CN1077438A - 高可见光、低紫外光和低红外光透射率的绿色玻璃组合物 - Google Patents
高可见光、低紫外光和低红外光透射率的绿色玻璃组合物 Download PDFInfo
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Abstract
用习用的玻璃熔化和炼制设备,不使用CeO2或
其它UV吸收添加剂生产出一种有利于光谱的黄色
谱带而不是浅蓝谱带的钠-钙-硅绿色玻璃,通过控
制铁(以Fe2O3表示)还原成FeO及这两种氧化物的
百分率可使生产出的玻璃具有如下特性:高可见光透
射率、低红外能量透射率、低紫外辐射透射率和低总
太阳能量透射率。
Description
本发明涉及具有高可见光、低紫外光、和低红外光透射率的玻璃组合物。更具体地说,本发明涉及具有作为汽车玻璃(包括挡风板)的独特用途,以及建筑用途的这种玻璃组合物。
人们早已知道,在配料中加入不同数量的铁可以使钠-钙-硅玻璃呈绿色。在这点上,习惯上常常把总的铁含量表示为Fe2O3的重量百分率,尽管铁在玻璃中可以以不同化合价状态存在。然而,人们也熟知,在总铁含量中氧化亚铁(FeO)和氧化铁(Fe2O3)的平衡可以使所得到的绿色的深浅以及玻璃的其它特性具有很大的差别。例如,一般来说,相对于Fe2O3而言,随着FeO浓度的增加,玻璃的颜色由黄绿色变为较低可见光透射率的暗绿色或兰绿色。
随着FeO与Fe2O3关系(即亚铁和铁含量)的改变,玻璃的其它特性也会改变。例如,还知道,二价状态(FeO)的铁在玻璃中是一种红外能量吸收剂。可惜的是,随着在消耗Fe2O3时,FeO含量的增加,紫外能量的吸收就减少,因为Fe2O3是一种UV吸收剂。还有报导说,在某种被认为对于高红外吸收来说是所希望的相当高的FeO浓度时,热量传递到玻璃熔体中受到严重的限制,因此必须采用特殊的熔融和炼制设备才能得到均匀的玻璃。
在本发明之前,熟悉本技术的人员所知道的关于制造具有较高可见光、低紫外光和低红外光透射率的含铁的钠-钙-硅绿玻璃的上述知识和其它有关资料的代表是美国专利No.4,792,536和No.5,007,133所公开的讨论和发明以及这里所引用和讨论的先有技术。
在这两篇先有技术专利比较好的具体实施方案中,以其自己的方式力图平衡玻璃中铁和亚铁的含量,其办法是通过改变氧化状态来改变其各自的量,以达到发明人所选定的一定的红外吸收水平,同时保持所需要的可见光透射度。此外,为了得到必要紫外吸收率和适合的总太阳光透射水平,这两篇专利都报导要添加氧化铈(CeO2)到组合物中。美国专利No.4,792,536确实公开了可以用来代替CeO2的某些其它UV(紫外光)吸收添加剂,如TiO2、V2O5和MoO3。另一方面,美国专利No.5,007,133声称在实施其发明中关键是使用CeO2,但又预料说,可用TiO2与CeO2掺合来补充一些CeO2。
所有这些UV吸收添加剂都是昂贵的,特别是CeO2。此外,这些添加剂在组合物中会产生它们本身的问题。例如,据报导,除了CeO2以外,添加剂对可见光透射率有不利的影响。另一方面,除了昂贵和本身对可见光透射率有不利的影响之外,CeO2还会抑制Fe2O3还原成FeO(即铁还原成亚铁)。
按美国专利No.4,792,536所报导的,关于制造可接受的绿玻璃的另一个问题是玻璃中硫的存在会抑制Fe2O3还原成FeO。遗憾的是,硫,例如以硫酸钠(“盐饼”NaSO4)形式存在的硫,是一种已知的、价廉的和有价值的钠-钙-硅玻璃炼制剂,特别是要用习用的“浮法”制造的在建筑和/或汽车方面使用的平板玻璃。由于硫对Fe2O3还原成FeO的抑制作用,美国专利No.4,792,536力图严格限制玻璃组合物中硫(SO3)的含量。此外,为了达到其总的目的,该专利把总的铁含量减到最小值,较好减至玻璃组合物总重量的约0.45%至0.65%(以保留可光见透射率)并且在还原条件下形成玻璃,以便从该适当的铁含量产生占总铁含量35%以上且最好至少50%(重量)的亚铁(FeO)。据称达到红外透射率不大于15%。
按照536专利所述的实例,当玻璃还原至达到这一IR透射率时,且由于低的总铁含量,UV透射率会由于少量三价铁的留下而增加。反之,对于UV吸收而言,这就需要添加剂,如CeO2等。因此,在大多数实例中可见光透射率(记为“LTA”)仍然很少接近达到对汽车玻璃所希望的、且往往是必要的70%的可见光透射水平。例如,在该专利中报导的没有使用特殊UV吸收剂(例如CeO2)的专利发明的组合物中,只有组合物14才具有70%或更高的可见光透射率。(实例11就是这样,但据说还原不充分,且使用1.0%氧化铈)。组合物14由于没有使用CeO2或任何其它上述吸收UV的氧化物(即TiO2、MoO3或V2O5),因此紫外光透射率,即使在5毫米厚时,也是很高的(51.3%)。这后一数值使得这些玻璃对于某些汽车的使用更不能接受。此外,在某些例子中,朝兰绿色的“倾斜”也使许多这样的组合物对于某些用户的技术要求不理想。
这篇536专利也叙述了四种“先有技术”玻璃组合物。组合物1是普通绿玻璃,其对太阳光的阻当显得较差。组合物2-4,尽管铁含量与我们的发明的玻璃有点接近。然而,与本发明的玻璃比较,即使当厚度减到小于5毫米时,在其太阳光控制特性上仍有一个或几个方面受损。在这方面,组合物2实际上与我们的发明是不同的玻璃,因为它的Al2O3和K2O含量高,使得难以采用特别适用于本发明的“浮法”生产。组合物3的SO3含量与本发明的玻璃也是大不相同的(一个约为0.20-0.25%(重量)的较窄的和较严格的范围,如下面所述),使得该组合物的玻璃难以炼制。与我们的发明相比,它的FeO/Fe2O3含量也是很高的,因此,当其厚度小于5毫米时,导致较高的UV透射率。组合物4是如此高度还原以致与我们的玻璃相比,其UV透射率非常高。此外,这种组合物只能用特殊技术生产,不适用于浮法。
与美国专利No.4,792,536的铁含量最小的低硫组合物相反,美国专利No.5,077,133的玻璃组合物力图通过使用较高总铁含量浓度来得到绿色玻璃。为了精炼的目的这种玻璃在其配料中也用了惯用的盐饼,且据说只需普通的熔融和精炼设备。这种玻璃通常着色成黄绿色,与536专利的兰绿色相反。
美国专利5,077,133力图使其本身与上述美国专利4,792,536不同(见第2栏第40行及以下等)。该专利这样做部分地是通过指出在后一篇专利中使用了相当低水平的铁含量并指出从而在最终的玻璃中所达到的特性。相反,美国专利5,077,133声称,该专利的玻璃使用了较高水平的总铁含量,并通过精心控制FeO与总铁含量(表示为Fe2O3)的比例和严格使用某些特定浓度的CeO2(单独或与TiO2一起),得到了比较好的颜色和透射性能。
更具体地说,美国专利声称,使用在某些极限范围的高总铁含量、某些特定的FeO与总铁含量比例(通过还原)和特定的CeO2值,施照体A可见光透射率大于70%,总太阳能透射率小于约46%,紫外辐射透射率小于约38%,且较好是小于34%。该专利还声称,施照体C的主波长是约498-约525毫微米,且该玻璃显示的色纯度是约2%-4%,与此相比,先有技术356专利的兰玻璃据说高达约10%。当然,这些特性可至少有一些是取决于厚度的,且由于这个原因,要说明的是,就总厚度为3-5毫米的玻璃而言(单片或多片)达到了这些缩合结果。
尽管美国专利5,077,133声称该专利的玻璃达到了“低红外能量”透射率(例如见第7栏,第1-2行),但它没有透露是何数值或数值范围。用美国专利4,792,536(见第13栏,第50行)中提出的式子可以计算出该133专利的IR透射率(TSIR)为约17-33%数量级。
美国专利5,077,133中报告的透射率、纯度和颜色特性是所希望达到的特性,特别是在汽车领域中用作挡风屏、侧面和后面的玻璃窗以及其它汽车玻璃。但是,正如在先有技术专利4,792,536中所述,使用CeO2,不论单独或与TiO2一起,对该专利所公开的发明是所不希望和有害的一个缺点。
因此,从上面来看很明显,在本技术中需要有一种玻璃组合物,它无需使用先有技术中迄今认为要达到适合的UV吸收所必需的特殊UV吸收添加剂,如CeO2,就能达到通常如美国专利5,077,133中所公开的透射率和颜色特性。
本发明的一个目的就是要满足这一点和本技术中的其它需要,下述公开一旦给出,熟练的技术人员就更明白这点。
一般来说,本发明通过提供一种吸收红外能量和紫外辐射的绿色玻璃满足了本技术的上述需要,这种玻璃按重量计基本组成如下:约71-74% SiO2;约12-20% Na2O;约8-10% CaO;约3-5% MgO;约0.10-0.30% Al2O3;约0-0.1% K2O;约0.20-0.25% SO3;约0.7-0.95%以Fe2O3表示的总铁;约0.19-0.24%以FeO表示的亚铁(较好0.20-0.24%),且其中厚度约为3.7-4.8毫米的玻璃的可见光透射率大于约70%;紫外光透射率小于约38%;总太阳光透射率小于约44.5%。
在一些较好的具体实施方案中,本发明的玻璃当厚度为约3.7-4.8毫米时除了具有上述的透射率外,还具有约2-4%的色纯度和约495-约510毫微米,最好约500-502毫微米的施照体C主波长。这个波长与约2-4%的色纯度一起代表了一种非常令人喜爱和审美的绿色,稍微靠近淡黄一侧,与光谱的浅兰一侧相对。因此,它能符合汽车工业中所要求的最终使用物的某些规格。
在一些更好的具体实施方案中,上述玻璃是在这样的还原条件下生产的,即按美国专利4,792,536的方法计算的FeO与总铁(以Fe2O3表示)的比值是约0.24-0.27,而按美国专利5,077,133的方法计算的还原成FeO的百分率是约25-29%。
美国专利5,077,133在该专利第4栏第28-44行报导了计算总铁还原百分率的方法。这一公开和方法列入本文作为参考,同样,美国专利4,792,536中所用的计算FeO与总铁的比值的方法也列入本文作为参考。除非另有规定,否则总铁还原成FeO的百分率就表示由133专利的方法和光学密度公式所得到的数值,而FeO与总铁的比值则表示按上述536专利方法计算出的比值。
在本发明所设想的所有具体实施方案中,玻璃组合物不含足以显著吸收紫外辐射的任何有效量的CeO2、TiO2、MoO3或V2O5(即只有微量固有杂质可以存在于配料中,因此,只有极少量,通常小于0.1%(重量),如约0.02%的TiO2)。确实,不使用这种添加剂是本发明与众不同的目的和特征。“基本组成”一词这里用来表示本发明玻璃组合物的这一目的和特征。
要理解的是,上述专利中所提到的和本文所用的IR和UV透射率及总透射率是指太阳能的透射率。为精确起见,本发明中所述的这些太阳能透射率(可见光透射率除外)的测定是按习用的Simpson(辛卜生)抛物线法则积分法计算的。该方法在一些基本教科书中有所描述,例如见Gillet,《Calculus and Analytical Geometry》D.C.Health & Co,第10章,第440页。然而,在这方面,红外辐射透射率既可用Simpson(辛卜生)法则具体测定,也可在一旦知道其它数值后用下面公式计算:
TSET=0.44LTA+0.53TSIR+0.03TSUV
式中:TSET是总太阳能透射率,LTA是光或可见光透射率,TSLR是红外光透射率、TSUV是紫外光透射率。用此公式计算或通过测定,本发明较好的玻璃在厚度为约3.7-4.8毫米时其红外光透射率通常在约18-21%之间。就这些透射率而言,可见光透射率是用施照体A方法(380-770毫微米)测定的;总太阳光透射率是用Simpson(辛卜生)法则(300-2100毫微米)测定的;UV透射率是用Simpson法则(300-400毫微米)测定的,IR透射率是用Simpson法则测定的或按上述公式计算(800-2100毫微米)。颜色用主波长和色纯度表示并参考施照体C和/或施照体D-65。色纯度和主波长用标准施照体CX,Y色度图解法测定。所有上述概念都是本领域中的技术人员所熟知的普通名称。
关于上述特性,要进一步理解的是,多数特性都是依赖于厚度的。因此,在提到这些特性的范围时,仅当玻璃的厚度为3.7-4.8毫米时,才看作适用。但是,这不必意味着单片玻璃就是这个厚度。这只不过表示如果玻璃在结构上的总厚度落在这个范围内,则它就具有这些特性。例如,在汽车玻璃中,尽管某些玻璃板单片厚度为4毫米,但是常常可以把厚度各为2毫米的两块玻璃板放在一起(例如用作挡风板和某些车身玻璃)。作为另一个例子,一些较厚的挡风板要求两块2.3毫米厚的玻璃板。当然,已经知道且通常要求在两块挡风板之间采用一块约0.8毫米厚的塑料层压板(例如杜邦公司的Butecite或日本Sekisui公司制造的乙烯层压板,各都具有与玻璃相同的折射率,且都可以调节各自的UV吸收特性)。在玻璃板的厚度为2毫米的情况下,层压挡风板的总厚度约为4.8毫米(虽然总的玻璃厚度是4毫米)。在玻璃板的厚度为2.3毫米的情况下,挡风板的总厚度约为5.1毫米(虽然总的玻璃厚度是4.6毫米)。所有这些都应认为是在本发明的范围之内。
现在就本发明的某些具体实施方案并参考一些附图来说明本发明。
图1是可用来生产本发明玻璃的习用熔融和炼制设备的顶视图。
图2是装有习用料斗的图1设备的侧视图。
本发明预期的玻璃可从本技术熟知的标准配料成分配料。然后可用习用设备和方法将这些配料成分进行熔融和炼制。在这点上不需要如美国专利4,792,536中所示的特殊设备。
参看图1-2,它表示了一个典型(习用)的玻璃生产设备的示意图,该设备各部分及其操作是熟练的技术人员所熟知的。这种设备可用来形成本发明的玻璃。在这方面,图1说明了制造玻璃的三个基本的顺序区,液态玻璃按箭头X方向流动。A区是熔化器。B区习惯上称为“腰”区。C区是加工区。玻璃的炼制发生在部件4与腰区B之间。这个区域通常标为“R”。液态玻璃从该加工区C流到一玻璃成形工序以使玻璃固化成其所需形状。为了本发明的目的,较好的成形工序是标准的浮法玻璃工序,该工序用于按照已知的浮法玻璃技术制造平板玻璃。但是,要理解的是,本发明不局限于这种或任何其它平板玻璃制造工序。用本发明的玻璃可以制得圆形、空心或其它形状的玻璃。这些情况也是存在的。
图2是图1设备的一个侧视图,所不同的是加了一个典型的料斗7和进料器9,这是用于将未熔化的原料送进熔化区A的定型设备。通过四个交叉的喷射气体/空气燃烧器部件1、2、3、4以习用方式加热熔化区A。这就产生了厚度为T的玻璃熔体。典型地这就在玻璃熔体11中在交叉部件3和4附近和之间的某个部位产生了一个“热点”。熔化区A通常就在腰区B之前装有撇渣槽13。而在腰区B中则装有一个腰部冷却器15和搅拌器组17。在实施本发明时发现,在分批生产中通过适当的操作控制腰部冷却器15的冷却效果和搅拌器17可以维持适当的混合和对流,从而使美国专利4,792,536中所报导的关于由于在熔体中在还原条件下所形成的FeO量的增加而产生的热穿透问题不显著,而且可以得到优质的玻璃流和稳定性。因此,这也就不需要如这篇专利中所述的特殊的熔化炼制设备。
在加工区C进行玻璃熔体的习用加工,以使玻璃准备进入随后的玻璃成形工序。然后将玻璃从C区经过普通的通道19送至成形工序。
在实施本发明中,当以习用方式操作上述设备时除了通常所能达到的条件外,不需要特殊的气氛还原条件。这是因为铁还原成FeO的过程是由配料中的还原成分和氧化成分所控制的,如分别使用碳和盐饼(Na2SO4)。在这方面,已经发现在实施本发明中较严格的是使成品玻璃中SO3的含量在约为0.20-0.25%(重量)的某一较窄的范围内,以便能达到本文中所提出的太阳透射率及颜色方面的特性。这个较窄的SO3含量反映了玻璃在形成时玻璃中氧化状态得到控制,这就产生了这些预期的特性。
适用于实施本发明的配料材料包括砂、苏打灰、白云石、石灰石、硫酸钠(盐饼)、市售氧化铁和碳(例如通常的玻璃制造商的碳)。氧化铁是一种普通的材料,基本上全部是Fe2O3。可用于实施本发明制备厚度约为2.3毫米玻璃板的典型配料如下:
材料 磅/批料 重量%
砂 2424 59.66
苏打灰 759 18.68
白云石 592 14.57
石灰石 197.6 4.86
盐饼 63.0 1.55
氧化铁* 25.25 0.62
碳 2.30 0.06
4063.15 100.00
*该氧化铁是普通的红铁粉,经分析其组成为(重量):97.39% Fe2O3;0.51% MgO;0.11% CaO;0.070% TiO2;1.13% SiO2;和1.24% Al2O3。
以理论的氧化物为基础该玻璃的组成如下:
材料 重量%
Na2O 13.75
MgO 3.90
Al2O30.15
SO30.23
K2O 0.04
CaO 8.72
(代表总铁量)Fe2O30.78
SiO272.41
FeO 0.19
这种玻璃,当按上述3.7-4.8毫米厚度范围生产时,将具有本发明所设想的范围内的太阳光控制特性、主波长和色纯度。
可用于本发明中制造2毫米和4毫米厚玻璃板的另一种典型的配料如下:
材料 磅/批料 重量%
砂 2424 59.60
苏打灰 759 18.66
白云石 592 14.56
石灰石 197.6 4.86
盐饼 63.0 1.55
氧化铁* 29.0 0.71
碳 2.3 0.06
4066.90 100.00
*与上述相同的红铁粉。
当用按照上述的设备用习用的熔融技术使这种配料熔化和炼制并用习用的浮法制成2毫米或4毫米厚的玻璃板时,能达到下列特性:
2毫米 4毫米
施照体A(%) 80.9 71.1
UV透射率(%) 53.1 36.6
总太阳能透射率(%) 60.6 42.9
IR透射率(%) 47.0 19.8
施照体D-65L 92.6 88.5
(平均)a -4.35 -8.31
b 0.89 1.55
施照体C
主波长 501 501
(平均)X .3050 .2996
Y .3207 .3245
色纯度(%) 1.6 3.3
FeO/总铁(以Fe2O3表示) 0.2475(24.75%)
*%Fe2O3(总铁)还原成FeO 27%
*按133专利的方法计算。
经分析发现该玻璃具有下列组成(按氧化物计):
材料 重量%
Na2O 13.67
MgO 3.91
Al2O30.17
SO30.21
K2O 0.04
CaO 8.70
(代表总铁量)Fe2O30.889
SiO272.41
FeO 0.22
将上述FeO与总铁(用Fe2O3表示)比为0.2475、Fe2O3(总铁)还原成FeO的%为27%(按133专利的方法计算)的玻璃组合物制成各种厚度的玻璃板并测定其施照体C的主波长和色纯度。测试结果表明了厚度对色纯度的影响并表明对主波长的影响较小。
厚度
英寸 毫米(mm) 主波长 光学纯度
.224*5.7mm 500.8 4.6
.155 3.9mm 501.5 3.3
.1585 4.0mm 502.0 3.3
.157 4.0mm 501.5 3.3
.1565 4.0mm 500.9 3.3
.187 4.75mm 502.5 3.8
.165 4.2mm 500.7 3.5
.116 2.9mm 500.5 2.6
.178**4.5mm 501.2 3.7
.112 2.8mm 500.9 2.3
.167***4.2mm 500.5 3.5
.162***4.1mm 501.2 3.3
.167***4.2mm 500.5 3.5
.081 2.06mm 501.2 1.6
.085 2.15mm 501.5 1.7
*两块0.112英寸厚的玻璃板之间夹一层折射率(RI)油。
**两块0.089英寸厚的玻璃板之间夹一层RI油。
***两块相同厚度的玻璃板之间夹一层RI油。
上述两种玻璃既是本发明优选的具体实施方案,也是本发明用于较窄定义类型的钠-钙-硅玻璃的实用性的代表。在较好的形式中,这种玻璃含有下列成分。
材料 重量%
Na2O 约12-20
MgO 约3-5
Al2O3约0.10-0.30
SO3约0.20-0.25
K2O 约0-0.1
CaO 约8-10
Fe2O3(代表总铁量) 约0.7-0.95
SiO2约71.0-74.0
FeO 约0.19-0.24
(较好0.20-0.24)
FeO/总铁(用Fe2O3表示) 约0.24-0.27
Fe2O3还原成FeO的% 约25-29%
(按133专利的方法)
这种玻璃按照本发明成形时不用CeO、TiO2、MoO3或V2O5作为UV吸收添加剂且其厚度为约3.7-4.8毫米时可达到下列预期特性:
特性 范围
施照体A(%) >70%
UV透射率(%) <38%
总太阳能透射率(%) <44.5%
IR透射率(%) 约18-21%
施照体C主波长 约495-510毫微米
施照体D-65L 约87-91%
a 约-8±3
b 约2±2
色纯度 约2-4%
一旦给出了上述公开内容,许多其它特点、修改和改进对于熟练的技术人员来说将是很明显的。因此,这些其它特点、修改和改进应认为是本发明的一部分,其范围由下述权利要求限定。
Claims (11)
1、一种能吸收红外能量和紫外辐射的绿色玻璃,其基本组成为SiO2、Na2O、CaO、约0.20-0.25%SO3、约0.7-0.95%表示为Fe2O3的总铁、0.19-0.24%表示为FeO的亚铁,且其中所述玻璃当厚度为约3.7-4.8毫米之间时,其可见光透射率大于约70%,紫外辐射透射率小于约38%,总太阳能透射率小于约44.5%。
2、按照权利要求1的绿色玻璃,其中所述玻璃的基本组成按氧化物计算为:
材料 重量%
Na2O 约12-20
MgO 约3-5
Al2O3约0.10-0.30
SO3约0.20-0.25
K2O 约0-0.1
CaO 约8-10
Fe2O3(代表总铁) 约0.7-0.95
SiO2约71.0-74.0
FeO 约0.20-0.24
%FeO还原 约25-29%
FeO/总铁(用Fe2O3表示) 约0.24-0.27%
3、按照权利要求2的绿色玻璃,其中所述玻璃当厚度为约3.7-4.8毫米之间时具有下述特性:
特性 范围
施照体A(可见光透射率) >70%
UV透射率(%) <38%
总太阳能透射率 <44.5%
IR透射率 18-21%
施照体C主波长 约495-510毫微米
施照体D-65L 约87-91%
a 约-8±3
b 约2±2
色纯度 约2-4%
4、按照权利要求1的绿色玻璃,其中所述玻璃的基本组成按氧化物计算为:
材料 重量%
Na2O 约13.75
MgO 约3.9
Al2O3约0.15
SO3约0.23
K2O 约0.04
CaO 约8.72
Fe2O3(代表总铁) 约0.78
SiO2约72.41
FeO 约0.19
5、按照权利要求4的绿色玻璃,其中所述玻璃在层压汽车挡风板中的玻璃厚度(不包括层压夹层)为约4.6毫米。
6、按照权利要求4的绿色玻璃,它是由具有下述基本重量组成的配料材料形成的:
材料 重量%
砂 约59.66
苏打灰 约18.68
白云石 约14.57
石灰石 约4.86
盐饼 约1.55
氧化铁 约0.62
碳 约0.06
7、按照权利要求3的绿色玻璃,其中所述玻璃的基本组成按氧化物计算为:
材料 重量%
Na2O 约13.67
MgO 约3.91
Al2O3约0.17
SO3约0.21
K2O 约0.04
CaO 约8.70
Fe2O3(代表总铁) 0.889
SiO272.41
FeO 0.22
8、按照权利要求7的绿色玻璃,其中所述玻璃的厚度约为4毫米而且是一种汽车玻璃制品。
9、按照权利要求7的绿色玻璃,它是由具有下述基本重量组成的配料材料形成的:
材料 重量%
砂 约59.6
苏打灰 约18.66
白云石 约14.56
石灰石 约4.86
盐饼 约1.55
氧化铁 约0.71
碳 约0.06
而且其中在这样所形成的玻璃中表示为Fe2O3的总铁的百分率还原是约27%。
10、按照权利要求3的绿色玻璃,其中所述的施照体C的主波长是约500-502。
11、按照权利要求1的绿色玻璃,其中所述的玻璃是浮法玻璃。
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US (1) | US5214008A (zh) |
EP (1) | EP0565835B1 (zh) |
JP (1) | JPH07121815B2 (zh) |
KR (1) | KR930021558A (zh) |
CN (1) | CN1037958C (zh) |
AT (1) | ATE179684T1 (zh) |
AU (1) | AU660212B2 (zh) |
BR (1) | BR9301559A (zh) |
CA (1) | CA2085264C (zh) |
CZ (1) | CZ60093A3 (zh) |
DE (1) | DE69324726T2 (zh) |
DK (1) | DK0565835T3 (zh) |
ES (1) | ES2133335T3 (zh) |
HU (1) | HU213955B (zh) |
MX (1) | MX9301842A (zh) |
NO (1) | NO931416L (zh) |
NZ (1) | NZ247433A (zh) |
PL (1) | PL175413B1 (zh) |
RU (1) | RU2094402C1 (zh) |
SK (1) | SK33193A3 (zh) |
TR (1) | TR28283A (zh) |
ZA (1) | ZA932086B (zh) |
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CN1042826C (zh) * | 1993-04-27 | 1999-04-07 | 利比-欧文斯-福特公司 | 玻璃组合物 |
CN103641303A (zh) * | 2013-11-27 | 2014-03-19 | 常熟市赛蒂镶嵌玻璃制品有限公司 | 绿色浮法玻璃的制备工艺 |
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- 1993-02-19 AU AU33190/93A patent/AU660212B2/en not_active Ceased
- 1993-02-25 DE DE69324726T patent/DE69324726T2/de not_active Expired - Fee Related
- 1993-02-25 EP EP93102995A patent/EP0565835B1/en not_active Expired - Lifetime
- 1993-02-25 DK DK93102995T patent/DK0565835T3/da active
- 1993-02-25 AT AT93102995T patent/ATE179684T1/de active
- 1993-02-25 ES ES93102995T patent/ES2133335T3/es not_active Expired - Lifetime
- 1993-03-24 ZA ZA932086A patent/ZA932086B/xx unknown
- 1993-03-31 MX MX9301842A patent/MX9301842A/es not_active IP Right Cessation
- 1993-04-07 TR TR00310/93A patent/TR28283A/xx unknown
- 1993-04-07 KR KR1019930005813A patent/KR930021558A/ko not_active Application Discontinuation
- 1993-04-07 CZ CZ93600A patent/CZ60093A3/cs unknown
- 1993-04-09 JP JP5107762A patent/JPH07121815B2/ja not_active Expired - Lifetime
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- 1993-04-14 PL PL93298501A patent/PL175413B1/pl not_active IP Right Cessation
- 1993-04-16 RU RU9393005314A patent/RU2094402C1/ru active
- 1993-04-16 HU HU9301111A patent/HU213955B/hu not_active IP Right Cessation
- 1993-04-16 BR BR9301559A patent/BR9301559A/pt not_active IP Right Cessation
- 1993-04-16 NO NO93931416A patent/NO931416L/no unknown
- 1993-04-17 CN CN93105012A patent/CN1037958C/zh not_active Expired - Fee Related
- 1993-04-19 NZ NZ247433A patent/NZ247433A/en unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1042826C (zh) * | 1993-04-27 | 1999-04-07 | 利比-欧文斯-福特公司 | 玻璃组合物 |
CN103641303A (zh) * | 2013-11-27 | 2014-03-19 | 常熟市赛蒂镶嵌玻璃制品有限公司 | 绿色浮法玻璃的制备工艺 |
Also Published As
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ZA932086B (en) | 1993-10-15 |
ATE179684T1 (de) | 1999-05-15 |
SK33193A3 (en) | 1993-11-10 |
ES2133335T3 (es) | 1999-09-16 |
BR9301559A (pt) | 1993-10-26 |
CN1037958C (zh) | 1998-04-08 |
NZ247433A (en) | 1994-09-27 |
HU9301111D0 (en) | 1993-08-30 |
JPH06166536A (ja) | 1994-06-14 |
PL175413B1 (pl) | 1998-12-31 |
DK0565835T3 (da) | 1999-11-01 |
AU660212B2 (en) | 1995-06-15 |
JPH07121815B2 (ja) | 1995-12-25 |
CZ60093A3 (en) | 1994-11-16 |
RU2094402C1 (ru) | 1997-10-27 |
EP0565835A3 (en) | 1994-10-26 |
CA2085264C (en) | 1997-01-28 |
HU213955B (en) | 1997-11-28 |
NO931416L (no) | 1993-10-18 |
DE69324726D1 (de) | 1999-06-10 |
NO931416D0 (no) | 1993-04-16 |
DE69324726T2 (de) | 1999-12-09 |
AU3319093A (en) | 1993-10-21 |
EP0565835A2 (en) | 1993-10-20 |
PL298501A1 (en) | 1994-01-10 |
EP0565835B1 (en) | 1999-05-06 |
US5214008A (en) | 1993-05-25 |
KR930021558A (ko) | 1993-11-22 |
HUT68637A (en) | 1995-07-28 |
MX9301842A (es) | 1994-02-28 |
TR28283A (tr) | 1996-04-17 |
CA2085264A1 (en) | 1993-10-18 |
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