KR101238417B1 - Method of coating a surface using nanoporous materials for controlling heat transfer, coating layer using the same, substrate having the coating layer, and heat control element having the coating layer - Google Patents

Abstract

The present invention relates to a surface treatment method for heat transfer control, and more particularly, to a method for coating a nanoporous body on the surface of a substrate for heat transfer control.

According to the present invention, preparing a nanoporous body; Functionalizing an organic functional group on a surface of the nanoporous body; Functionalizing an organic functional group on the surface of the substrate to be coated with the nanoporous body; Covalently bonding the nanoporous body to the surface of the substrate; Provided is a nanoporous coating method for heat transfer control comprising a.

Nanoporous coating method for heat transfer control according to the present invention has the following effects. First, the coating layer according to the present invention has a lot of nucleation sites (active nucleation site), can trap the gas in the pores, the contact area of the liquid and gas is large, the capillary pressure is high, wetting (wetting) well, bubbles Are combined well with each other and the bubble detachment frequency is high. Thus, the temperature at which boiling begins is lowered and the critical heat flux and heat transfer coefficient are high. Second, the coating layer according to the present invention can be made of a thin film of a few micro or less can be used to cool the substrate generating a large amount of heat in a small area, such as computer CPU, LED and mobile phone. In addition, the coating layer can solve the problem of increasing the thermal resistance. Third, because the nanoporous body has a large surface area, the coating layer of the present invention is excellent in hygroscopicity and water repellency. Fourth, the coating layer according to the present invention is strongly bonded to the surface so as not to fall even after a vibration for a long time has a high long-term stability.

Nanostructures, Zeolites, Mesoporous Materials, Porous Organic-Inorganic Hybrids, Functionalization

Description

TECHNICAL OF COATING A SURFACE USING NANOPOROUS MATERIALS FOR CONTROLLING HEAT TRANSFER, COATING LAYER USING THE SAME, SUBSTRATE HAVING THE COATING LAYER, AND HEAT CONTROL ELEMENT HAVING THE COATING LAYER}

The present invention relates to a method of heat transfer control, and more particularly, to a method of coating a nanoporous body on the surface of a substrate for heat transfer control.

Recently, as the degree of integration of semiconductors increases, speed increases, and complex functions are added, heat flux per unit area generated in semiconductor chips continues to increase. Accordingly, as the temperature of the chip increases, the function and the life of the product decrease, and various cooling methods have been developed to solve this problem.

When there is a limit in air cooling method, liquid cooling method is used. Among liquid cooling methods, phase change cooling using boiling, evaporation, condensation, etc. of liquid is used. Phase change cooling method has been studied a lot. An example of phase-change cooling is the thermosyphon, whose performance is limited by boiling and condensing performance.

By improving the surface of the heating element to improve boiling performance, (1) increasing the bubbling point, (2) increasing the boiling surface area, and (3) allowing the liquid to rewet to the surface, 1) the initiating nucleate boiling temperature decreases, (2) the temperature difference between the liquid and the surface decreases, and the heat transfer coefficient (h) increases, and (3) the critical heat flux (CHF) increases, It may be possible to use.

    For example, Nakayama (W.Nakayama, Enhancement of heat trasfer, in: Proceedings of the 7th Int. Heat Transfer Conference, vol 1, 1982, pp.223-) 240), Tome (JR Thome, Enhanced Boiling Heat Transfer, Hemisphere, NY, 1990), Kakac (S. Kakac, B. Kikis, FA Kulacki, F. Arinic, Convective Heat and Mass Transfer, Kluwer Academic Publishers 1991, pp. 1007-1030), Webb (RL Webb, Principles of Enhanced Heat Transfer, John Wiley & Sons, Inc., NY, 1994). However, these methods (plasma spraying, electrochemical plating, mechanical forming) have the disadvantages that the production cost is expensive and the surface structure that can be used is limited.

Recently, various structures are made by using MEMS (Micro Electro Mechanical System) technology, which can be classified into protruding structure, cavity structure, and porous structure.

First of all, Honda (Honda, H., Takamatsu, H., Wei, JJ, 2002, Enhanced Boiling of FC-72 on Silicon Chips With Micro-Pin-Fins and Submicron-Scale Roughness, Journal of Heat) Transfer, 124, pp. 383-390.) Dry etch silicon to make pin fins (50x50x60um, width; thickness; height) at 100um intervals, and SiO ₂ sputtering As a result of boiling experiments with wet etching, the surface roughness of about 30nm was created on the surface, and the critical heat flux improved about twice as much as that of general silicon. Through this experiment, it was confirmed that not only the micro-scale fin structure but also the nano-scale surface shape greatly influence the boiling characteristics.

Mitrovic (Mitrovic, J., Hartmann, F., 2004, A New Microstructure for Pool Boiling, Superlattices and Microstructures, 35, pp. 617-628) has a diameter of 1 µm to 25 µm through electrocoating and etching processes. Boiling experiments were made of cylindrical copper fins with a height of 10 µm to 20 µm in height, and the heat transfer coefficient improved approximately twice as much as without the fins.

Mudawar (Sebastine Ujereh, Timothy Fisher, Issam Mudawar, 2007, Effects of carbon nanotube arrays on nucleate pool boiling, International Journal of Heat and Mass Transfer, 50, pp. 40234038) has carbon nanotubes 50 nm in diameter and 20-30 μm in length. The carbon nanotubes were grown on the surface of the silicon and the critical heat flux was improved by about 45%.

Yu (Chih Kuang Yu, Ding Chong Lu, and Tsung Chieh Cheng, 2006, Pool boiling heat transfer on artificial-cavity surfaces in dielectric fluid FC-72 , J. Micromech.Microeng. 16, pp.2092-2099) is a critical heat flux obtained by comparing the critical heat fluxes through different intervals through cylindrical cavity with diameter of 50um ~ 200um and depth of 110um / 299um. Up to 2.5 times improvement was found.

Vemuri and Kim (S.Vemuri, K.Kim, 2005, Pool boiling of saturated FC-72 on nano-porous surface, International Communications in Heat and Mass Transfer, 32, pp. 27-31) are known as Aluminum Anodized Oxide (AOA). By creating a cavity with a diameter of 50-250nm and a depth of 70um, the temperature at which boiling starts can be reduced by 30%.

Porous layer coating is also used as a way to promote boiling. You (You SM, Simon TW, and Bar-Cohen A., 1991, A technique for enhancing boiling heat transfer with application to cooling of electronic equipment, IEEE Transactions of the CPMT, 15 (5), pp.90-96) Through particle layering, 0.3 ~ 3um of alumina (Al ₂ O ₃ ) particles are sprayed and combined with van der waals molecular attraction force to reduce the temperature at which boiling starts by 50%, and the critical heat flux Increased by 32%.

O'Connor and You (O'Connor JP and You SM, 1995, A painting technique to enhance pool boiling heat transfer in saturated FC-72, ASME Journal of Heat Transfer, 117 (2), pp.387-393). Based on the method, boiling facilitating paints containing 3-10 μm of silver flakes were made, reducing the temperature at which boiling started by 80% and increasing the critical heat flux by 109%.

O'Cornnor et al. (O'Connor JP, You SM, and Price DC, 1995, Thermal management of high power microelectronics via immersion cooling, IEEE Transactions of the CPMT, 18 (3), pp.656-663). Similar results were obtained with a dielectric paint made of diamond particles of ~ 12um.

Chang and You (Chang JY and You SM, 1996, Heater orientation effects on pool boiling of micro-porous-enhanced surfaces in saturated FC-72, ASME Journal of Heat Transfer, 118 (4), pp.937-943) By using ~ 50um copper particles and 1 ~ 20um aluminum particles, the temperature at which boiling starts can be reduced by 80 ~ 90%.

Porous graphite was also used, Mohamed (Mohamed S. El-Genk, Jack L. Parker, 2004, Enhanced boiling of HFE-7100 dielectric liquid on porous graphite, Energy Conversion and Management, 46, pp. 2455- 2481) achieved a 60% improvement in critical heat flux over ordinary copper by using porous graphite with pores of tens to hundreds of um.

As a theoretical and experimental approach to porous structure, Kaviany (Scott G. Liter and Massoud Kaviany, 2001, Pool-boiling CHF enhancement by modulated porous-layer coating: theory and experiment, International Journal of Heat and Mass Transfer, 44, pp. 4287-4311) was used to make a porous structure having a uniform thickness and a porous structure with a periodically varying thickness using 200um size copper particles. As a result, it is theoretically and experimentally able to prove that the critical heat flux of the porous structure with uniform thickness is improved by 2 times, but the controlled porous layer coating with the periodically changing thickness is improved by 3 times or more. there was. This controlled porous structure improves critical heat flux because it effectively regulates the flow path between liquid and gas to minimize the friction between liquid and gas. It is said to improve heat flux further.

However, all of the above-mentioned methods are tens of microns or more thick, too thick for use inside microchannels, resulting in thermal and flow resistance, and require processes that require high temperatures. Difficult to use for cooling the device.

The present invention has been made in order to solve this problem, by coating the nanoporous body on the surface of the substrate that needs heat exchange using an organic functional group, phase change heat transfer such as boiling, evaporation, condensation, etc. An object of the present invention is to provide a nanoporous coating method and a thermal control material system using the same.

According to the present invention, preparing a nanoporous body; Functionalizing an organic functional group on a surface of the nanoporous body; Functionalizing an organic functional group on the surface of the substrate to be coated with the nanoporous body; Covalently bonding the nanoporous body to the surface of the substrate; Provided is a nanoporous coating method for heat transfer control comprising a.

In addition, a coating layer formed by the coating method is provided.

Also provided is a substrate, a thermal control element, and a system comprising a coating layer formed by the coating method.

 Nanoporous coating method for heat transfer control according to the present invention has the following effects.

First, the coating layer according to the present invention has a lot of nucleation sites (active nucleation site), can trap the gas in the pores, the contact area of the liquid and gas is large, the capillary pressure is high, wetting (wetting) well, bubbles Are combined well with each other and the bubble detachment frequency is high. Thus, the temperature at which boiling begins is lowered and the critical heat flux and heat transfer coefficient are high.

Second, the coating layer according to the present invention can be made of a thin film of a few microns or less can be used in a system such as a heat pipe for cooling a substrate generating a large amount of heat in a small area, such as computer CPU, LED and mobile phone. In addition, the coating layer can solve the problem of increasing the thermal resistance.

Third, because the nanoporous body has a large surface area, the coating layer of the present invention is excellent in hygroscopicity and water repellency.

Fourth, the coating layer according to the present invention is strongly bonded to the surface so as not to fall even after a vibration for a long time has a high long-term stability.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention comprises the steps of preparing a nanoporous body, functionalizing the organic functional group on the surface of the nanoporous body, functionalizing the organic functional group on the surface of the substrate to be coated with the nanoporous body, the nanoporous body of the substrate Nanoporous coating method for heat transfer control comprising covalently bonding to the surface (see FIG. 1).

In the present invention, the nanoporous body refers to a material having pores in nano units, a zeolite having pores of 2 nm or less, a mesoporous body having pores of 2-100 nm, and a porous organic-inorganic hybrid having pores of 10 nm or less. {Metal organic framework (MOF), metal organic polyhedra (MOP), Zeolitic imidazolate framework (ZIF) and the like can be used. The porous organic-inorganic hybrid refers to a porous organic-inorganic high molecular compound formed by combining a central metal ion with an organic ligand.

Preparation of Porous Organic-Inorganic Hybrids

In the present invention, the porous organic-inorganic hybrid is not particularly limited, but may be prepared through a method of heating a reactant mixture containing a metal source, an organic material that can act as a ligand, and a solvent. The heating is not limited to the method, and may be selected and used in an electric heating method, a micro irradiation or a method of irradiating sound waves, but in order to prepare a nano-sized porous organic-inorganic hybrid crystals, the electric heating method or The method using a microwave is more preferable.

The metal material, which is one member of the porous organic-inorganic hybrid, can be any metal. In particular, transition metals which make coordination compounds well are preferred. Among the transition metals, chromium, vanadium, iron, nickel, cobalt, copper, titanium, zinc, vanadium, molybdenum, niobium, zirconium, manganese, and the like are more preferable. In addition to transition metals, rare earth metals such as lanthanum are possible, as well as typical elements that make up coordination compounds. Among the typical elements, calcium, magnesium, lithium, tin, aluminum and silicon are preferable, and among lanthanum metals, cerium and lanthanum are preferable. As the metal source, any compound of the metal may be used as well as the metal itself.

Organics, another member of the porous organic-inorganic hybrid, are also called linkers and can be any organic having coordinating functional groups. Coordinating functional groups are carboxylic acid groups, carboxylic acid anion groups, amino groups (-NH). ₂ ), imino group, amide group (-CONH ₂ ), sulfonic acid group (-SO ₃ H), sulfonic acid anion group (-SO _3- ), methanedithioic acid group (-CS ₂ H), methanedithioic acid anion group ( -CS _2- ), pyridine group or pyrazine group and the like can be exemplified. In addition, the primary organic ligand participating in coordination bonds with metal ions may be secondaryly substituted with an amino group (-NH ₂ ), an imino group, an amide group (-CONH ₂ ), a sulfonic acid group (-SO ₃ H), or the like. . For example, an amino group (-NH ₂ ), an imino group, an amide group (-CONH ₂ ), and a sulfonic acid at any one or more positions in a 2,3,5 carbon position of a benzene ring of 1,4-BDC (Benzendicarboxylic acid) Group (-SO ₃ H) and the like may be further substituted. In order to induce a more stable organic-inorganic hybrid, organic materials having two or more coordinating sites, for example, bidentate or tridentate, are advantageous. As organic materials, if there is a position to coordinate, neutral organic materials such as bipyridine and pyrazine, anionic organic materials such as terephthalate, naphthalenedicarboxylate, benzenetricarboxylate, glutarate, anion of carboxylic acid which can be exemplified by succinate, etc. Of course, cationic materials are also possible. In the case of the carboxylic acid anion, for example, anion of a linear carboxylic acid such as formate as well as an anion having a non-aromatic ring such as cyclohexyl dicarbonate can be used, in addition to having an aromatic ring such as terephthalate. Organics with coordinating sites, as well as potentially coordinating sites, can also be changed to coordinate under reaction conditions. That is, even if an organic acid such as terephthalic acid is used, it can be combined with a metal component with terephthalate after the reaction. Representative examples of organic materials that can be used include benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalenetricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid and hexanedioo Organic acids selected from Ixic acid, heptanedioic acid, or cyclohexyldicarboxylic acid and their anions, pyrazine, bipyridine and the like.

It is also possible to mix and use one or more organics.

In addition to the metal source and organic matter, an appropriate solvent is required for the synthesis of the organic-inorganic hybrid, and alcohols such as water, methanol, ethanol and propanol, ketones such as acetone and methyl ethyl ketone, and hydrocarbons such as hexane, heptane and octane Substances may be used, or two or more solvents may be mixed and water is most suitable.

Representative examples of porous organic-inorganic hybrids include chromium terephthalate, titanium terephthalate, zirconium terephthalate, chromium tricarboxylate, vanadium terephthalate, vanadium tricarboxylate, iron terephthalate, iron tricarboxylate, and aluminum terephthalate. Phthalates, aluminum tricarboxylates, and zinc imidazonates, among which chromium terephthalate, aluminum tricarboxylate, iron tricarboxylate, zirconium terephthalate, and zinc imidazonium are particularly excellent in hydrothermal stability. Rate is preferred.

<Zeolite>

In the present invention, the zeolite may have at least one inorganic material such as Si, Al, Ga, P, or the like, and may have an organic group such as -CH _2- , -C ₂ H _4- , but is not particularly limited, but MFI, It is suitable to have BEA, FER, AFI, CHA, FAU, LTA structure.

<Meso taxation body>

In the present invention, the mesoporous body may have at least one inorganic material such as Si, Al, Ga, P, or the like, or may have an organic group such as -CH _2- , -C ₂ H _4- , -C ₆ H _4-, and the like. Although not particularly limited, it is suitable to use MCM-based, SBA-based, MSU-based, KIT-based, and MCF (mesoporous cellular foam) series. In addition, a carbon replica of mesoporous body can also be used.

<Functionalizing the surface of the nanoporous body and the surface of the substrate to be coated>

As the organic functional precursor that can functionalize the surface of the nanoporous body and the surface of the substrate to be coated with the nanoporous body, one or more selected from the compounds represented by Chemical Formulas 1 to 6 may be used, but not limited thereto.

Si (OR) _4-x R _x (0.1≤x≤3)

Si (OR) _{4- (x + y)} R _x Z _y (0.1≤x + y≤3.9)

Si (OR) _{4- x} R _x Si (0.1≤x≤3)

Si (OR) _{4- (x + y)} R _x Z _y Si (0.1≤x + y≤3.9)

(Wherein Z is a halogen element, R is an alkyl group, alkenyl group, alkynyl group, vinyl group, amino group, cyano group, and mercapto group (-SH) of C ₁ to C ₂₀ substituted or unsubstituted with halogen element) A substituent selected from the group consisting of 3 to 3 carbon atoms are suitable.)

H ₂ NM-R1

HS-M-R2

Wherein M is C ₁ to C ₂₀ alkylene, aralkylene group, or R 1 to R 2 are independently a halogen element, vinyl group (-C = CH), amino group (-NH ₂₎ ), Imino group (-NHR), mercapto group (-SH), hydroxy group (-OH) or carboxylic acid group (-COOH), sulfonic acid group (-SO ₃ H), alkoxy group (-OR), phosphoric group (- Organic substance substituted or unsubstituted with one or more selected from PO (OH) ₂ ).

It is more preferable to proceed with the pretreatment step of removing the water or the solvent component bonded to the unsaturated metal site before the surface functionalization of the nanoporous body. The pretreatment may use any method as long as it can remove water or solvent components without causing deformation of the nanoporous body, and more specifically, it is preferable to heat at least 100 hours at a temperature of 100 ° C. or higher, and 150 ° C. or higher under reduced pressure. More preferably heating at least 4 hours at temperature.

Embodiments of the surface functionalization method of the nanoporous body according to the present invention include (a) removing an organic solvent such as water or an alcohol coordinated at an unsaturated metal site on the surface of the nanoporous body, (b) organosilane or Adding an organic silane compound solution prepared by dissolving an organic amine compound in an organic solvent, such as toluene, to perform a reflux reaction by adding the pretreated nanoporous material, and (c) nano-functionalized organic silane or organic amine compound. Purifying the pore may be included.

In addition, when surface-functionalizing a nanoporous body using highly volatile organosilane and an organic amine compound, the organic silane compound in a gaseous state is brought into contact with the nanoporous body in the same manner as in the chemical vapor deposition method to form an unsaturated metal site of the nanoporous body. May optionally be bound to

<Step of covalently bonding the nanoporous body to the surface of the substrate>

Methods for immobilizing the functionalized nanoporous body on the functionalized surface of the substrate by covalent bonding include a method in which the functionalized nanoporous body and the substrate are put in a solvent and stirred while applying ultrasonic waves and electromagnetic waves and refluxing. In addition, there are methods such as dip coating and infiltration.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited only to these Examples.

Example 1

Preparation of Porous Organic-Inorganic Hybrids (Cu-BTC)

Porous organic-inorganic hybrid copperbenzenetricarboxylates having a pore size of 1 nm or more were prepared by previously reported methods (Science, 283, 1148, 1999). In the preparation method, Cu (NO ₃ ) ₃ 9H ₂ O and 1,3,5-benzenetricarboxylic acid (BTCA) are added to a Teflon reactor, distilled water and ethanol are added, and the final molar ratio of the reactant is Cu: BTCA: H 2 O: Ethanol = 1: 0.5: 184: 103. The reaction mixture was maintained in an oven at 120 ° C. for 8 hours to react, cooled to room temperature, centrifuged, washed with distilled water, and dried to obtain an organic-inorganic hybrid copperbenzene tricarboxylate. X-ray diffraction analysis of the solid confirmed the same structure as that reported in the literature (Science, 283, 1148, 1999).

<Organic-inorganic nanoporous body functionalized with amino group>

1 g of porous organic-inorganic hybrid copperbenzenetricarboxylate is pretreated in a 200 ° C. vacuum oven for 12 hours to dehydrate water coordinated to unsaturated metal sites. 2 ml of ethylenediamine (Ethylenediamine, ED) was distilled off and adsorbed to dehydrated copper benzenetricarboxylate to prepare a porous organic-inorganic hybrid having an amino functional group coordinated at an unsaturated metal site (NH2-CuBTC). The X-ray diffraction patterns before and after supporting ethylenediamine showed no change in the structure of the porous organic-inorganic hybrid. In addition, using infrared spectroscopy ethylene diamine amino group (-NH ₂₎ and an ethyl group was confirmed that there is at 2800-3000cm ^-1 and ^{_{3200-3400 cm -1 (-CH 2 CH 2}} ). This means that ethylenediamine is coordinated.

Since the -OH group (3550-3650cm ^-1 ) of the porous organic-inorganic hybrid was hardly changed before and after the coordination of ethylenediamine, it can be seen that the ethylenediamine reacted selectively to the unsaturated metal site in the organic-inorganic hybrid. have.

<Preparation of Chlorine Functionalized Silicon Wafer>

A 2cm * 2cm silicon wafer is fixed on a Teflon holder and placed in a beaker containing 50ml toluene and filled with nitrogen. 1 ml of 3-chloropropyltriethoxysilane was added to the beaker using 3 ml of syringe and refluxed at 110 ° C. for 24 hours. After the reflux process, cool to room temperature and store the silicon wafer in toluene solution.

<Manufacturing of Silicon Wafer Coated with NH2-CuBTC>

A chlorinated functionalized 2cm * 2cm silicone wafer is fixed on a Teflon holder and placed in a beaker containing 50ml toluene. 0.1 g of NH2-CuBTC dried at 150 ° C. in a vacuum oven for 12 hours was placed in a beaker containing the silicon wafer and filled with nitrogen, and refluxed at 110 ° C. for 12 hours. As a result of confirming the coating degree of the prepared Si-NH-CuBTC electron microscope, it was confirmed that the coating uniformly.

[Example 2]

Preparation of Porous Organic-Inorganic Hybrids (MCM-48)

Porous organic-inorganic hybrid MCM-48 (surface area 1050 m ² / g) having a pore size of 1 nm or more was prepared by the previously reported method.

<Production of MCM-48 Functionalized with Amino Groups>

1 g of MCM-48 is dried in a vacuum oven at 200 ° C. for 12 hours. The dehydrated MCM-48 is placed in 50 ml toluene and charged with nitrogen. The solution was added with 1.87 ml 3-aminopropyltriethoxysilane using 3 ml of syringe and refluxed at 110 ° C. for 12 hours. After reflux, cool to room temperature and filter with paper filter. Wash thoroughly with water and ethanol.

<Preparation of Chlorine Functionalized Silicon Wafer>

A 2cm * 2cm silicon wafer is fixed on a Teflon holder and placed in a beaker containing 50ml toluene and filled with nitrogen. 1 ml of 3-chloropropyltriethoxysilane was added to the beaker using 3 ml of syringe and refluxed at 110 ° C. for 24 hours. After the reflux process, cool to room temperature and store the silicon wafer in toluene solution.

<Manufacture of Silicon Wafers coated with NH ₂ -MCM-48>

MCM-48 is coated on a silicon wafer in a similar manner to Example 1. A chlorinated functionalized 2cm * 2cm silicone wafer is fixed on a Teflon holder and placed in a beaker containing 50ml toluene. 0.1 g of NH ₂ -MCM-48 dried at 150 ° C. in a vacuum oven for 12 hours was placed in a beaker containing the silicon wafer, filled with nitrogen, and refluxed at 110 ° C. for 12 hours to coat NH ₂ -MCM-48 on a silicon substrate. It was. XRD and SEM analysis confirmed that the NH ₂ -MCM-48 is coated.

[Example 3]

NH ₂ -MIL-101 functionalized with an amino group was prepared by using MIL-101 as a porous organic-inorganic hybrid in Example 1 instead of copperbenzenetricarboxylate. As a result of analyzing the XRD pattern before and after the coating, it was confirmed that the crystal structure is the same as that reported in the existing results (Science 309, 2040, 2005) (see FIG. 2). Infrared spectroscopy confirmed that the amine was bound to MIL-101. The NH ₂ -MIL-101 was bonded to a chlorine-functional silicon wafer by the same method as in Example 1 (Si-NH-MIL-101). SEM analysis showed that NH ₂ -MIL-101 was well bonded to the Si substrate (see FIG. 3).

Example 4

NH ₂ -MOF-5 functionalized with amino groups was prepared in the same manner using MOF-5 instead of copperbenzenetricarboxylate as the porous organic-inorganic hybrid in Example 1. Infrared spectroscopy confirmed that the amine was bound to MOF-5. NH ₂ -MOF-5 was bonded to a chlorine-functional silicon wafer in the same manner as in Example 1 (Si-NH-MOF-5).

[Example 5]

NH ₂ -Cr-MOF having an amino group functionalized by the same method was prepared using chromium terephthalate instead of copperbenzenetricarboxylate as the porous organic-inorganic hybrid in Example 1. Analysis of the XRD pattern before and after coating confirmed that the crystal structure is the same as that reported in the previous studies (Science 309, 2040, 2005). Infrared spectroscopy confirmed that the amine was bound to chromium terephthalate. The NH ₂ -Cr-MOF was bonded to a chlorine-functional silicon wafer by the same method as in Example 1 (Si-NH-Cr-MOF). SEM analysis showed that NH ₂ -Cr-MOF was well bonded to the Si substrate.

[Example 6]

NH ₂ -ZIF-8 functionalized with an amino group was prepared in the same manner using ZIF-8 instead of copperbenzenetricarboxylate as the porous organic-inorganic hybrid in Example 1. Infrared spectroscopy confirmed that the amine was bound to ZIF-8. NH ₂ -ZIF-8 was bonded to a chlorine-functional silicon wafer in the same manner as in Example 1 (Si-NH-ZIF-8).

<Measurement of critical heat flux>

Boiling performance of the nanoporous coated silicon wafer and the uncoated silicon wafer prepared in Example 3 were evaluated using a Pool Boiling Experiment apparatus (see FIG. 4). A silicon wafer with a 10 mm x 10 mm heater is attached to a 30 mm x 30 mm printed circuit board, which is then placed on a Teflon block with cavities and fixed by vacuum. This allows the bottom surface of the sample to be insulated when it is heated. 3M PF-5060 with boiling point of 56 ^o C was used. The refrigerant was placed in a double jacket beaker and maintained at a constant temperature (56 ^o C). The boiled and evaporated refrigerant was condensed through the condenser and returned. The sample mounted on the Teflon block is heated by an external DC power supply in a state of being immersed in the refrigerant, and the temperature of the sample and the refrigerant is measured by using a sensor. Boiling test results show that the nanofluidic coating on the silicon wafer with the Reflux method has a critical heat flux of 20W, which is nearly twice the 11W of the sample without the nanoporous body. It could be confirmed (see FIG. 5).

1 is a conceptual diagram related to a nanoporous coating method according to the present invention,

Figure 2 shows the XRD pattern of the surface functionalized porous organic-inorganic hybrid (a) MIL-101, (b) shows the XRD pattern of DE-MIL-101.

3 is an electron micrograph of the surface functionalized porous organic-inorganic hybrid prepared in Example 3,

4 is a schematic diagram of an experimental apparatus for measuring the critical heat flux,

Figure 5 shows the results of the measurement of the critical heat flux (a) is a silicon wafer coated with the nanoporous body of Example 3, (b) is a view showing the results of the measurement of the critical heat flux of the uncoated silicon wafer.

Claims (16)

In the coating method for heat transfer control, Functionalizing an organic functional group on a surface of a nanoporous body having nano pores; Functionalizing an organic functional group on the surface of the substrate to be coated with the nanoporous body; Covalently bonding the nanoporous body to the surface of the substrate; The nanoporous body nanoporous coating method for heat transfer control, characterized in that the porous organic-inorganic hybrid. delete delete delete delete delete The method of claim 1, The porous organic-inorganic hybrid is a nanoporous body coating method for heat transfer control, characterized in that the crystalline polymer compound of the pore structure formed by combining the central metal ion with the organic ligand. The method of claim 7, wherein The core metal of the porous organic-inorganic hybrid (MOF) is chromium, vanadium, iron, nickel, cobalt, copper, titanium, zirconium, niobium, molybdenum, zinc, manganese, calcium, magnesium, lithium, aluminum, Nanoporous coating method for heat transfer control, characterized in that it comprises at least one metal selected from the group consisting of silicon, cerium and lanthanum. The method of claim 1, Functionalizing the organic functional group on the surface of the nanoporous body and functionalizing the organic functional group on the surface of the substrate to be coated with the nanoporous body, The nanoporous body coating method comprising the step of reacting by mixing the nanoporous material or the substrate, the organic functional precursor and the solvent. 10. The method of claim 9, The nanoporous body coating method for heat transfer control, characterized in that at least one selected from the compounds represented by the following formulas 1 to 6 as the organic functional group precursor. [Formula 1] Si (OR) _4-x R _x (0.1≤x≤3) [Formula 2] Si (OR) _{4- (x + y)} R _x Z _y (0.1≤x + y≤3.9) (3) Si (OR) _4-x R _x Si (0.1≤x≤3) [Formula 4] Si (OR) _{4- (x + y)} R _x Z _y Si (0.1≤x + y≤3.9) (Wherein Z is a halogen element, R is an alkyl group, alkenyl group, alkynyl group, vinyl group, amino group, cyano group, and mercapto group (-SH) of C ₁ to C ₂₀ substituted or unsubstituted with halogen element) A substituent selected from the group consisting of groups) [Chemical Formula 5] H ₂ NM-R1 [Formula 6] HS-M-R2 Wherein M is C ₁ to C ₂₀ alkylene, aralkylene group, or R 1 to R 2 are independently a halogen element, vinyl group (-C = CH), amino group (-NH ₂₎ ), Imino group (-NHR), mercapto group (-SH), hydroxy group (-OH) or carboxylic acid group (-COOH), sulfonic acid group (-SO ₃ H), alkoxy group (-OR), phosphoric group (- Organic substance substituted or unsubstituted with one or more selected from PO (OH) ₂ ). The method of claim 1, Covalently bonding the nanoporous body to the surface of the substrate is nanoporous coating for heat transfer control, characterized in that using a method selected from ultrasonic, electromagnetic waves, dip coating, infiltration or reflux method Way. The method of claim 1, In the step of functionalizing the organic functional group on the surface of the substrate to be coated with the nanoporous body, The substrate is a nanoporous coating method for heat transfer control, characterized in that the heat generating electronic components. The coating layer formed by the coating method of any one of Claims 1-7. A substrate comprising a coating layer formed by the coating method of any one of claims 1 and 7-12. 13. A thermal control element comprising a coating layer formed by the coating method of any one of claims 1 and 7. delete

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