WO2022166345A1 - 一种三维多孔纳米复合降温薄膜的规模化制备方法 - Google Patents

一种三维多孔纳米复合降温薄膜的规模化制备方法 Download PDF

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WO2022166345A1
WO2022166345A1 PCT/CN2021/134098 CN2021134098W WO2022166345A1 WO 2022166345 A1 WO2022166345 A1 WO 2022166345A1 CN 2021134098 W CN2021134098 W CN 2021134098W WO 2022166345 A1 WO2022166345 A1 WO 2022166345A1
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nano
microspheres
dimensional porous
cooling film
parts
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French (fr)
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唐少春
张�荣
相波
申煜椿
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HAIAN INSTITUTE OF HIGH-TECH RESEARCH NANJING UNIVERSITY
Nanjing University
Nanjing Tech University
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HAIAN INSTITUTE OF HIGH-TECH RESEARCH NANJING UNIVERSITY
Nanjing University
Nanjing Tech University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/28—Polysaccharides or derivatives thereof
    • C04B26/285—Cellulose or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0016—Granular materials, e.g. microballoons
    • C04B20/002—Hollow or porous granular materials
    • C04B20/0036—Microsized or nanosized
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0016—Granular materials, e.g. microballoons
    • C04B20/002—Hollow or porous granular materials
    • C04B20/004—Hollow or porous granular materials inorganic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/005—High shear mixing; Obtaining macro-defect free materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B29K2001/08—Cellulose derivatives
    • B29K2001/12—Cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler

Definitions

  • the invention belongs to the technical field of polymer and inorganic composite materials, and particularly relates to a preparation method of a three-dimensional porous nanocomposite cooling film.
  • Radiation cooling is an effective cooling method. Radiation cooling utilizes the basic physical principle that all surfaces greater than absolute zero radiate energy in the form of electromagnetic waves. The temperature of outer space outside the atmosphere is close to absolute zero, so the temperature of outer space is close to absolute zero, which is a kind of "cold source", and infrared radiation can transfer heat from the earth's surface to outer space.
  • the Earth's atmospheric window is transparent to infrared radiation (thermal radiation) in the 7-14 ⁇ m band.
  • Passive radiative cooling is of great interest because it can spontaneously cool surfaces by radiating heat in the form of infrared radiation (8-13 ⁇ m) into cold outer space, while being highly transparent to its atmosphere .
  • This radiative cooling mechanism leads to the most promising cooling strategies based on pure passive cooling without any additional energy input such as electricity, refrigerants or mechanical pumps.
  • nighttime PRC can be achieved.
  • high-efficiency daytime PRC remains a daunting challenge because of the heat generated by sunlight at the surface, only a few percent solar absorptivity can offset or even exceed the cooling effect from infrared radiation.
  • the comparative invention adopts micron material additives such as silica, hollow glass microspheres, hollow ceramic microspheres, etc., with functions such as heat dissipation and cooling,
  • micron material additives such as silica, hollow glass microspheres, hollow ceramic microspheres, etc.
  • it cannot achieve the phenomenon that the true passive cooling effect that is, the temperature of the coating body
  • the coating cannot achieve the cooling effect under sunlight during the day
  • Refrigeration coating CN108250873A compared with the invention patent, it uses silica, hollow glass microspheres, nano-infrared ceramic powder and other material additives, which has the ability to reflect sunlight and strong infrared radiation ability, but its preparation method has high cost and high performance. Poor repeatability.
  • the invention provides a large-scale preparation method of a three-dimensional porous nanocomposite cooling film, which utilizes the high reflectivity of the film itself to reduce the absorption of sunlight, and at the same time removes the excess heat of the main body by radiating heat to the outside world, thereby realizing passive cooling Effect;
  • the present invention also provides a large-scale preparation method of a three-dimensional porous nanocomposite cooling film, which utilizes the three-dimensional structure of cellulose acetate (CA) and the self-deposition technique of a phase inversion method to prepare a composite cooling film with 3D CA/nano-microspheres, and constructs a 3D composite cooling film.
  • CA cellulose acetate
  • the hybrid structure of CA/nano-microspheres, and the low-cost and large-area composite cooling film can be prepared, which has strong universality.
  • a three-dimensional porous nano composite cooling film comprises the following raw materials: 0.1-0.5 parts of cellulose acetate, 1-5 parts of water, 20-100 parts of acetone, other additives and 10-20 parts of nano-microspheres .
  • the volume ratio of the water and acetone is 1:20.
  • the nano-microsphere is one or any of SiO 2 , SiC and TiO 2 ; the diameter of the spherical body of the nano-microsphere is 1 ⁇ m-800 ⁇ m.
  • the three-dimensional porous nanocomposite cooling film has micropores.
  • the nano-microspheres are enriched on one side of the three-dimensional porous nano-composite cooling film.
  • the auxiliary agent includes N,N dimethylformamide, hexafluoroisopropanol or formic acid.
  • the present invention also provides a large-scale preparation method of the three-dimensional porous nanocomposite cooling film described in the above technical solution, and the preparation of the above-mentioned composite cooling film includes the following steps:
  • S3 uses the Stoubel method to synthesize nano-microspheres of uniform size, and the obtained nano-microsphere particles are separated by centrifugation, washed with deionized water, and then vacuum-dried at 70 °C to obtain pre-dried nano-microspheres;
  • S4 disperse the pre-dried nano-microspheres in the precursor solution, and use a magnetic stirrer to stir at 400-600r/min, and the stirring time is 4-6h to form a milky white suspension;
  • S5 put the milky white suspension into the casting machine for natural volatilization, thereby obtaining a large-area cellulose acetate/nano-microsphere composite cooling film, that is, a 3D CA/nano-microsphere composite cooling film, the area and thickness of the film are all controllable.
  • the stirring speed of the magnetic stirrer is 400r/min, 500r/min or 600r/min;
  • the stirring time is 4h, 5h or 6h.
  • the auxiliary agent is added to the system with acetone in S1.
  • the present invention leads to the separation of CA from the aqueous phase through the rapid evaporation of volatile acetone, forming a large number of microdroplets in the CA matrix. After that, with the evaporation of the droplets, many micropores with narrow size distribution were generated, and at the same time, the nano-microspheres were deposited on one side of the composite film due to gravity, resulting in the formation of nano-microspheres enriched on one side of the film.
  • the 3D CA/nano-microsphere composite cooling film of the present invention has an optimal pore size, and the randomly distributed microspheres have a higher volume percentage, which is beneficial to highly enhanced solar reflection and infrared radiation.
  • the present invention adopts a general production process to realize the large-area preparation of the thin film. Using the natural drying process of the casting method, a large-area organic-inorganic composite cooling film with a 3D microstructure is prepared at low cost, and the problems of production efficiency and cost are solved.
  • the organic/inorganic composite cooling film with a 3D structure prepared by the present invention exhibits ultra-high r solar energy and ⁇ infrared values of 96% to 95%, and is comparable to that in the daytime. Under night conditions, it can be up to 6-8 °C lower than the surrounding environment, and has a good cooling effect.
  • test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are obtained from conventional commercial channels or prepared by conventional methods.
  • a three-dimensional porous nanometer composite cooling film the raw material of the composite cooling film: 0.1 part of cellulose acetate, 1 part of water, 20 parts of acetone, other auxiliary agents and 10 parts of nanometer microspheres.
  • the present invention also provides a large-scale preparation method of the three-dimensional porous nano composite cooling film.
  • the preparation of the composite cooling film includes the following steps:
  • S2 dissolves 0.1 part of CA in a mixed solvent of water and acetone to form a transparent precursor solution
  • S3 uses the Stoubel method to synthesize nano-microspheres of uniform size, and the obtained nano-microsphere particles are separated by centrifugation, washed with deionized water, and then vacuum-dried at 70 °C to obtain pre-dried nano-microspheres;
  • a three-dimensional porous nanometer composite cooling film the raw material of the composite cooling film: 0.25 parts of cellulose acetate, 2.5 parts of water, 50 parts of acetone, other auxiliary agents and 15 nanometer microspheres.
  • the present invention also provides a large-scale preparation method of a three-dimensional porous nano composite cooling film.
  • the preparation of the composite cooling film includes the following steps:
  • S3 uses the Stoubel method to synthesize nano-microspheres of uniform size, and the obtained nano-microsphere particles are separated by centrifugation, washed with deionized water, and then vacuum-dried at 70 °C to obtain pre-dried nano-microspheres;
  • a three-dimensional porous nanometer composite cooling film the raw material of the composite cooling film: 0.5 parts of cellulose acetate, 5 parts of water, 100 parts of acetone, other auxiliary agents and 20 parts of nano-microspheres.
  • the present invention also provides a large-scale preparation method of a three-dimensional porous nano composite cooling film.
  • the preparation of the composite cooling film includes the following steps:
  • S2 dissolves 0.5 part of CA in a mixed solvent of water and acetone to form a transparent precursor solution
  • S3 uses the Stoubel method to synthesize nano-microspheres of uniform size, and the obtained nano-microsphere particles are separated by centrifugation, washed with deionized water, and then vacuum-dried at 70 °C to obtain pre-dried nano-microspheres;
  • the large-scale preparation method of a three-dimensional porous nanocomposite cooling film disclosed by the invention is prepared by synergistic preparation of cellulose acetate, nano-microsphere material and other auxiliary agents, wherein three-dimensional porous cellulose acetate and nano-microsphere material are used.
  • the composite film material obtained by self-deposition has the effect of absorbing heat and enhancing the rate of external infrared radiation and external radiation, which can significantly reduce the radiation temperature and achieve the effect of rapid and strong cooling.
  • the film does not require external power and other active cooling equipment/methods Under the circumstance, the two mechanisms of 3D composite material structure and infrared passive radiation are combined, so as to achieve the purpose of effective cooling in the presence or absence of sunlight, and at the same time, the casting method is used to prepare a large area of organic-inorganic with 3D microstructure at low cost.
  • the composite cooling film solves the problems of production efficiency and cost.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

一种三维多孔纳米复合降温薄膜及其规模化制备方法。该降温薄膜材料采用0.1‑0.5份醋酸纤维素、1‑5份水、20‑100份丙酮、其他助剂以及10‑20份纳米微球作为原料，通过醋酸纤维素、纳米微球粒子和其他助剂三者协同配合制备得到，采用醋酸纤维素与纳米微球自沉积方式获得复合薄膜，成膜过程中液体挥发导致三维多孔生成；该薄膜具有增强向太空辐射红外热量的效果，可显著降低基体表面温度，实现快速强降温，在无需外部电力等主动降温设备、有/无太阳光照射的情况下，都能达到有效降温目的。

Description

一种三维多孔纳米复合降温薄膜的规模化制备方法
本申请要求于2021年02月04日提交中国专利局、申请号为CN202110150147.9、发明名称为“一种三维多孔纳米复合降温薄膜的规模化制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于高分子与无机复合材料技术领域，特别涉及一种三维多孔纳米复合降温薄膜的制备方法。
背景技术
目前，全球变暖的趋势不断加剧，尤其在赤道附近低纬度地区，建筑物和汽车等在户外直接暴露于太阳照射下的物体，内部温度很高，需要消耗大量的能源来降温。辐射降温是一种有效的降温方法，辐射降温利用了所有大于绝对零度的物体表面都在以电磁波的形式向外辐射能量的基本物理学原理。大气层外的外太空温度接近于绝对零度，因此外太空的温度接近绝对零度，是一种“冷源”，红外辐射可将地球表面的热量传输到外太空。地球的大气窗口在7-14μm波段范围对红外辐射(热辐射)是透明的。
被动辐射冷却(PRC)引起了人们的高度关注，因为它可以通过将热量以红外辐射(8-13μm)的形式辐射到冷外层空间，从而自发地冷却表面，而对其大气是高度透明的。这种辐射冷却机制导致了基于纯被动冷却的最有前途的冷却策略，而不需要任何额外的能量输入，如电力、制冷剂或机械泵。只有通过依靠优良的红外辐射性能，可以实现夜间PRC。然而，高效率的白天PRC仍然是一个巨大的挑战，因为阳光在表面产生的热量的影响，只有百分之几的太阳吸收率可以抵消甚至超过来自红外辐射的冷却效果。对比发明专利名称“高耐候性环境友好型散热降温涂料及其制备方法CN102558988A”，对比发明采用了二氧化硅、空心玻璃微球、空心陶瓷微球等微米材料助剂，具有散热降温等功能，但其达不到真正被动式降温效果(即涂料本体温度)低于环境温度的现象，所述涂料无法实现白天在太阳光照下的降温作用；对比发明专利名称“室外用全天候太阳 光反射与红外辐射制冷涂料CN108250873A”，对比发明专利采用了二氧化硅、空心玻璃微球、纳米红外陶瓷粉等材料助剂，具有太阳光反射能力、较强的红外辐射能力，但其制备方法成本高，且性能重复性较差。
因此，不难看出，现有技术仍存在着一些缺陷，特别是现有技术无法实现零能耗降温薄膜的规模化制备。
发明内容
本发明提供一种三维多孔纳米复合降温薄膜的规模化制备方法，利用薄膜自身高反射率从而减少对于太阳光的吸收，同时通过向外界进行热辐射的形式，去除主体多余的热量，实现被动降温的效果；
本发明还提供一种三维多孔纳米复合降温薄膜的规模化制备方法，利用醋酸纤维素(CA)的三维结构和倒相法自沉积技术，制备具有3D CA/纳米微球复合降温薄膜，构筑3D CA/纳米微球杂化结构，并且可以制备出低成本大面积的复合降温薄膜，有较强的普适性。
本发明的技术方案如下：
一种三维多孔纳米复合降温薄膜，所述复合降温薄膜包含以下的原料：0.1-0.5份醋酸纤维素、1-5份水、20-100份丙酮、其他助剂以及10-20份纳米微球。
优选的，所述水和丙酮的体积比为1：20。
优选的，所述纳米微球为SiO 2、SiC和TiO 2中一种或任意几种；所述纳米微球的球形体的直径尺寸为1μm-800μm。
优选的，所述三维多孔纳米复合降温薄膜具有微孔。
优选的，所述纳米微球富集在所述三维多孔纳米复合降温薄膜的一面。
优选的，所述助剂包括N,N二甲基甲酰胺、六氟异丙醇或甲酸。
本发明还提供上述技术方案所述三维多孔纳米复合降温薄膜的规模化制备方法，制备上述复合降温薄膜，包括以下步骤：
S1称取一定量的水和丙酮进行混合，水：丙酮的体积比为＝1：20，形成混合溶剂；
S2将一定量的CA溶解在所述混合溶剂中，从而形成透明的前体溶液；
S3采用斯托贝尔法合成均匀大小的纳米微球，经离心分离得到的纳米微球颗粒，并用去离子水洗涤，然后在70℃下真空干燥，得到预干燥的纳米微球；
S4将预干燥的纳米微球分散在所述前体溶液中，采用磁力搅拌机以400-600r/min进行搅拌，搅拌时间为4-6h，形成乳白色悬浮液；
S5将所述乳白色悬浮液放入到流延机中进行自然挥发，从而得到大面积的醋酸纤维素/纳米微球复合降温薄膜，即3D CA/纳米微球复合降温薄膜，薄膜的面积和厚度均可控。
优选的，所述S4中，所述磁力搅拌机的搅拌速度为400r/min、500r/min或600r/min；
所述搅拌时间为4h、5h或6h。
优选的，所述助剂在S1中随丙酮加入体系。
与现有技术相比，本发明的有益效果如下：
第一，本发明通过挥发性丙酮的快速蒸发导致CA与水相分离，在CA基体中形成大量的微滴。在此之后，随着微滴的蒸发，许多具有窄尺寸分布的微孔产生，同时，纳米微球由于重力沉积于复合薄膜的一面，导致了纳米微球富集在薄膜的一面形成。
第二，本发明3D CA/纳米微球复合降温薄膜，具有最佳的孔径，随机分布的微球具有较高的体积百分比，有利于高度增强的太阳反射和红外辐射。
第三，本发明采用一条通用的生产工艺实现薄膜的大面积制备。采用流延法自然干燥工艺，低成本地制备出大面积具有3D微结构的有机-无机复合降温薄膜，解决生产效率以及成本的问题。
第四，本发明制备的所述具有3D结构的有机/无机复合降温薄膜，该3D CA/纳米微球复合降温薄膜表现出超高r太阳能和ε红外值达到96％～95％，在白天与夜间条件下最多可比周围环境低6-8℃，具备良好的降温效果。
当然，实施本发明的任一产品，并不一定需要同时达到以上所述的所有优点。
具体实施方式
下面结合实施例对本发明作进一步地详细说明，但本发明的实施方式不限于此。
下述实施例中所述试验方法或测试方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均从常规商业途径获得，或以常规方法制备。
下面结合具体实施例，进行进一步的说明。
实施例1
一种三维多孔纳米复合降温薄膜，复合降温薄膜的原料：0.1份醋酸纤维素、1份水、20份丙酮、其他助剂以及10份纳米微球。
本发明还提供一种三维多孔纳米复合降温薄膜的规模化制备方法，制备上述复合降温薄膜，包括以下步骤：
S1称取1份水和20份丙酮的进行混合，水：丙酮的体积比为＝1：20，形成混合溶剂；
S2将0.1份的CA溶解在水和丙酮的混合溶剂中，从而形成透明的前体溶液；
S3采用斯托贝尔法合成均匀大小的纳米微球，经离心分离得到的纳米微球颗粒，并用去离子水洗涤，然后在70℃下真空干燥，得到预干燥的纳米微球；
S4将预干燥的纳米微球称取10份分散在前体溶液中，采用磁力搅拌机以400r/min进行搅拌，搅拌时间为4h，形成乳白色悬浮液；
S5将乳白色悬浮液放入到流延机机中进行自然挥发，从而得到3D CA/纳米微球复合降温薄膜。
实施例2
一种三维多孔纳米复合降温薄膜，复合降温薄膜的原料：0.25份醋酸纤维素、2.5份水、50份丙酮、其他助剂以及15纳米微球。
本发明还提供一种三维多孔纳米复合降温薄膜的规模化制备方法，制备上述复合降温薄膜，包括以下步骤：
S1称取2.5份水和50份丙酮进行混合，水：丙酮的体积比为＝1：20，形成混合溶剂；
S2将0.25份CA和其他助剂溶解在水和丙酮的混合溶剂中，从而形 成透明的前体溶液；
S3采用斯托贝尔法合成均匀大小的纳米微球，经离心分离得到的纳米微球颗粒，并用去离子水洗涤，然后在70℃下真空干燥，得到预干燥的纳米微球；
S4将预干燥的纳米微球称取10份分散在前体溶液中，采用磁力搅拌机以500r/min进行搅拌，搅拌时间为5h，形成乳白色悬浮液；
S5将乳白色悬浮液放入到流延机机中进行自然挥发，从而得到3D CA/纳米微球复合降温薄膜。
实施例3
一种三维多孔纳米复合降温薄膜，复合降温薄膜的原料：0.5份醋酸纤维素、5份水、100份丙酮、其他助剂以及20份纳米微球。
本发明还提供一种三维多孔纳米复合降温薄膜的规模化制备方法，制备上述复合降温薄膜，包括以下步骤：
S1称取5份水和100份丙酮进行混合，水：丙酮的体积比为＝1：20，形成混合溶剂；
S2将0.5份的CA溶解在水和丙酮的混合溶剂中，从而形成透明的前体溶液；
S3采用斯托贝尔法合成均匀大小的纳米微球，经离心分离得到的纳米微球颗粒，并用去离子水洗涤，然后在70℃下真空干燥，得到预干燥的纳米微球；
S4将预干燥的纳米微球称取10份分散在前体溶液中，采用磁力搅拌机以600r/min进行搅拌，搅拌时间为6h，形成乳白色悬浮液；
S5将乳白色悬浮液放入到流延机中进行自然挥发，从而得到大面积的3D CA/纳米微球复合降温薄膜。
本发明公开的一种三维多孔纳米复合降温薄膜的规模化制备方法，通过醋酸纤维素、纳米微球材料和其他助剂三者协同配制备得到，其中采用三维多孔醋酸纤维素与纳米微球材料自沉积方式获得复合薄膜材料，具有吸收热量，增强向外红外辐射外辐射热量率的效果，可显著降低辐射温度，实现快速强降温的效果，该薄膜在无需外在电力等主动降温设备/方式情况下，结合采用3D复合材料结构和红外被动辐射两种机制，从而达到有 /无太阳光时有效降温的目的，同时采用流延法低成本地制备出大面积具有3D微结构的有机-无机复合降温薄膜，解决生产效率以及成本的问题。
以上公开的本发明优选实施例仅用于帮助阐述本发明。优选实施例并没有详尽叙述所有的细节，也不限制该发明仅为所述的具体实施方式。显然，根据本说明书的内容，可作很多的修改和变化。本说明书选取并具体描述这些实施例，是为了更好地解释本发明的原理和实际应用，从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受到权利要求书及其全部范围和等效物的限制。

Claims (7)

  1. 一种三维多孔纳米复合降温薄膜，其特征在于，包含以下的原料：0.1-0.5份醋酸纤维素、1-5份水、20-100份丙酮、其他助剂以及10-20份纳米微球。
  2. 根据权利要求1所述的三维多孔纳米复合降温薄膜，其特征在于，所述水和丙酮的体积比为1：20。
  3. 根据权利要求1所述的三维多孔纳米复合降温薄膜，其特征在于，所述纳米微球为SiO 2、SiC和TiO 2中一种或任意几种；所述纳米微球的球形体的直径尺寸为1μm-800μm。
  4. 根据权利要求1所述的三维多孔纳米复合降温薄膜，其特征在于，所述三维多孔纳米复合降温薄膜具有微孔。
  5. 根据权利要求1所述的三维多孔纳米复合降温薄膜，其特征在于，所述纳米微球富集在所述三维多孔纳米复合降温薄膜的一面。
  6. 一种三维多孔纳米复合降温薄膜的规模化制备方法，其特征在于，包括以下步骤：
    S1称取一定量的水和丙酮进行混合，水：丙酮的体积比为1：20，形成混合溶剂；
    S2将一定量的酸纤维素溶解在所述混合溶剂中，从而形成透明的前体溶液；
    S3采用斯托贝尔法合成均匀大小的纳米微球，经离心分离得到的纳米微球颗粒，并用去离子水洗涤，然后在70℃下真空干燥，得到预干燥的纳米微球；
    S4将预干燥的纳米微球分散在所述前体溶液中，采用磁力搅拌机以400-600r/min进行搅拌，搅拌时间为4-6h，形成乳白色悬浮液；
    S5将所述乳白色悬浮液放入到流延机中进行自然挥发，从而得到大面积的醋酸纤维素/纳米微球复合降温薄膜，且薄膜厚度可以调控。
  7. 根据权利要求6所述的规模化制备方法，其特征在于，所述S4中，所述磁力搅拌机的搅拌速度为400r/min、500r/min或600r/min；
    所述搅拌时间为4h、5h或6h。
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