CN110330818A - 一种红外选择性辐射降温纳米功能组合物及其制备方法 - Google Patents
一种红外选择性辐射降温纳米功能组合物及其制备方法 Download PDFInfo
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- CN110330818A CN110330818A CN201910695003.4A CN201910695003A CN110330818A CN 110330818 A CN110330818 A CN 110330818A CN 201910695003 A CN201910695003 A CN 201910695003A CN 110330818 A CN110330818 A CN 110330818A
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- 230000005855 radiation Effects 0.000 title claims abstract description 69
- 238000001816 cooling Methods 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 32
- -1 rare earth silicate compound Chemical class 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 150000002910 rare earth metals Chemical class 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000003836 solid-state method Methods 0.000 abstract 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- HCVNJMOLULRIQD-UHFFFAOYSA-N [La].[Si](O)(O)(O)O Chemical compound [La].[Si](O)(O)(O)O HCVNJMOLULRIQD-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910004647 CaMoO4 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- VFDSMZLBQCGYHH-UHFFFAOYSA-N dysprosium silicic acid Chemical compound [Dy].[Si](O)(O)(O)O VFDSMZLBQCGYHH-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910017964 MgMoO4 Inorganic materials 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 238000002310 reflectometry Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
本发明公开了一种红外选择性辐射降温纳米功能组合物及其制备方法,该组合物由二氧化硅、稀土硅酸盐化合物和钼酸盐化合物按照质量比例1:(0.5~2):(0.5~2)通过球磨均匀混合而成,二氧化硅、稀土硅酸盐化合物和钼酸盐化合物分别在8~10μm、9~12μm和10~14μm范围内具有强的红外选择性辐射性能。根据化学计量比SiO2‑(0.5~2)Re2O3‑(0.1~1.0)Na2O(Re=La、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Y、Sc)和RMoO4(R=Mg、Ca、Sr、Ba),通过溶胶‑凝胶和高温固相法制得稀土硅酸盐化合物和钼酸盐化合物。该红外选择性辐射降温纳米功能组合物可用于制备日夜双效辐射降温器等功能器件,实现建筑物、粮油库、太阳能电池背板等提供零耗能降温冷却和节能增效。
Description
技术领域
本发明属于热辐射技术领域,涉及一种红外选择性辐射降温纳米功能组合物及其制备方法。
背景技术
随着全球经济的快速发展,能源危机问题日显突出,空调降温在能源消耗中占有相当的比例,发展高效辐射降温技术,对于减少电能消耗、保护环境具有重要意义。辐射降温是指地球上的物体通过红外大气窗口将热量传递至外太空的过程,辐射降温材料就是基于这一原理制备出的具有自发降温功能的材料。在热量传播过程中,大气是红外辐射的主要传输介质,虽然大气对可见光是透明的,但是在红外波段有很大一部分的红外辐射无法透过大气。这是由于大气中存在的H2O、CO2、O3和CH4等多原子气体分子在红外辐射传输过程中会引起分子中电偶极距的变化,导致红外辐射的吸收或散射,且实际大气中,还存在很多固体或液体的悬浮物,如烟、雾、雨、雪、灰尘等,它们也会对红外辐射的传输起阻碍作用。根据对大气透过率的研究,发现在8~14μm波段各种气体分子的吸收较弱,红外辐射可以透过大气层向远方传播,因此该区域被称为“大气窗口”。
在太阳光照环境下,辐射降温器在工作过程中的热量交换主要包括以下几种:第一,吸收的太阳辐射;第二,吸收大气中的红外辐射;第三,通过红外窗口排出的红外辐射;第四,自然空气下的热对流及热传导。为实现达到最佳的被动降温效果,辐射降温材料需要在8~14μm红外波段具有高的发射率以及在0.38~2.5μm太阳光谱波段具有高的反射率。辐射降温器通常包括红外辐射层和太阳光反射层,红外辐射层的作用是将物体的热量通过红外大气窗口排出至太空,太阳光反射层的作用是高效地反射太阳光,减少太阳光热吸收。
目前,在夜晚无光照条件下的辐射降温器已实现,但是在白天光照条件下达到满足实用性能要求的高性能辐射降温器尚未出现。现有公开报道的辐射降温器主要有以下方法:一种是通过光刻蚀技术以及纳米等离子沉积技术,构筑纳米结构的辐射降温器,这种结构的光子辐射降温器造价成本高,无法实现大规模生产,且光子辐射降温器结构强度低、易破坏、长期稳定性差。另一种是将钛白粉、玻璃微球等无机功能物质与聚合物复合粘结到高反射金属基底上得到辐射降温器,但是由于钛白粉、玻璃微球等功能物质在红外光谱区的吸收选择性不够,制得的辐射降温器在8~14μm范围外的非红外大气窗口具有高的吸收率和发射率,选择性辐射能力差,易于从环境中吸收大量额外的大气热辐射,进而使辐射器整体降温效果减弱,有效降温功率不够理想。目前,可用于满足日夜双效辐射降温器功能要求,且易于大规模低成本制造的红外选择性辐射降温纳米功能组合物及其制备工艺还未见报道。
发明内容
本发明的目的是提供一种能解决现有技术中存在缺陷的红外选择性辐射降温纳米功能组合物,本发明的另一目的是提供上述红外选择性辐射降温纳米功能组合物的制备方法。
为达到上述目的,本发明是通过以下技术方案实现的:一种红外选择性辐射降温纳米功能组合物,该红外选择性辐射降温纳米功能组合物由纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物,按质量比例1:(0.5~2):(0.5~2),经球磨均匀混合而成;其中纳米二氧化硅在8~10μm范围内具有强的红外选择性辐射性能(红外辐射吸收系数大于0.8);稀土硅酸盐化合物符合化学计量比SiO2-(0.5~2)Re2O3-(0.1~1.0)Na2O且在9~12μm范围内具有强的红外选择性辐射性能(红外辐射吸收系数大于0.8),其中Re为La、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Y或Sc;钼酸盐化合物符合化学计量比RMoO4且在10~14μm范围内具有强的红外选择性辐射性能(红外辐射吸收系数大于0.8),其中R为Mg、Ca、Sr或Ba。
更优选稀土硅酸盐化合物SiO2-(0.5~2.0)RE2O3-(0.1~1.0)Na2O,RE为La、Gd、Tm、Y、Sc中任意一种或几种组合,进一步优选La、Gd、Y中任意一种或几种组合。
所述钼酸盐化合物符合化学计量比RMoO4中R优选为Mg、Ca中任意一种或二种组合。
该纳米功能组合物在8~14μm大气窗口具有强的选择性吸收-辐射性能,且对紫外-可见-近红外太阳光透明。
本发明还提供了一种制备上述的一种红外选择性辐射降温纳米功能组合物的方法,其具体步骤如下:
(a)根据稀土硅酸盐化合物的化学计量比,准确称取纳米二氧化硅、稀土硝酸盐和硝酸钠,混合分散到乙醇水混合溶液中;在水浴搅拌条件下蒸发溶剂得到凝胶;经120~150℃低温预烧处理3~6小时后,再在600~900℃热处理3~12小时得到稀土硅酸盐化合物;
(b)根据钼酸盐化合物的化学计量比,准确称取钼酸铵和碱土金属硝酸盐,溶解到去离子水中;配置柠檬酸溶液,滴加入到上述溶液中,边加边剧烈搅拌,调节pH至3.0~4.0,在水浴搅拌条件下蒸发溶剂得到凝胶;经120~150℃低温预烧处理3~6小时后,再800~1000℃热处理3~12小时后,即得到钼酸盐化合物;
(c)按照纳米功能组合物质量比例,称取一定量纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物,利用高速研磨分散机处理后,即获得红外选择性辐射降温纳米功能组合物。
优选步骤(a)中的水浴温度为70~80℃。优选步骤(b)中柠檬酸溶液的质量浓度为5%~10%;用氨水调节pH;水浴温度为70~80℃。优选步骤(c)中高速研磨分散机的转速为300~400转/分钟,处理时间为2~6小时。
有益效果:
本发明将在8~10μm范围内具有强红外选择性辐射性能的纳米二氧化硅、在9~12μm范围内具有强的红外选择性辐射性能的稀土硅酸盐化合物和在10~14μm范围内具有强的红外选择性辐射性能的钼酸盐化合物组合获得对紫外-可见-近红外太阳光透明且在8~14μm红外大气窗口具有强红外选择性辐射降温特性的纳米功能组合物,为低成本大规模制造高性能日夜双效辐射降温器、自主辐射降温涂层等降低了技术难度,为建筑物、粮油库、大功率电子设备、冷藏箱包等零耗能冷却降温,实现大规模节能增效提供新的技术途径。
附图说明
图1是以实施例1的红外选择性吸收/辐射光谱图。
具体实施方式
为了更好地理解本发明,特例举以下实施例对本发明进行详细阐述,但本发明的内容绝不仅仅限于下面的实施例。本发明的优点和特点会随着描述而更加清楚,但并不作为对本发明做任何限制的依据。本领域技术人员应该理解的是,在阅读了本发明之后,对本发明的各种等价形式的修改或替换均落于本发明保护范围内。
实施例1
本实施例公开了一种红外选择性辐射降温纳米功能组合物及其制备工艺,包括以下步骤:
(a)根据稀土硅酸镧化合物化学计量比SiO2-La2O3-0.5Na2O,准确称取30g纳米二氧化硅(50nm,市售)、324.9g硝酸镧和85g硝酸钠,溶解到乙醇水混合溶液中,在水浴70℃搅拌条件下蒸发溶剂得到凝胶,在120℃热处理6小时得到稀土硅酸镧预烧粉,在700℃热处理12小时得到颗粒平均尺寸为106nm稀土硅酸镧化合物。
(b)根据钼酸钙化学式CaMoO4,准确称取82g硝酸钙和170g二钼酸铵,溶解到去离子水中。配置8%柠檬酸溶液,逐滴加入到上述溶液中,边加边剧烈搅拌,用氨水调节pH至3.5,在水浴70℃搅拌条件下蒸发溶剂得到凝胶,在150℃热处理6小时得到钼酸钙预烧粉,在900℃热处理6小时得到颗粒平均尺寸为103nm钼酸钙。
(c)按功能粉体组合物重量比例1:1:1,分别称取40g纳米二氧化硅(50nm,市售)、40g步骤(a)中的稀土硅酸镧化合物和40g步骤(b)中的钼酸钙,共同加入高速研磨分散机的球磨罐中,球磨转速为300转/分钟,球磨时间为6小时,得到所需的红外选择性辐射降温纳米功能组合物,该纳米功能组合物在8~14μm红外波长范围的吸收/辐射率最高达0.90。其红外选择性吸收/辐射光谱图如图1所示。
实施例2
本实施例公开了一种红外选择性辐射降温纳米功能组合物及其制备工艺,包括以下步骤:
(a)根据稀土硅酸镧化合物化学计量比SiO2-1.5Sm2O3-0.25Na2O,准确称取24g纳米二氧化硅(50nm,市售)、134.5g硝酸钐和42.5g硝酸钠,溶解到乙醇水混合溶液中,在水浴70℃搅拌条件下蒸发溶剂得到凝胶,在150℃热处理3小时得到稀土硅酸镧预烧粉,在900℃热处理3小时得到颗粒平均尺寸为115nm稀土硅酸镧化合物。
(b)根据钼酸钙化学式MgMoO4,准确称取72.2g硝酸镁和85g二钼酸铵,溶解到去离子水中。配置10%柠檬酸溶液,逐滴加入到上述溶液中,边加边剧烈搅拌,用氨水调节pH至3.0,在水浴80℃搅拌条件下蒸发溶剂得到凝胶,在120℃热处理6小时得到钼酸钙预烧粉,在1000℃热处理3小时得到颗粒平均尺寸为103nm钼酸钙。
(c)按功能粉体组合物重量比例1:1.5:0.5,分别称取40g纳米二氧化硅(50nm,市售)、60g步骤(a)中的稀土硅酸镧化合物和15g步骤(b)中的钼酸钙,共同加入高速研磨分散机的球磨罐中,球磨转速为350转/分钟,球磨时间为4小时,得到所需的红外选择性辐射降温纳米功能组合物,该纳米功能组合物在8~14μm红外波长范围的吸收/辐射率最高达0.89。
实施例3
本实施例公开了一种红外选择性辐射降温纳米功能组合物及其制备工艺,包括以下步骤:
(a)根据稀土硅酸镧化合物化学计量比SiO2-1.5La2O3-0.5Na2O,准确称取30g纳米二氧化硅(30nm,市售)、487.4g硝酸镧和42.5g硝酸钠,溶解到乙醇水混合溶液中,在水浴80℃搅拌条件下蒸发溶剂得到凝胶,在120℃热处理6小时得到稀土硅酸镧预烧粉,在650℃热处理12小时得到颗粒平均尺寸为94nm稀土硅酸镧化合物。
(b)根据钼酸钙化学式CaMoO4,准确称取82g硝酸钙和170g二钼酸铵,溶解到去离子水中。配置8%柠檬酸溶液,逐滴加入到上述溶液中,边加边剧烈搅拌,用氨水调节pH至4.0,在水浴70℃搅拌条件下蒸发溶剂得到凝胶,在150℃热处理3小时得到钼酸钙预烧粉,在900℃热处理3小时得到颗粒平均尺寸为90nm钼酸钙。
(c)按功能粉体组合物重量比例1:0.5:2,分别称取35g纳米二氧化硅(50nm,市售)、17.5g步骤(a)中的稀土硅酸镧化合物和70g步骤(b)中的钼酸钙,共同加入高速研磨分散机的球磨罐中,球磨转速为300转/分钟,球磨时间为6小时,得到所需的红外选择性辐射降温纳米功能组合物,该纳米功能组合物在8~14μm红外波长范围的吸收/辐射率最高达0.91。
实施例4
本实施例公开了一种高选择性光子辐射降温器的制备方法,包括以下步骤:
(a)根据稀土硅酸镝的化学计量比SiO2-0.5La2O3-0.1Gd2O3-1.0Na2O,准确称取30g纳米二氧化硅、162.5g硝酸镧、34.3g硝酸钆和85g硝酸钠,溶解到体积乙醇水混合溶液中,在水浴70℃搅拌条件下蒸发溶剂得到凝胶,在150℃热处理3小时得到稀土硅酸镝预烧粉,在750℃热处理10小时得到颗粒平均尺寸为120nm的稀土硅酸镝钆化合物。
(b)根据钼酸钙CaMoO4化学式,准确称取41g硝酸钙和85g二钼酸铵,溶解到去离子水中。配置5%柠檬酸溶液,逐滴加入到上述溶液中,边加边剧烈搅拌,用氨水调节pH至4.0,在水浴80℃搅拌条件下蒸发溶剂得到凝胶,在150℃热处理4小时得到钼酸钙预烧粉,在850℃热处理12小时得到颗粒平均尺寸为85nm钼酸钙。
(c)按功能粉体组合物重量比例1:2:1.5,分别称取28g纳米二氧化硅(50nm,市售)、56g步骤(a)中的稀土硅酸镝钆化合物和42g步骤(b)中的钼酸钙,共同加入高速研磨分散机的球磨罐中,球磨转速为300转/分钟,球磨时间为6小时,得到所需的红外选择性辐射降温纳米功能组合物,该纳米功能组合物在8~14μm红外波长范围的吸收/辐射率最高达0.92。
Claims (6)
1.一种红外选择性辐射降温纳米功能组合物,该红外选择性辐射降温纳米功能组合物由纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物,按质量比例1:(0.5~2):(0.5~2),经球磨均匀混合而成;其中稀土硅酸盐化合物符合化学计量比SiO2-(0.5~2)Re2O3-(0.1~1.0)Na2O且在9~12μm范围内具有强的红外选择性辐射性能,其中Re为La、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Y或Sc;钼酸盐化合物符合化学计量比RMoO4且在10~14μm范围内具有强的红外选择性辐射性能,其中R为Mg、Ca、Sr或Ba。
2.根据权利要求1所述的一种红外选择性辐射降温纳米功能组合物,其特征在于该纳米功能组合物在8~14μm大气窗口具有强的选择性吸收-辐射性能,且对紫外-可见-近红外太阳光透明。
3.一种制备如权利要求1所述的一种红外选择性辐射降温纳米功能组合物的方法,其具体步骤如下:
(a)根据稀土硅酸盐化合物的化学计量比,准确称取纳米二氧化硅、稀土硝酸盐和硝酸钠,混合分散到乙醇水混合溶液中;在水浴搅拌条件下蒸发溶剂得到凝胶;经120~150℃低温预烧处理3~6小时后,再在600~900℃热处理3~12小时得到稀土硅酸盐化合物;
(b)根据钼酸盐化合物的化学计量比,准确称取钼酸铵和碱土金属硝酸盐,溶解到去离子水中;配置柠檬酸溶液,搅拌滴加入到上述溶液中,调节pH至3.0~4.0,在水浴搅拌条件下蒸发溶剂得到凝胶;经120~150℃低温预烧处理3~6小时后,再800~1000℃热处理3~12小时后,即得到钼酸盐化合物;
(c)按照纳米功能组合物质量比例,称取一定量纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物,利用高速研磨分散机处理后,即获得红外选择性辐射降温纳米功能组合物。
4.根据权利要求3所述的方法,其特征在于步骤(a)中的水浴温度为70~80℃。
5.根据权利要求3所述的方法,其特征在于步骤(b)中柠檬酸溶液的质量浓度为5%~10%;用氨水调节pH;水浴温度为70~80℃。
6.根据权利要求3所述的方法,其特征在于步骤(c)中高速研磨分散机的转速为300~400转/分钟,处理时间为2~6小时。
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