CN107867804A - 可膜面向下钢化的低辐射节能玻璃 - Google Patents
可膜面向下钢化的低辐射节能玻璃 Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 58
- 238000005496 tempering Methods 0.000 title claims abstract description 31
- 239000010410 layer Substances 0.000 claims abstract description 140
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011241 protective layer Substances 0.000 claims abstract description 22
- 230000005855 radiation Effects 0.000 claims abstract description 21
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 20
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 239000002346 layers by function Substances 0.000 claims abstract description 9
- KBEVZHAXWGOKCP-UHFFFAOYSA-N zinc oxygen(2-) tin(4+) Chemical compound [O--].[O--].[O--].[Zn++].[Sn+4] KBEVZHAXWGOKCP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002310 reflectometry Methods 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 241000227425 Pieris rapae crucivora Species 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001120 nichrome Inorganic materials 0.000 description 4
- 229910004205 SiNX Inorganic materials 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005329 float glass Substances 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910007717 ZnSnO Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000004134 energy conservation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 239000005344 low-emissivity glass Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
本发明公开了一种可膜面向下钢化的低辐射镀膜玻璃,属于环保节能建筑材料领域。该低辐射镀膜玻璃的膜层结构依次为:玻璃基片、第一层打底层氮化硅层、第二层保护层镍铬层、第三层介质层氧化锌锡层、第四层种子层氧化锌层、第五层功能层银层、第六层保护层镍铬层、第七层介质层氮化硅层、第八层石墨保护层。本发明的产品钢化后室外反射率低于6%,单片透过率达到80%以上。合成中空产品后,产品遮阳系数高于0.65,光热比(LSG)大于1.4,辐射率低于0.10,属于高透型低辐射产品,非常适用北方寒冷地区使用。同时,由于其反射比普通白玻低,透过率较高又兼具热阻隔的作用,该款产品可在博物馆,展柜等场所得到广泛使用。
Description
技术领域
本发明涉及环保节能建筑材料领域,特别涉及一种可膜面向下钢化的低辐射节能玻璃。
背景技术
低辐射镀膜玻璃(“Low-E”玻璃)是一种对波长4.5~25μm的红外线有较高反射比的镀膜玻璃。这种镀膜玻璃对可见光具有高透光性,保证了室内的采光,又对远红外光具有高反射性,从而做到阻止玻璃吸收室外热量再产生热辐射将热量传入室内,又将室内物体产生的热量反射回来,达到降低玻璃的热辐射通过量的目的。从而实现降低建筑物供暖制冷的能耗。Low-E玻璃的性能主要靠可见光透过率、遮阳系数以及选择系数来衡量。其中:遮阳系数,玻璃遮挡或抵御太阳光能的能力,英文为Shading Coefficient,实际通过玻璃的热量与通过厚度为3mm厚标准玻璃的热量与的比值。选择系数,镀膜玻璃选择系数是国家承认的,在玻璃行业里面衡量玻璃节能型的重要指标。选择系数=透过率/遮阳系数。所以,如果low-e玻璃的遮阳系数越低,可见光透过率越高,其节能性就越好。常见单银low-E节能玻璃的选择系数为1.0~1.2,双银low-E节能玻璃的选择系数为1.2~1.5。
目前市场上的高透型单银低辐射节能玻璃,其主要存在以下不足:
(1)现有的性能较好的高透型单银,均采用先钢化后镀膜的技术。即浮法原片钢化后,再进行镀膜,然后进行其他加工。这种生产方式效率较低,主要在生产时镀膜线的排片将根据具体产品尺寸进行,不能达到镀膜的最大装载率。同时,这种生产模式如果产生次品后,补片不够及时,对于产品的齐片交货期存在一定的影响。
(2)现有的可钢化高透型单银低辐射节能玻璃,其机械性能强度不够,在运输过程中需要对膜面进行贴膜保护。此种方式,极大地增加了产品的成本,导致产品价格较高,不利于节能环保建材的推广使用。另外,由于现有产品的机械性能不足,导致在切割、磨边等加工过程中,极易对膜面造成损失,致使该类产品的加工效率低下,成品率较低。
(3)现有的高透型可钢化单银产品膜面强度不够,因此钢化时均采用膜面向上进行钢化。这种钢化方式产品的加热时间较长,边部容易过热。钢化后的产品容易出现成像质量差,待产品安装上墙后,容易出现反射影像扭曲的现象。且由于加热过时间相对较长,所以生产时,单位产品的生产能耗较高,生产成本相对较大。
中国专利申请CN102336529A公开了一种高透可钢化低辐射玻璃及其制造方法,其技术方案中的膜层结构为glass/SiNx/ZnSnO/ZnO/Ag/NiCr/ZnSnO/SiNx,虽然钢化后单片该镀膜玻璃可见光透过率能够达到85%,但其反射率也有8%以上,并且不能实现膜面向下钢化,该产品的光热比性能也较差。
发明内容
本发明的目的在于克服现有高透型低辐射节能玻璃所存在的上述不足,提供一种可膜面向下钢化的低辐射节能玻璃。该低辐射节能玻璃钢化后室外反射低于6%,单片透过率达到80%以上。合成中空产品后,产品遮阳系数高于0.65,光热比(LSG)大于1.4,辐射率低于0.10,属于高透型低辐射产品,非常适用北方寒冷地区使用。
为了实现上述发明目的,本发明提供了以下技术方案:
一种可膜面向下钢化的低辐射镀膜玻璃,该玻璃膜层结构依次为:玻璃基片、第一层打底层氮化硅层、第二层保护层镍铬层、第三层介质层氧化锌锡层、第四层种子层氧化锌层、第五层功能层银层、第六层保护层镍铬层、第七层介质层氮化硅层、第八层石墨保护层。
进一步地,上述低辐射镀膜玻璃采用离线磁控溅射镀膜制成。
进一步地,上述第一层打底层氮化硅层的厚度在10nm到20nm之间。在本方案中,根据不同实例的需要,氮化硅层可以是按照化学计量比的Si3N4,也可以是含有富裕Si类型的氮化硅层。镀膜玻璃在钢化时,温度可以达到600℃至700℃,因此,含有自由Si的氮化硅层可以阻挡玻璃中Na离子的迁移,从而避免因Na离子迁移对功能层Ag层产生的破坏作用。
进一步地,上述第二层保护层镍铬层的厚度在0.5nm到4nm之间。在本方案中,保护层为NiCr,该层不仅能够保护功能层Ag层在玻璃钢化加热过程中免受氧化,还有一定的吸收作用,在产品颜色调节上起到一定的作用。保护层通过NiCr合金靶材在纯氩气分为下进行溅射沉积,Ni和Cr的比例可以任意。
进一步地,上述第三层介质层氧化锌锡层的厚度在18nm到42nm之间。玻璃在钢化炉高温受热时,氧化锌锡可以有效的提高膜层颜色的稳定性。氧化锌锡层通过ZnSn合金靶在氩气和氧气氛围下进行溅射,Zn和Sn的比例为50∶50。
进一步地,上述第四层种子层氧化锌层的厚度在1nm到6nm之间。氧化锌可以提高整个膜层的平整度,以便于功能层Ag的沉积生长,平整连续的Ag层有助于提高整个膜层的红外反射率,减低膜层的面电阻。
进一步地,上述第五层功能层银层的厚度范围在6nm到14nm之间。此厚度范围内的银膜能形成连续膜,并且透明,这样能允许大部分的可见光透过,并能反射掉大多数的红外光。为了保证功能层Ag的效果,在Ag层上必须生长一层保护层。
进一步地,上述第六层保护层镍铬层的厚度在0.5nm到6nm之间。保护层通常位于Ag层之上,介于功能层Ag和介质层SiNx之间,本方案中的保护层为NiCr,该层不仅能够保护Ag在玻璃钢化加热过程中免受氧化,还有一定的吸收作用,在产品颜色调节上起到一定的作用。
进一步地,上述第七层介质层氮化硅层厚度在35nm到65nm之间。
进一步地,上述第八层石墨保护层的厚度范围在5nm到10nm之间。石墨具有良好的润滑作用,将石墨镀制在膜层最上层,可以有效提高膜层的机械性能,防止在运输、加工过程中膜面产生划伤。
与现有技术相比,本发明的有益效果:
本发明通过将不同膜层材料进行组合和膜层厚度设置,可以实现膜面朝下钢化,这样可以有效降低钢化能耗,减少钢化加热的时间。同时,相比膜面朝上钢化的产品,膜面向下钢化产品由于受热实际短,边部不会严重过热,产品成像效果较好,不会出现严重褶边,有利于提高幕墙成像效果。本发明的低辐射节能玻璃经钢化后室外反射率低于6%,室外反射色a*在-2~2之间,b*在-6~-12之间,单片透过率达到80%以上。合成中空产品后,产品遮阳系数高于0.65,光热比LSG大于1.4,辐射率低于0.10,属于高透型低辐射产品,非常适用北方寒冷地区使用。同时,由于其反射比普通白玻低,透过率较高又兼具热阻隔的作用,该款产品可在博物馆,展柜等场所得到广泛使用。
附图说明
图1为本发明所述一种可膜面向下钢化的低辐射节能玻璃的结构示意图。
图中标记:1-玻璃基片,2-第一层打底层氮化硅层,3-第二层保护层镍铬层,4-第三层介质层氧化锌锡层,5-第四层种子层氧化锌层,6-第五层功能层银层,7-第六层保护层镍铬层,8-第七层介质层氮化硅层,8-第八层石墨保护层。
具体实施方式
下面结合试验例及具体实施方式对本发明作进一步的详细描述。但不应将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明内容所实现的技术均属于本发明的范围。
实施例1
利用真空离线磁控溅射镀膜设备,在6mm优质浮法玻璃基片上,由内到外依次镀制12.5nm氮化硅层、1nm镍铬层、28nm氧化锌锡层、5nm氧化锌层、8nm银层、2nm镍铬层、44nm氮化硅层和5nm石墨层。
实施例2
利用真空离线磁控溅射镀膜设备,在6mm优质浮法玻璃基片上,由内到外依次镀制14nm氮化硅层、0.8nm镍铬层、30nm氧化锌锡层、5nm氧化锌层、9nm银层、1.8nm镍铬层、46nm氮化硅层和8nm石墨层。
实施例3
利用真空离线磁控溅射镀膜设备,在6mm优质浮法玻璃基片上,由内到外依次镀制13nm氮化硅层、1.2nm镍铬层、26nm氧化锌锡层、7nm氧化锌层、8.5nm银层、2.1nm镍铬层、43.5nm氮化硅层和10nm石墨层。
性能测试
按照GB/T18915.1-2012测定上述实施例制得低辐射玻璃钢化后的光学参数,进行对比,结果见表1。(a*和b*代表色度坐标,其中a*代表红-绿轴,b*代表黄-蓝轴):
表1:
Claims (10)
1.一种可膜面向下钢化的低辐射镀膜玻璃,其特征在于,该玻璃膜层结构依次为:玻璃基片、第一层打底层氮化硅层、第二层保护层镍铬层、第三层介质层氧化锌锡层、第四层种子层氧化锌层、第五层功能层银层、第六层保护层镍铬层、第七层介质层氮化硅层、第八层石墨保护层。
2.根据权利要求1所述低辐射镀膜玻璃,其特征在于,所述低辐射镀膜玻璃采用离线磁控溅射镀膜制成。
3.根据权利要求1所述低辐射镀膜玻璃,其特征在于,所述第一层打底层氮化硅层的厚度在10nm到20nm之间。
4.根据权利要求1所述低辐射镀膜玻璃,其特征在于,所述第二层保护层镍铬层的厚度在0.5nm到4nm之间。
5.根据权利要求1所述低辐射镀膜玻璃,其特征在于,所述第三层介质层氧化锌锡层的厚度在18nm到42nm之间。
6.根据权利要求1所述低辐射镀膜玻璃,其特征在于,所述第四层种子层氧化锌层的厚度在1nm到6nm之间。
7.根据权利要求1所述低辐射镀膜玻璃,其特征在于,所述第五层功能层银层的厚度范围在6nm到14nm之间。
8.根据权利要求1所述的低辐射镀膜玻璃,其特征在于,所述第六层保护层镍铬层厚度在0.5nm到6nm之间。
9.根据权利要求1所述的低辐射镀膜玻璃,其特征在于,所述第七层介质层氮化硅层厚度在35nm到65nm之间。
10.根据权利要求1所述低辐射镀膜玻璃,其特征在于,所述第八层石墨保护层的厚度范围在5nm到10nm之间。
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