在车辆(如运货车)的后部位置的隐密玻璃窗中。这些性质包括对可见光透射率低，以降低对车辆内容物的可见性，对红外光和对太阳总能量透射率低，以降低车辆内部吸收的热量，对紫外辐射透射率低，以保护织物和其它内部成分不使其变质，优选一种中性灰绿色，以与范围很宽的内部和外部面层色彩协调一致，以及与平板玻璃制造方法，如与常用的商业浮法玻璃过程相适应的玻璃组成。
红外吸收好的玻璃通常是由还原玻璃中的铁成亚铁状态，或加铜而生产的。这些材料给玻璃以兰色。加进玻璃以实现好的紫外辐射吸收材料是Fe3+、Ce、Ti或V。加入玻璃以达到所需紫外吸收水平的数量是例如为使玻璃具有黄色。使玻璃既有好的红外吸收又有好的紫外吸收这两者相结合，是绿色或兰色玻璃。已经建议生产防IR和UV辐射性好的车辆玻璃是灰色或赤褐色，但本发明建议的玻璃倾向于具有浅绿黄色。
先有技术中中性的和具有一种兰、绿、灰或褐色的热吸收玻璃，趋于具有比隐密玻璃窗所要求高得多的太阳光透射率。例如，Reissue的美国专利25312号提出含有下列组分的灰色玻璃：0.2-1％Fe2O3、0.003-0.05％ NiO、0.003-0.02％CoO和0.003-0.02％Se，它在0.25英寸厚时可见光的透射率为35-45％。
一种典型的深灰色现有玻璃具有下列组成：72.9％SiO2、13.7％Na2O、0.03％ K2O、8.95％ CaO、3.9％ MgO、0.10％ Al2O3、0.27％ SO3、0.06％ Fe2O3、0.015％ CoO和0.095％NiO。此类玻璃对太阳能的吸收不如用于本发明目的所要求的那样低。
最近，已提出不含镍的灰色热吸收玻璃，用于低透射率玻璃窗。这些玻璃的实例可见于美国专利号4104076和5023210号。然而，这两份专利均包括氧化铬为着色剂，可能需要不同于惯用的上方烘烤池窑型熔炼窑的熔炼操作/设备，以在熔炼期内提供生产所需玻璃所必须的还原条件，另外，其含有氧化铁、氧化钴和硒着色剂的浓度也可能生产不出这里所需各种性质的玻璃。
迄今发现最有希望适用于隐密用途的玻璃窗，需要其上具有薄膜或涂层的玻璃基质，以实现所要求的性质。这种特别有效的玻璃窗的一个实例描述于R.D.Goodman和P.J.Tausch的美国专利5087525号中。尽管这些带膜的玻璃窗事实上是有益的，并能“精细改变”若干光谱性质，但是，特别是从成本观点考虑，生产一种其本身可提供隐密玻璃窗所需的各种性质的玻璃还是有利的。
我们已发现：对优良的中性隐密玻璃的要求是在CIELAB体系中玻璃具有颜色参数范围在可见光透射率不超过25％，优选不超过20％时为：a*-5±5，优选-4±3，更理想-4：b*0±10，优选+4±1，更理想+3：及L*50±10，优选50±5，更理想48±2。更具体地说，在4mm名义参考厚度时，本发明的玻璃显示可见光透射率(C.I.E.照明A)不超过25％；全太阳能透过率不超过25％，最好不超过18％，并在任何情况下不超过可见光透射率；紫外辐射透射率不超过18％，最好不超过15％*(*这里所述辐射透射率值是基于下列波长范围：紫外：300-400nm，可见光：380-720nm，全太阳光：300-2130nm)。这些中性的绿灰色玻璃，其明暗度系数不超过0.53，最好不超过0.46，是用加入某种严格比例的氧化铁、氧化钴、氧化镍和硒到标准苏打-石灰-氧化硅浮法玻璃基组合物中生产的。更具体说，已经发现采用氧化镍与高总铁含量玻璃相结合可提供所需玻璃，其中Fe2O3被还原，以提供特定的FeO与Fe2O3(总铁)之比，习惯上称之谓亚铁值。
在上面的叙述中，玻璃工业中常将在玻璃组合物或批料中所含总铁称为“表达为Fe2O3的总铁”。然而，在玻璃批料熔炼中，一部分总铁还原为FeO，而其余的保留为Fe2O3。在熔体中氧化亚铁和氧化铁间的平衡是这种氧化还原平衡的结果。Fe2O3的还原不仅产生FeO，而且也产生氧气，因此，降低了在所得玻璃产品中两种铁化合物的结合重量。因此，在所得玻璃组合物中所含实际FeO和Fe2O3的结合重量比表达为Fe2O3的总铁的批料重量轻。为此理由，应当理解在这里和在权利要求中所用的“总铁”或“表达为Fe2O3的总铁”的意思是还原前含在玻璃批料中铁的总重量。也应当理解，在这里和在权利要求中所用的“亚铁值”被定义为在生成的玻璃中氧化亚铁的重量百分数除以表达为Fe2O3的总铁的重量百分数。
除非另有说明，这里和所附权利要求中的术语“百分数(％)”和“份”是指重量％和重量份。波长色散X射线荧光用于测定NiO、Co3O4、和Se以及表达为Fe2O3的总铁。总铁还原的百分数是用分光光度计在1060nm波长处对样品的辐射传输的首次测量测得。1060nm处的透射率值就被用于计算以下式表示的光密度：
光密度＝log10 To/TTo＝100-估计的反射损失＝92T＝在1060nm处的透射率然后用此光密度计算还原百分数：
还原％＝110×光密度/(玻璃厚度(以mm计)×总Fe2O3的重量％)。
本发明的中性深色玻璃可由使用下表范围的铁、钴、镍和硒着色剂生产出来：
| 占玻璃的重量％ | ||
| 组分 | 范围 | 优选范围 |
| Fe2O3(总铁) | 1.3-2 | 1.3-1.6 |
| NiO | 0.01-0.05 | 0.0225-0.0285 |
| Co3O4 | 0.02-0.04 | 0.020-0.026 |
| Se | 0.0002-0.0030 | 0.0010-0.0020 |
| 含铁值 | 18-30％ | 20-24％ |
一种灰绿色中性彩色玻璃是以低色纯度为特征。本发明的玻璃有利地显示＜10％的色纯度，在优选的实施方案中＜8％。本发明的玻璃的波长范围窄，为490-565nm，优选545-565nm。
本发明玻璃显示下列CIELAB颜色参数：a*＝-5±5：b*＝0±10；L*＝50±10。
镍(氧化镍)的存在对于本发明的组成而言是基本的。在稳态操作的常规浮法池窑是与一定水平的铁平衡的。此铁的水平取决于玻璃中铁的总量，火焰的氧化还原等。在优选的总铁水平下，浮法池窑的“平衡”亚铁值是如此，以致必须加入氧化镍以实现所需的全太阳能透过率和预定的明暗度系数。
在此平衡铁值时代替使用氧化镍的方法是加还原剂，例如碳，到批料中，以增加亚铁值，以此来降低全太阳能透过率。但这不合要求，因为这会冒着玻璃由于高含量的铁-铁结合而由硫化铁着色(形成琥珀玻璃)的危险。
钠-钙-硅玻璃的基本特征是按全玻璃的重量百分数计具有如下组成：
SiO2 68-75％
Na2O 10-18％
CaO 5-15％
MgO 0-5％
Al2O3 0-5％
K2O 0-5％其它次要组分，包括熔融和精炼助剂如SO3，也可含于此玻璃组成中。少量BaO和B2O3有时也已包括在平板玻璃中，并可考虑是可加可不加的。向此基本玻璃中加入上述本发明的着色组份。
此玻璃不同于那些具体提到的，是基本不含着色剂的，除了这些可以作为杂质存在的任何痕量着色剂外。本发明的玻璃可以在常规池窑型熔窑中连续熔炼，并可由浮法形成不同厚度的平板玻璃(当假定其为板形时)，在浮法中熔融玻璃支持于熔融金属池，如锡池之上，并被冷却。
实例1-6都是本发明满意的实施方案，显示出合意的中性灰绿色外观，并可提供大为降低的太阳能透过率以及极为理想的明暗度系数(明暗度系数是从Lawrence Berkely Laboratories′Window3.1软件程序计算出，该程序以室外温度32℃(89°F)、室内温度24℃(75°F)，太阳光强度248Btu/hr·ft2，(789W/m2)，及7.5mph(12kph)的风为基础的)。因此，在所有这些实例中，在参考厚度4mm时，光透射率(“Ill A”)均小于20％。每个实例中全太阳能透过率(“TS”)均小于18％，并在所有情况下小于光透射率。紫外辐射透射率在每个实例中均极低，无一超过13％。每例中的明暗度系数在所有场合不超过0.47。
表1
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | |
| 总Fe2O3 | 1.364 | 1.653 | 1.628 | 1.428 | 1.431 | 1.420 |
| ％亚铁 | 20.1 | 19.7 | 27.7 | 21.2 | 22.3 | 21.6 |
| ％Co3O4 | 0.0212 | 0.0236 | 0.0223 | 0.0198 | 0.0213 | 0.0242 |
| ％NiO | 0.0257 | 0.0256 | 0.0125 | 0.0409 | 0.0271 | 0.0283 |
| ％Se | 0.0020 | 0.0020 | 0.0015 | 0.0019 | 0.0017 | 0.0014 |
| Ill A | 19.6 | 16.0 | 17.8 | 19.6 | 18.1 | 18.0 |
| TS | 17.5 | 13.4 | 11.5 | 16.2 | 15.0 | 15.5 |
| UV | 12.3 | 7.9 | 10.3 | 11.6 | 11.3 | 10.1 |
| L* | 51.7 | 47.1 | 50.1 | 51.4 | 49.8 | 49.7 |
| a* | -3.14 | -4.32 | -6.65 | -3.51 | -3.78 | -3.70 |
| b* | +3.39 | +4.55 | -2.17 | +4.96 | +3.31 | +3.24 |
| 主要波长(nm) | 560.8 | 560.1 | 490.8 | 565.0 | 556.0 | 556.0 |
| ％纯度 | 4.5 | 6.5 | 8.0 | 7.0 | 4.3 | 4.3 |
实例6的基本玻璃组成如下
实例6的批料混合物是
| 组分 | 全玻璃的重量％ |
| SiO2 | 73.2 |
| Na2O | 13.9 |
| CaO | 7.8 |
| MgO | 3.4 |
| SO3 | 0.20 |
| Al2O3 | 0.17 |
| 组分 | 重量百分数 |
| 砂 | 154 grams(g) |
| 苏打灰 | 50g |
| 石膏 | 1g |
| 石灰石 | 11g |
| 白云石 | 33g |
| 硝酸钠 | 0.5g |
| 三氧化二铁 | 3.12g |
| 硒* | .025g |
| Co3O4 | .0465g |
| NiO | .0595g |
*假定10％的Se保留。
由浮法生产的玻璃典型厚度范围为约2-10mm。对于本发明优选的太阳能辐射控制特点，为得到这里所述的透射率性质，优选玻璃厚度范围3-5mm。
正如本领域中的技术人员所知，在不偏离权利要求所规定的本发明的范围情况下，还可以做出许多变化。
Claims (22)
1.一种包括如下基本组成的中性色彩的钠-钙-硅玻璃：1.3-2重量(wt)％Fe2O3(总铁)、0.01-0.05wt％NiO、0.02-0.04wt％Co3O4和0.0002-0.003wt％Se，并具有18-30％的亚铁值；该玻璃具有≤0.53的明暗度系数。
2.根据权利要求1的玻璃，它具有由如下CIELAB体系规定的颜色参数：a*＝-5±5、b*＝0±10、L*＝50±10。
3.根据权利要求1的玻璃，它具有由如下CIELAB体系规定的颜色参数：a*＝-4±3、b*＝+4±1、L*＝50±5。
4.根据权利要求1的玻璃，它具有由如下的主要波长范围为490-565nm，色纯度小于10。
5.根据权利要求1的玻璃，它具有由如下的主要波长范围为545-565nm，色纯度小于8。
6.根据权利要求1的玻璃，该玻璃在名义厚度4mm时，具有≤25％的可见光透射率，≤25％全太阳能透过率和≤15％的紫外辐射透射率。
7.根据权利要求6的玻璃，其中Fe2O3(总铁)的重量百分数范围为1.3-1.6％。
8.根据权利要求6的玻璃，其中NiO的范围为0.0225-0.0285wt％。
9.根据权利要求6的玻璃，其中Co3O4的范围为0.020-0.026wt％。
10.权利要求6的玻璃，其中Se的范围为0.0010-0.0020wt％。
11.权利要求6的玻璃，其中亚铁值范围为约19-28％。
12.权利要求11的玻璃，其中亚铁值范围为20-24％。
13.权利要求6的玻璃，它具有由下列CIELAB体系规定的颜色参数：a*＝-5±5、b*＝0±10、L*＝50±5。
14.权利要求1的玻璃，该玻璃在名义厚度4mm时，具有≤20％的可见光透射率，≤18％全太阳能透过率，并在任何情况下不超过可见光透射率，和≤15％的紫外辐射透射率。
15.权利要求14的玻璃，它具有的明暗度系数≤0.46％。
16.一种包括如下基本组分的中性色彩的钠-钙-硅玻璃：1.3-1.6wt％Fe2O3(总铁)、0.0225-0.0285wt％NiO、0.02-0.026wt％Co3O4和0.0010-0.0020wt％Se，并具有18-30％的亚铁值：该玻璃在名义厚度4mm时，具有≤25％的可见光透射率，≤25％全太阳能透过率和≤15％的紫外幅射透射率。
17.根据权利要求16的玻璃，它具有亚铁值范围为20-24。
18.根据权利要求17的玻璃，它具有≤20％的可见光透射率，≤18％全太阳能透过率，并在任何情况下不超过可见光透射率，和≤15％的紫外辐射透射率。
19.权利要求16的玻璃，它具有的明暗度系数≤0.46％。
20.权利要求16的玻璃，它具有的主要波长范围为545-565nm，色纯度≤8。
21.权利要求16的玻璃，它具有由下列CIELAB体系规定的颜色参数：a*＝-4±3、b*＝+4±1、L*＝50±5。
22.权利要求21的玻璃，它具有由下列CIELAB体系规定的颜色参数：a*＝-4、b*＝+3、L*＝48±2。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/057,742 US5308805A (en) | 1993-05-05 | 1993-05-05 | Neutral, low transmittance glass |
| US08/057,742 | 1993-05-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1109684A CN1109684A (zh) | 1995-10-04 |
| CN1040095C true CN1040095C (zh) | 1998-10-07 |
Family
ID=22012479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94190267A Expired - Lifetime CN1040095C (zh) | 1993-05-05 | 1994-05-03 | 中性的低透射率玻璃 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5308805A (zh) |
| EP (1) | EP0649391B1 (zh) |
| JP (1) | JP3247894B2 (zh) |
| KR (1) | KR100295379B1 (zh) |
| CN (1) | CN1040095C (zh) |
| AT (1) | ATE159234T1 (zh) |
| AU (1) | AU671546B2 (zh) |
| BR (1) | BR9405335A (zh) |
| CA (1) | CA2139334C (zh) |
| DE (1) | DE69406241T2 (zh) |
| FI (1) | FI950067A (zh) |
| PL (1) | PL178233B1 (zh) |
| RU (1) | RU2129101C1 (zh) |
| WO (1) | WO1994025408A1 (zh) |
| ZA (1) | ZA943029B (zh) |
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- 1994-05-03 KR KR1019950700009A patent/KR100295379B1/ko not_active IP Right Cessation
- 1994-05-03 ZA ZA943029A patent/ZA943029B/xx unknown
- 1994-05-03 RU RU95110884A patent/RU2129101C1/ru active
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- 1994-05-03 EP EP94916638A patent/EP0649391B1/en not_active Expired - Lifetime
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- 1994-05-03 WO PCT/US1994/004850 patent/WO1994025408A1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| AU671546B2 (en) | 1996-08-29 |
| US5308805A (en) | 1994-05-03 |
| DE69406241T2 (de) | 1998-04-16 |
| CN1109684A (zh) | 1995-10-04 |
| JP3247894B2 (ja) | 2002-01-21 |
| ZA943029B (en) | 1995-10-30 |
| RU2129101C1 (ru) | 1999-04-20 |
| BR9405335A (pt) | 1999-08-31 |
| CA2139334A1 (en) | 1994-11-10 |
| ATE159234T1 (de) | 1997-11-15 |
| FI950067A0 (fi) | 1995-01-05 |
| JPH07508971A (ja) | 1995-10-05 |
| CA2139334C (en) | 2004-07-20 |
| DE69406241D1 (de) | 1997-11-20 |
| FI950067A (fi) | 1995-01-05 |
| KR950702509A (ko) | 1995-07-29 |
| EP0649391A4 (en) | 1996-05-08 |
| KR100295379B1 (ko) | 2001-09-17 |
| EP0649391B1 (en) | 1997-10-15 |
| PL307136A1 (en) | 1995-05-02 |
| EP0649391A1 (en) | 1995-04-26 |
| PL178233B1 (pl) | 2000-03-31 |
| WO1994025408A1 (en) | 1994-11-10 |
| AU6823894A (en) | 1994-11-21 |
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