Rare-earth-based one-dimensional photonic crystal heat dissipation coating prepared from optical glass waste residues and preparation method and application thereof

Abstract

The invention provides a rare-earth-based one-dimensional photonic crystal heat dissipation coating prepared from optical glass waste residues and a preparation method and application of the rare-earth-based one-dimensional photonic crystal heat dissipation coating. The coating is formed by alternately arranging glass layers and rare-earth oxide layers on a base material. And the rare earth oxide layer is formed by depositing hafnium oxide-lanthanum cerium oxide heterojunction on the base material or the glass layer by adopting a magnetron sputtering process. The rare-earth-based one-dimensional photonic crystal heat dissipation coating provided by the invention has high emission performance and can realize passive heat dissipation, and meanwhile, the material is endowed with high reflectivity by the structure of the one-dimensional photonic crystal, so that the surface of a base station can reflect sunlight to a greater extent, the conversion of light energy into heat is reduced, and the heat dissipation efficiency is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional materials, and particularly relates to a rare earth-based one-dimensional photonic crystal heat dissipation coating prepared from optical glass waste residue, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, 5G technology has developed rapidly. In the mobile communication network, base stations are large power consumers, and approximately 80% of the energy consumption comes from the widely distributed base stations. In the technical standards, the frequency band of 5G is much higher than that of the 4G network, resulting in greater attenuation during the signal propagation process. Therefore, the base station density of the 5G network will be higher, which also means higher power consumption. Therefore, more effective heat dissipation is urgently needed during the popularization process of 5G base stations. Currently, most 5G base stations use heat dissipation teeth to achieve air convection heat dissipation. Not only is the heat dissipation efficiency low, but the volume of the heat dissipation device is large, making the base station box heavier and more difficult to install. At the same time, under sunlight irradiation, the temperature of the base station box will further increase, and this convection heat dissipation method cannot block sunlight. In view of the problems of the existing technology, it is particularly important to develop a new heat dissipation method that has little impact on the volume, weight, and installation difficulty of the box and can block sunlight. Summary of the Invention

[0003] In view of this, the present invention aims to overcome the defects in the existing technology and proposes a rare earth-based one-dimensional photonic crystal heat dissipation coating, a preparation method thereof, and an application thereof.

[0004] To achieve the above object, the technical solution of the present invention is realized as follows:

[0005] In a first aspect, the present invention provides a rare earth-based one-dimensional photonic crystal heat dissipation coating prepared from optical glass waste residue. The rare earth-based one-dimensional photonic crystal heat dissipation coating is formed by alternately arranging glass layers and rare earth oxide layers on a substrate. The rare earth oxide layer is formed by depositing a hafnium oxide-lanthanum cerium oxide heterojunction on the substrate or the glass layer by a magnetron sputtering process. The preparation method of the hafnium oxide-lanthanum cerium oxide heterojunction includes the following steps:

[0006] 1) Add hafnium oxide powder to a lanthanum cerium chloride solution. After mixing evenly, centrifuge the solution to separate out the solid powder.

[0007] 2) Add the solid powder obtained in step 1) to a surfactant solution and mix evenly to obtain a mixed solution.

[0008] 3) Heat the mixed solution obtained in step 2) to 50 - 80 °C, and dropwise add an alkali solution thereto. Continuously react for 2 - 5 h, and then perform sedimentation at room temperature for 6 - 12 h.

[0009] 4) Filter, wash, and dry the precipitate obtained in step 3), and calcine it at 600 - 900 °C for 2 - 6 h to obtain the hafnium oxide-lanthanum cerium oxide heterojunction.

[0010] Preferably, the molar concentration of the lanthanum cerium chloride solution is 0.05 - 0.1 mol / L, which is obtained by dissolving cerium chloride and lanthanum chloride with a molar ratio of (10 - 20):1 in water.

[0011] Preferably, the addition amount of hafnium oxide powder is 5 - 10 g per liter of the lanthanum cerium chloride solution.

[0012] Preferably, the concentration of the surfactant solution is 1 - 10 g / L.

[0013] Preferably, the mass ratio of the surfactant to the solid powder is (1 - 10):60.

[0014] Preferably, the surfactant is one or a mixture of several of dodecylphenol polyoxyethylene ether, polyoxyethylene sorbitan monolaurate, and glycerol monostearate.

[0015] Preferably, the glass layer is formed by vacuum evaporation coating of glass frit on the rare earth oxide layer, and the glass frit is prepared from fluorocrown optical glass powder and fluoride with a mass ratio of (70 - 82):(19 - 32).

[0016] Preferably, the fluoride includes one or a mixture of several of erbium fluoride, zinc fluoride, calcium fluoride, sodium fluoride, lanthanum fluoride, aluminum fluoride, and magnesium fluoride;

[0017] Preferably, the fluoride includes erbium fluoride, zinc fluoride, and calcium fluoride with a mass ratio of (10 - 15):(7 - 12):(2 - 5).

[0018] Preferably, the preparation method of the glass frit includes the following steps:

[0019] S1: Crush and grind the fluorocrown optical glass to obtain fluorocrown optical glass powder;

[0020] S2: Mix the fluorocrown optical glass powder and the fluoride to obtain a mixed powder:

[0021] S3: Heat the mixed powder to 1450 - 1600 °C to form a glass melt, continue heating and start stirring, and continue for 2 - 5 h;

[0022] S4: Pour the glass melt into a mold for casting, and anneal at 350 - 600 °C for 2 - 4 h to obtain the glass frit.

[0023] Preferably, the fluoride needs to be passed through a 200 - mesh sieve in advance to avoid too large particles.

[0024] The glass layer is prepared with waste slag of fluorocrown optical glass as raw material. In the production process of fluorocrown optical glass, a lot of waste and defective products will be generated. Reusing these wastes has considerable value. Fluorocrown optical glass is a low-refractive index glass. On its basis, fluoride is added again and re-smelted to make it have better low-refractive index performance. The composition of the fluorocrown glass is as follows by mass fraction: 2.5% LiPO3, 3% Mg(PO)2, 14% Al(PO3)2, 6% MgF2, 31% CaF2, 15.5% BaF2, 17.8% AlF3, 10.2% K2TiF6.

[0025] In a second aspect, the present invention also provides an application of the above-mentioned rare earth-based one-dimensional photonic crystal heat dissipation coating in the heat dissipation of a base station cabinet.

[0026] Preferably, the thickness of the rare earth oxide layer in the rare earth-based one-dimensional photonic crystal heat dissipation coating is 20 to 45 nm, and the thickness of the glass layer is 50 to 90 nm.

[0027] Preferably, a rare earth oxide layer is first deposited on the surface of the base station housing, and then a glass layer is deposited, which is regarded as a cycle, and the cycle is repeated to continue deposition, and the number of deposition cycles is 2 to 5.

[0028] In order to protect the bottom coating, the coating range of the topmost low-refractive-index glass layer should be slightly larger than the bottom coating, in a covering state.

[0029] The rare earth-based one-dimensional photonic crystal heat dissipation coating of the present invention is formed by periodically stacking two dielectric layers with different dielectric constants. Its characteristic is that Bragg scattering will occur on the surface of the dielectric layer, generating a photon bandgap, and light with energy in the bandgap cannot propagate, thereby generating a reflection of nearly 100% on the surface. The greater the refractive index ratio of the two dielectric layers, the wider the bandgap, and the fewer the number of periods required to form the bandgap. The key point proposed by the present invention is to apply the special periodic structure of this material to achieve high reflection performance of sunlight under outdoor conditions, and at the same time rely on the high emission performance of the material itself to achieve rapid heat dissipation.

[0030] Compared with the prior art, the present invention has the following advantages:

[0031] (1) Compared with the existing 5G base station method of heat dissipation through convection between heat dissipation teeth and air, the rare earth-based one-dimensional photonic crystal heat dissipation coating provided by the present invention has high emissive performance and can achieve passive heat dissipation. At the same time, the structure of the one-dimensional photonic crystal gives the material high reflectivity, so that the base station surface can reflect sunlight to a greater extent, reduce the conversion of light energy into heat, and improve the heat dissipation efficiency.

[0032] (2) The rare earth-based one-dimensional photonic crystal heat dissipation coating provided by the present invention has no impact on the volume and mass of 5G base stations, saves the box space, and is also beneficial to the installation of the base station box. Description of the Drawings

[0033] Figure 1 It is a schematic structural diagram of the heat dissipation test device;

[0034] Figure 2 It is a schematic structural diagram of the PTC heating sheet;

[0035] Figure 3 It is a schematic structural diagram of the rare earth-based one-dimensional photonic crystal heat dissipation coating prepared from the optical glass waste residues in Examples 1 to 4;

[0036] Figure 4 It is the heat dissipation effect diagram of the embodiments and comparative examples of the present invention.

[0037] Description of the reference numerals:

[0038] 1. Mobile power supply; 2. PTC heating sheet; 3. Rare earth-based one-dimensional photonic crystal heat dissipation coating; 4. Stainless steel coating substrate; 5. Wire; 6. Patch-type thermocouple; 7. Glass layer; 8. Rare earth oxide layer. Detailed Embodiments

[0039] The embodiments of the present invention will be described in detail below. The following described embodiments are exemplary and are only used to explain the present invention, and should not be construed as a limitation to the present invention.

[0040] In this article, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs.

[0041] In this article, when a value is described as a range, it should be understood that such disclosure includes the disclosure of all possible sub-ranges within that range, as well as specific numerical values falling within that range, regardless of whether the specific numerical values or specific sub-ranges are explicitly indicated.

[0042] In this article, when referring to "a plurality of", etc., unless otherwise specifically defined, it means greater than 2 or equal to 2 in quantity. For example, "one or more" means one or greater than or equal to two.

[0043] In this article, when referring to "preferred", "more preferred", it is only for describing embodiments or examples with better effects, and it should be understood that it does not constitute a limitation to the protection scope of the present invention.

[0044] In this article, when referring to "further", etc., it is used for descriptive purposes and represents a difference in content, but it should not be construed as a limitation to the protection scope of the present invention.

[0045] In this text, the term "and / or" describes the relationship between objects and indicates that three relationships can exist. For example, A and / or B means: A or B, or the three relationships of A and B.

[0046] In this text, the term "about" means + / - 10% of the specified value, preferably + / - 5%, more preferably + / - 1%.

[0047] In this text, the terms "comprising", "including", "having", "containing", etc. are all open-ended terms, meaning including but not limited to.

[0048] Unless otherwise specified, all technical and scientific terms used in this text have the same meaning as commonly understood by those of ordinary skill in the art to which this invention pertains. Although this invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described in this text can also be used in the implementation or testing of this invention.

[0049] The present invention will be described in detail below in conjunction with examples.

[0050] Example 1

[0051] The preparation method of the glass layer in the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue is as follows:

[0052] (1) The fluorocrown optical glass is crushed and then ground in the ball mill tank of a planetary ball mill at a rotation speed of 300 r / min for 3 h. Then it is screened with a 200-mesh sieve to remove coarser particles, obtaining fluorocrown optical glass powder.

[0053] (2) The fluoride raw materials are passed through a 200-mesh sieve and then mixed with the fluorocrown optical glass powder. The specific composition of each component by mass fraction is as follows:

[0054] 80 parts of fluorocrown optical glass powder;

[0055] 10 parts of erbium fluoride;

[0056] 8 parts of zinc fluoride;

[0057] 2 parts of calcium fluoride.

[0058] (3) The mixed powder obtained after mixing is poured into a furnace with stirring, heated to 1450 °C to form a glass melt, and continue heating and start stirring for 3 hours.

[0059] (4) The glass melt is poured into a mold for casting and annealed at 450 °C for 2.5 hours to obtain a low refractive index glass frit.

[0060] The material of the rare earth oxide layer of the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue is a hafnium oxide-lanthanum cerium oxide heterojunction. The specific preparation method of the hafnium oxide-lanthanum cerium oxide heterojunction is as follows:

[0061] 1) Weigh cerium chloride and lanthanum chloride according to a molar ratio of 10:1. Add an appropriate amount of deionized water to prepare a 0.1 mol / L lanthanum cerium chloride solution.

[0062] 2) Add 10 g of hafnium oxide powder to each liter of the lanthanum cerium chloride solution and ultrasonicate for 5 h. Then centrifuge the solution to separate the solid powder.

[0063] 3) Dissolve a small amount of dodecylphenol polyoxyethylene ether in deionized water to prepare a 10 g / L solution. Take out 500 mL of the solution and add 30 g of the solid powder separated in step 2) to it, and shake to disperse it evenly.

[0064] 4) Pour the solution described in step 3) into a flask, heat it to 80 °C, and add 300 mL of ammonia water dropwise to it. Keep reacting for 5 h, and then carry out sedimentation at room temperature for 12 h.

[0065] 5) Filter, wash, and dry the precipitate, and calcine it at 900 °C for 2 h to obtain the hafnium oxide-lanthanum cerium oxide heterojunction.

[0066] The specific preparation method of the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue is as follows:

[0067] S1: Ultrasonically clean the stainless steel substrate with absolute ethanol for 30 min, dry the substrate and let it cool down.

[0068] S2: Place the stainless steel substrate in the vacuum chamber of a magnetron sputtering coater, evacuate to 10 -3 Pa, with the volume ratio of argon to oxygen gas being 30:70, and set the air pressure to 0.2 MPa. Use a rotary cathode to magnetron sputter the hafnium oxide-lanthanum cerium oxide heterojunction on the stainless steel substrate to form a rare earth oxide layer, and control the thickness of this coating to be 42 nm.

[0069] S3: Take out the stainless steel substrate that has completed step S2 and put it into a vacuum evaporation instrument. Evaporate the low refractive index glass frit, set the evaporation temperature to 1500 °C, and set the vacuum degree to 5×10 -5 Pa, and control the thickness of this glass layer to be 54 nm.

[0070] S4: Repeat the operation in step S2, and change the thickness of the rare earth oxide layer to 22 nm. After the coating is completed, repeat the operation in step S3 again, and change the thickness of the glass layer to 87 nm, as Figure 3 shown.

[0071] Example 2

[0072] The preparation method of the glass layer in the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue is as follows:

[0073] (1) Crush the fluorocrown optical glass, put it into the ball mill tank of a planetary ball mill, grind it at a rotation speed of 300 r / min for 3 h, and then screen it with a 200-mesh sieve to remove coarser particles, obtaining fluorocrown optical glass powder.

[0074] (2) Pass the fluoride raw material through a 200-mesh sieve and then mix it with the fluorocrown optical glass powder. The specific composition of each component by mass fraction is as follows:

[0075] 75 parts of fluorocrown optical glass powder;

[0076] 12 parts of lanthanum fluoride;

[0077] 10 parts of sodium fluoride;

[0078] 3 parts of magnesium fluoride.

[0079] (3) Pour the mixed powder obtained after mixing into a furnace with stirring, heat it up to 1500 °C to make a glass melt, continue heating and start stirring, and keep it for 3.5 hours.

[0080] (4) Pour the glass melt into a mold for casting and annealing at 450 °C for 3.5 hours to obtain a low-refractive-index glass frit.

[0081] The material of the rare earth oxide layer in the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue is a hafnium oxide-lanthanum cerium oxide heterojunction. The specific preparation method is as follows:

[0082] 1) Weigh cerium chloride and lanthanum chloride according to a molar ratio of 20:1. Add an appropriate amount of deionized water to prepare a 0.05 mol / L lanthanum cerium chloride solution.

[0083] 2) Add 5 g of hafnium oxide powder to each liter of the above solution and sonicate for 2 h. Then centrifuge the solution to separate the solid powder.

[0084] 3) Dissolve a small amount of polyoxyethylene sorbitan monolaurate in deionized water to prepare a 1 g / L solution. Take out 500 mL of the solution, add 30 g of the solid powder described in step 2) to it, and shake it to make it disperse evenly.

[0085] 4) Pour the solution described in step 3) into a flask, heat it up to 50 °C, and add 300 mL of ammonia water dropwise to it, continuously react for 2 h, and then carry out sedimentation at room temperature for 6 h.

[0086] 5) Filter, wash, and dry the precipitate, and calcine it at 600 °C for 2 h to obtain a hafnium oxide-lanthanum cerium oxide heterojunction.

[0087] The specific preparation method of the rare earth-based one-dimensional photonic crystal heat dissipation coating is as follows:

[0088] S1: Ultrasonically clean the stainless steel substrate with absolute ethanol for 30 min, dry the substrate and let it cool down.

[0089] S2: Place the stainless steel substrate in the vacuum chamber of a magnetron sputtering coater, evacuate to 10 -3 Pa, with the volume ratio of argon to oxygen gas being 30:70, and set the air pressure to 0.2 MPa. Use a rotating cathode to magnetron sputter a hafnium oxide-lanthanum cerium oxide heterojunction on the stainless steel substrate to form a rare earth oxide layer, and control the thickness of this coating to be 44 nm.

[0090] S3: Take out the stainless steel substrate that has completed step S2, put it into a vacuum evaporation instrument, evaporate the low refractive index glass frit, set the evaporation temperature to 1500 °C, and set the vacuum degree to 5×10 -5 Pa, and control the thickness of this glass layer to be 56 nm.

[0091] S4: Repeat the operation in step S2, and change the thickness of the rare earth oxide layer to 37 nm. After the coating is completed, repeat the operation in step S3, and change the thickness of the glass layer to 72 nm. Repeat the operation in step S2 again, and change the thickness of the rare earth oxide layer to 26 nm. Repeat the operation in S3 again, and change the thickness of the glass layer to 83 nm, as Figure 3 shown.

[0092] Example 3

[0093] The preparation method of the glass layer in the rare earth-based one-dimensional photonic crystal heat dissipation coating is as follows:

[0094] (1) Crush the fluorocrown optical glass, put it into the ball milling tank of a planetary ball mill, grind at a speed of 300 r / min for 3 h, and then screen with a 200-mesh sieve to remove coarser particles to obtain fluorocrown glass powder.

[0095] (2) Pass other fluoride raw materials through a 200-mesh sieve, and then mix them with the fluorocrown optical glass powder. The specific composition of each component by mass is as follows:

[0096] 70 parts of fluorocrown optical glass powder;

[0097] 14 parts of aluminum fluoride;

[0098] 12 parts of zinc fluoride;

[0099] 4 parts of lanthanum fluoride.

[0100] (3) Pour the mixed powder obtained after mixing into a furnace with stirring, heat it up to 1600 °C to make a glass melt, continue heating and turn on the stirring for 4 hours.

[0101] (4) Pour the glass melt into a mold for casting, and anneal it at 450 °C for 4 hours to obtain a glass frit with a low refractive index.

[0102] The material of the rare earth oxide layer of the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue is a hafnium oxide-lanthanum cerium oxide heterojunction. The specific preparation method of the hafnium oxide-lanthanum cerium oxide heterojunction is as follows:

[0103] 1) Weigh cerium chloride and lanthanum chloride according to a molar ratio of 15:1. Add an appropriate amount of deionized water to prepare a 0.08 mol / L lanthanum cerium chloride solution.

[0104] 2) Add 8 g of hafnium oxide powder to each liter of the lanthanum cerium chloride solution, and ultrasonicate for 3 h. Then centrifuge the solution to separate out the solid powder.

[0105] 3) Dissolve a small amount of polyoxyethylene sorbitan monolaurate in deionized water to prepare a 5 g / L solution. Take out 500 mL of the solution, add 30 g of the solid powder separated in step 2) to it, and shake to disperse it evenly.

[0106] 4) Pour the solution prepared in step 3) into a flask, heat it up to 70 °C, and add 300 mL of ammonia water dropwise to it, continue the reaction for 3 h, and then carry out sedimentation at room temperature for 10 h.

[0107] 5) Filter, wash and dry the precipitate, and calcine it at 800 °C for 2 h to obtain a hafnium oxide-lanthanum cerium oxide heterojunction.

[0108] The specific preparation method of the rare earth-based one-dimensional photonic crystal heat dissipation coating is as follows:

[0109] S1: Ultrasonically clean the stainless steel substrate with absolute ethanol for 30 min, dry the substrate and let it cool down.

[0110] S2: Put the stainless steel substrate into the vacuum chamber of a magnetron sputtering coater, evacuate to 10 -3 Pa, use an argon-to-oxygen gas volume ratio of 30:70, and set the gas pressure to 0.2 MPa. Use a rotating cathode to magnetron sputter a hafnium oxide-lanthanum cerium oxide heterojunction on the stainless steel substrate to form a rare earth oxide layer, and control the thickness of this coating to be 45 nm. Use this as the first film layer.

[0111] S3: Take out the stainless steel substrate that has completed step S2, put it into a vacuum evaporation apparatus, evaporate the low refractive index glass frit, set the evaporation temperature to 1500 °C, and set the vacuum degree to 5×10 -5Control the thickness of the glass layer to be 50 nm. This is used as the second film layer.

[0112] S4: Repeat the coating process of the subsequent cycles alternately by the methods in Step S2 and Step S3. The third, fifth, and seventh film layers are all rare earth oxide layers, with film thicknesses of 39 nm, 31 nm, and 25 nm respectively. The fourth, sixth, and eighth film layers are all glass layers, with film thicknesses of 58 nm, 76 nm, and 85 nm respectively, as Figure 3 shown.

[0113] Example 4

[0114] The preparation method of the glass layer in the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue is as follows:

[0115] (1) Crush the fluorocrown optical glass, put it into the ball mill tank of a planetary ball mill, grind it at a rotational speed of 300 r / min for 3 h, and then screen it with a 200-mesh sieve to remove coarser particles to obtain fluorocrown optical glass powder.

[0116] (2) Pass the fluoride raw material through a 200-mesh sieve and then mix it with the fluorocrown optical glass powder. The specific composition of each component by mass fraction is as follows:

[0117] 82 parts of fluorocrown optical glass powder;

[0118] 15 parts of erbium fluoride;

[0119] 7 parts of sodium fluoride;

[0120] 4 parts of magnesium fluoride.

[0121] (3) Pour the mixed powder obtained after mixing into a furnace with stirring, heat it to 1450 °C to make a glass melt, continue heating and start stirring for 3 hours.

[0122] (4) Pour the glass melt into a mold for casting and anneal it at 450 °C for 2.5 hours to obtain a low-refractive-index glass frit.

[0123] The material of the rare earth oxide layer in the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue is a hafnium oxide-lanthanum cerium oxide heterojunction. The specific preparation method of the hafnium oxide-lanthanum cerium oxide heterojunction is as follows:

[0124] 1) Weigh cerium chloride and lanthanum chloride in a molar ratio of 10:1. Add an appropriate amount of deionized water to prepare a 0.1 mol / L lanthanum cerium chloride solution.

[0125] 2) Add 10 g of hafnium oxide powder to each liter of the lanthanum cerium chloride solution, sonicate for 5 h. Then centrifuge the solution to separate out the solid powder.

[0126] 3) Dissolve a small amount of dodecylphenol polyoxyethylene ether in deionized water to prepare a solution with a concentration of 10 g / L. Take out 500 mL of the solution, add 30 g of the solid powder separated in step 2), and shake to disperse it evenly.

[0127] 4) Pour the solution described in step 3) into a flask, heat it up to 80 °C, and dropwise add 300 mL of ammonia water, continuously react for 5 h, and then carry out sedimentation at room temperature for 12 h.

[0128] 5) Filter, wash, and dry the precipitate, and calcine it at 900 °C for 2 h to obtain hafnium oxide - lanthanum cerium oxide heterojunction.

[0129] The specific preparation method of the rare earth - based one - dimensional photonic crystal heat - dissipation coating made from optical glass waste residue is as follows:

[0130] S1: Ultrasonically clean the stainless - steel substrate with absolute ethanol for 30 min, dry the substrate and let it cool down.

[0131] S2: Put the stainless - steel substrate into the vacuum chamber of a magnetron sputtering coater, evacuate to 10 -3 Pa, use argon and oxygen with a volume ratio of 30:70, and set the air pressure to 0.2 MPa. Use a rotating cathode to magnetron sputter hafnium oxide - lanthanum cerium oxide heterojunction on the stainless - steel substrate to form a rare - earth oxide layer, and control the thickness of this coating to be 32 nm.

[0132] S3: Take out the stainless - steel substrate that has completed step S2, put it into a vacuum evaporation instrument, evaporate the low - refractive - index glass frit, set the evaporation temperature to 1500 °C, and set the vacuum degree to 5×10 -5 Pa, and control the thickness of this glass layer to be 65 nm.

[0133] S4: Repeat the operation in step S2, and change the thickness of the rare - earth oxide layer to 40 nm. After the coating is completed, repeat the operation in step S3, and change the thickness of the glass layer to 75 nm.

[0134] Comparative Example 1

[0135] The difference between the rare - earth - based one - dimensional photonic crystal heat - dissipation coating made from optical glass waste residue and Example 1 is that the raw material of the rare - earth oxide layer is 5N - grade cerium oxide, and other steps are the same as those in Example 1.

[0136] Comparative Example 2

[0137] The difference between the rare - earth - based one - dimensional photonic crystal heat - dissipation coating made from optical glass waste residue and Example 1 is that the raw material of the rare - earth oxide layer is lanthanum cerium oxide, and the specific preparation method is as follows:

[0138] 1) Weigh cerium chloride and lanthanum chloride according to a molar ratio of 10:1. Add an appropriate amount of deionized water to prepare a 0.1 mol / L cerium-lanthanum chloride solution.

[0139] 2) Centrifuge the cerium-lanthanum chloride solution to separate out the solid powder.

[0140] 3) Dissolve a small amount of dodecylphenol polyoxyethylene ether in deionized water to prepare a 10 g / L solution. Take out 500 mL of the solution and add 30 g of the solid powder separated in step 2) to it, and shake to disperse it evenly.

[0141] 4) Pour the solution described in step 3) into a flask, heat it to 80 °C, and add 300 mL of ammonia water dropwise to it, continue the reaction for 5 h, and then carry out sedimentation at room temperature for 12 h.

[0142] 5) Filter, wash, and dry the precipitate, and calcine it at 900 °C for 2 h to obtain cerium-lanthanum oxide.

[0143] All other steps are the same as those in Example 1.

[0144] Comparative Example 3

[0145] The difference between the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue and Example 1 is that the raw material of the rare earth oxide layer is hafnium oxide, and all other steps are the same as those in Example 1.

[0146] Comparative Example 4

[0147] The difference between the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue and Example 1 is that the fluorocrown optical glass powder in the material of the glass layer is replaced by ordinary white glass, and all other steps are the same as those in Example 1.

[0148] Comparative Example 5

[0149] The difference between the rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue and Example 1 is that the rare earth oxide layer uses a mixture of cerium-lanthanum oxide and hafnium oxide, and its specific preparation method is as follows:

[0150] 1) Dissolve a small amount of dodecylphenol polyoxyethylene ether in deionized water to prepare a 10 g / L solution, and take out 500 mL of the solution.

[0151] 2) Weigh cerium chloride and lanthanum chloride in amounts of 0.273 mol and 0.027 mol respectively, and add them to the solution in step 1).

[0152] 3) Pour the solution described in step 2) into a flask, heat it to 80 °C, and add 300 mL of ammonia water dropwise to it, continue the reaction for 5 h, and then carry out sedimentation at room temperature for 12 h.

[0153] 4) The precipitate was subjected to suction filtration, washing, and drying, and then calcined at 900 °C for 2 h to obtain lanthanum cerium oxide.

[0154] 5) The obtained lanthanum cerium oxide was mixed with 30 g of hafnium oxide at high speed to obtain the raw material for the rare earth oxide layer.

[0155] All other steps were the same as those in Example 1.

[0156] The performance parameters of a rare earth-based one-dimensional photonic crystal coating prepared from the optical glass waste residue provided by the present invention are shown in Table 1. The heat dissipation test device for the coating is shown in Figure 1 and Figure 2 , and the test process was carried out under a simulated light source. As Figure 1 shown, the rare earth-based one-dimensional photonic crystal heat dissipation coating 3 is composed of a stainless steel substrate 4 and a rare earth oxide layer and a glass layer provided on the surface of the stainless steel substrate 4. The rare earth-based one-dimensional photonic crystal heat dissipation coating 3 is fixed on the surface of the PTC heating sheet 2 with thermal conductive silica gel. The mobile power supply 1 is electrically connected to the PTC heating sheet 2 through a wire 5. A voltage of 12 V is applied to the PTC heating sheet 2 by the mobile power supply 1, so that the PTC heating sheet 2 gradually heats up. At the same time, relying on the high reflection and high reflectivity performance of the coating, the heat is continuously dissipated into the surrounding environment, and the absorption of heat from the light source is reduced. During the test, the PTC heating sheet 2 was used to simulate the heat generation during the operation of a 5G base station, and the simulated light source was used to replace outdoor sunlight. A patch-type thermocouple 6 was arranged on the surface of the PTC heating sheet 2 to measure the temperature on the surface of the PTC heating sheet 2 in real time (as Figure 2 shown). The heat dissipation effect is shown in Figure 4 .

[0157] Table 1

[0158]

[0159] Table 1 shows the reflectivity and emissivity data of the examples and the comparative examples. The reflectivity reflects the reflection performance of the coating to sunlight. The higher the reflectivity, the less heat is absorbed from sunlight, and the temperature rise can be reduced. The emissivity reflects the heat emission performance of the coating in the range of 8-13 μm. High emissivity means that the coating can dissipate more heat into the environment. Examples 1 to 4 all have high reflection performance (above 95%) and emission performance (above 94%), and theoretically can have good heat dissipation.

[0160] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue, characterized in that: The rare earth-based one-dimensional photonic crystal heat dissipation coating is formed by alternately arranging glass layers and rare earth oxide layers on a substrate; the rare earth oxide layer is formed by depositing a hafnium oxide-lanthanum cerium oxide heterojunction on the substrate or the glass layer by a magnetron sputtering process, and the preparation method of the hafnium oxide-lanthanum cerium oxide heterojunction includes the following steps: 1) Add hafnium oxide powder to the lanthanum cerium chloride solution, mix evenly, and then centrifuge the solution to separate out the solid powder; 2) Add the solid powder obtained in step 1) to the surfactant solution and mix evenly to obtain a mixed solution; 3) Heat the mixed solution obtained in step 2) to 50-80 °C, and dropwise add an alkali solution thereto, continuously react for 2-5 h, and then carry out sedimentation at room temperature for 6-12 h; 4) Filter, wash, and dry the precipitate obtained in step 3), and calcine it at 600-900 °C for 2-6 h to obtain a hafnium oxide-lanthanum cerium oxide heterojunction.

2. The rare earth-based one-dimensional photonic crystal heat dissipation coating made from the optical glass waste residue according to claim 1, wherein: The molar concentration of the lanthanum cerium chloride solution is 0.05-0.1 mol / L, and is obtained by dissolving cerium chloride and lanthanum chloride with a molar ratio of (10-20):1 in water.

3. The rare earth-based one-dimensional photonic crystal heat dissipation coating made from the optical glass waste residue according to claim 2, wherein: The addition amount of the hafnium oxide powder is 5-10 g per liter of the lanthanum cerium chloride solution.

4. The rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residue according to claim 1, wherein: The concentration of the surfactant solution is 1-10 g / L.

5. The rare earth-based one-dimensional photonic crystal heat dissipation coating made from the optical glass waste residue according to claim 1, characterized in that: The mass ratio of the surfactant to the solid powder is (1-10):

60.

6. The rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residues according to claim 1, wherein: The surfactant is one or a mixture of several of dodecylphenol polyoxyethylene ether, polyoxyethylene sorbitan monolaurate, and glycerol monostearate.

7. The rare earth-based one-dimensional photonic crystal heat dissipation coating made from the optical glass waste residue according to claim 1, wherein: The glass layer is formed by plating a glass frit on the rare earth oxide layer by a vacuum evaporation process, and the glass frit is prepared from fluorocrown optical glass powder and fluoride with a mass ratio of (70-82):(19-32); preferably, the fluoride includes one or a mixture of several of erbium fluoride, zinc fluoride, calcium fluoride, sodium fluoride, lanthanum fluoride, aluminum fluoride, and magnesium fluoride; preferably, the fluoride includes erbium fluoride, zinc fluoride, calcium fluoride, sodium fluoride, lanthanum fluoride, aluminum fluoride, and magnesium fluoride with a mass ratio of (10-15):(7-12):(2-5).

8. The rare earth-based one-dimensional photonic crystal heat dissipation coating made from optical glass waste residues according to claim 1, wherein: The preparation method of the glass frit includes the following steps: S1: Crush and grind the fluorocrown optical glass to obtain fluorocrown optical glass powder; S2: Mix the fluorocrown optical glass powder and the fluoride to obtain a mixed powder; S3: Heat the mixed powder to 1450-1600 °C to form a glass melt, continue heating and start stirring, and continue for 2-5 h; S4: Pour the glass melt into a mold for casting, and anneal it at 350-600 °C for 2-4 h to obtain a glass frit.

9. Application of the rare earth-based one-dimensional photonic crystal heat dissipation coating according to any one of claims 1-7 in heat dissipation of a base station box.

10. The application according to claim 9, characterized in that: The thickness of the rare earth oxide layer in the rare earth-based one-dimensional photonic crystal heat dissipation coating is 20-45 nm, and the thickness of the glass layer is 50-90 nm; Preferably, the rare earth oxide layer is first deposited on the surface of the base station box, and then the glass layer is deposited, taking this as a cycle, and the cycle is repeated to continue deposition, and the number of deposition cycles is 2-5.

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