Porous oil-injected anti-icing material supported by a metal skeleton, its preparation method and application

Abstract

The present invention discloses a porous oil-injected anti-icing material supported by a metal skeleton, its preparation method and application, belonging to the technical field of anti-icing surface engineering. The porous oil-injected anti-icing material supported by a metal skeleton comprises a metal skeleton substrate with a porous structure, and the interior of the substrate is filled with a polymer composed of polydimethylsiloxane (PDMS), an oil-based injection liquid and an aerogel substance. The percentage of the oil-based injection liquid in the total mass of the polymer is 17-22%, and the percentage of the aerogel substance in the total mass of the polymer is 1-6%; the surface of the substrate is coated with a polymer coating. The present invention uses a porous metal skeleton as the substrate, makes full use of the advantage of the large specific surface area of the aerogel powder to absorb the phase change oil liquid, combines with the use of the polymer material PDMS, designs and regulates its structure, and utilizes the PDMS polymer coating surrounding the porous metal skeleton support and the solid state of the phase change liquid in the icing temperature range to improve its mechanical durability and anti-icing stability.

Description

Technical Field

[0001] The present invention relates to a porous oil-injected anti-icing material supported by a metal skeleton, its preparation method and application, belonging to the technical field of anti-icing surface engineering. Background Art

[0002] Uncontrolled icing behavior on the surfaces of engineering applications such as transportation, infrastructure, and energy may cause serious socio-economic impacts or even disasters. Therefore, it is of great significance to study the icing and ice accretion problems under these extreme working conditions. Currently, the main solution is to effectively reduce the ice and snow disasters in engineering applications by using anti-icing coatings. As a currently popular anti-icing surface for research, it is the liquid-injected surface. However, the oil liquid injected therein has always had the problem of being quickly depleted, and its anti-icing performance will also deteriorate rapidly as the liquid injection is depleted.

[0003] The current liquid-injected anti-icing surfaces are mainly composed of polymer materials because the chain network inside the polymer can effectively store and properly distribute the oil liquid. However, the injection of the oil liquid will also significantly weaken the mechanical properties of the polymer network, resulting in insufficient mechanical durability of the coating structure. When serving under extreme conditions (including mechanical impacts such as scratches, abrasions, or high-speed impacts), the injected oil liquid may be quickly reduced or even depleted.

[0004] The present invention mainly solves the problems of insufficient mechanical durability and liquid injection leakage of the liquid-injected anti-icing surface to simultaneously meet the coexistence of the anti-icing performance and durability of the anti-icing coating. Summary of the Invention

[0005] The technical problem to be solved by the present invention is that the present invention provides a porous oil-injected anti-icing material supported by a metal skeleton, which can improve durability and anti-icing ability.

[0006] Meanwhile, the present invention provides a preparation method of a porous oil-injected anti-icing material supported by a metal skeleton, which can form a multiphase composite system, enhance the deformation incoordination of local areas, and improve the mechanical de-icing ability.

[0007] Meanwhile, the present invention provides an application of a porous oil-injected anti-icing material supported by a metal skeleton in the surface of engineering components.

[0008] To solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0009] The porous oil-injected anti-icing material supported by a metal skeleton includes a metal skeleton substrate with a porous structure. The inside of the substrate is filled with a polymer composed of polydimethylsiloxane, an oil-based liquid injection, and an aerogel substance. The percentage of the oil-based liquid injection in the total mass of the polymer is 17% - 22%, and the percentage of the aerogel substance in the total mass of the polymer is 1% - 6%. The surface of the substrate is coated with a coating of the polymer.

[0010] The metal skeleton substrate with a porous structure has a length and width both between 20 and 500 mm and a thickness between 0.2 and 1.5 mm, and includes porous nickel mesh or aluminum foam.

[0011] The oily injection liquid includes peanut oil, coconut oil or silicone oil.

[0012] The aerogel material includes Aluminiumoxid C aerogel powder or silica aerogel powder.

[0013] The thickness of the coating is 60 - 100 μm.

[0014] A preparation method of a porous oil-injected anti-icing material supported by a metal skeleton includes the following steps:

[0015] Step 1: Prepare the sample, cut it, ultrasonically clean it, dry it for standby, and cover the bottom surface of the sample with high-temperature resistant tape to obtain a metal skeleton substrate with a porous structure;

[0016] Step 2: Prepare the oily injection liquid and the aerogel material, mix the aerogel material and the oily injection liquid, where the added mass ratio of the oily injection liquid to the aerogel material is between 22:1 and 17:6, and continuously stir magnetically, with the stirring speed controlled at 300 - 400 rpm and the stirring time controlled at 2 - 3 hours;

[0017] Step 3: After the oily injection liquid and the aerogel material are stirred evenly to obtain a mixed solution, transfer the mixed solution into a vacuum furnace, conduct vacuum treatment at room temperature without heating treatment, control the vacuum degree at 0.03 - 0.05 atmospheres, and the treatment time is 8 - 12 hours to enable the aerogel material to fully absorb the injected oily injection liquid to obtain an aerogel - oil liquid mixture, and then leave it for standby;

[0018] Step 4: Prepare a polydimethylsiloxane solution, place its part A and part B in a beaker in a mass ratio of 10:1 in sequence, add a magnetic rotor and stir thoroughly, control the stirring speed at 200 - 300 rpm, and the stirring time at 2 - 4 hours to obtain a polydimethylsiloxane solution and leave it for standby;

[0019] Step 5: Mix the aerogel - oil liquid mixture obtained in Step 3 and the polydimethylsiloxane solution obtained in Step 4 in a beaker, the mass percentage of the aerogel - oil liquid mixture to the polydimethylsiloxane solution is 23:77, ensure that the percentage of the added oily injection liquid in the total mass is 17 - 22%, and the percentage of the added aerogel material in the total mass is 1 - 6%. After mixing, continue to stir magnetically, keep the stirring speed at 300 - 400 rpm, and control the stirring time at 2 - 3 hours to obtain a filling solution;

[0020] Step 6: Immerse the metal framework substrate with a porous structure obtained in Step 1 into the filling solution obtained in Step 5. After at least 10 minutes of immersion, take it out. Prepare another polytetrafluoroethylene (PTFE) plate and spray a release agent on it. Place the metal framework substrate with a porous structure filled with the filling solution on the PTFE plate, and use a scraper to remove the excess filling solution around the sample. Then transfer the PTFE plate and the sample together to a vacuum furnace. Perform vacuum pumping, control the vacuum degree at 0.08 - 0.12 atmospheres, and at the same time raise the temperature. The heating temperature is maintained at 38 - 42 °C, which is the temperature to keep the oily injection liquid in a liquid state, and the heating treatment time is 28 - 32 minutes, so that the filling solution can fully fill the voids of the metal framework substrate with a porous structure.

[0021] Step 7: Further raise the temperature of the vacuum furnace to 83 - 87 °C. At this time, the vacuum degree is maintained at 0.08 - 0.12 atmospheres, and the heating treatment time is 350 - 380 minutes to fully cure the sample. After the heating time reaches, take out the sample. During the process of taking out the sample, slowly release the vacuum. The entire air intake process lasts for 3 - 5 minutes, and ensure that the rotation speed of the vacuum degree pointer remains at 30 - 50 ° / min.

[0022] Step 8: Use the spin - coating method to evenly coat the filling solution obtained in Step 5 on the surface of the sample obtained in Step 7. The spin - coating process parameters are 1500 - 2000 rpm, the spin - coating time for each time is controlled at 30 - 60 seconds, and the number of spin - coating times is 3 - 5 times. After the spin - coating operation is completed, transfer the sample to an oven for secondary curing. Heat - treat at 38 - 42 °C for 28 - 32 minutes, then raise the temperature to 83 - 87 °C and treat for 350 - 380 minutes, and cool with the furnace. Take out the sample and remove the high - temperature - resistant tape attached to the back to obtain the finished product.

[0023] In Step 1, the high - temperature - resistant tape is a Teflon tape.

[0024] In Step 1, the method of ultrasonic cleaning is: clean with deionized water and absolute ethanol respectively. The power used for each ultrasonic cleaning is 180W, and the ultrasonic time is 40 - 60 min.

[0025] The filling solution obtained in Step 5 is continuously magnetically stirred during the processes of Step 6 and Step 8. The magnetic stirring rate is maintained at 300 - 400 rpm; that is, during the immersion operation in Step 6 and the spin - coating operation in Step 7, the filling solution needs to be magnetically stirred to prevent stratification or agglomeration.

[0026] In Step 6, the size of the PTFE plate is 500 mm × 300 mm, the release agent is a rubber release agent, and the manufacturer is Dow Corning PDMS 184 special release agent.

[0027] Application of a porous oil-injected anti-icing material supported by a metal skeleton on the surface of engineering components, where the engineering components include energy equipment and / or communication equipment, the energy equipment includes wind turbines and / or transmission lines; the communication equipment includes radios and / or communication towers.

[0028] The anti-icing material of the present invention has a metal skeleton with a porous structure. The porosity of the metal skeleton is between 85% and 90%. The interior of the porous structure is filled with aerogel powder, oil liquid, and polydimethylsiloxane substances. The length and width of the metal skeleton are not restricted and can be between 20 and 500 mm, and the thickness is between 0.2 and 1.5 mm. The metal skeleton includes porous nickel mesh or aluminum foam, etc. The metal skeleton is an existing commercially available product. For example, the porous nickel mesh selects TMAX-Nickel-Foam from Xiamen TMAX Battery Equipment Company. The Aluminiumoxid C aerogel powder is alumina aerogel powder.

[0029] The oil liquid injected in the present invention includes liquids with phase change characteristics, such as peanut oil, coconut oil, or silicone oil.

[0030] The high-temperature resistant tape is a Teflon tape (Kafuwei'er TE3499, fiberglass cloth). The main purpose is to prevent PDMS from remaining at the bottom of the sample (causing adhesion) during the subsequent polydimethylsiloxane (PDMS) impregnation process.

[0031] The polydimethylsiloxane selected is the Sylgard 184 solution from Dow Corning Corporation. The polydimethylsiloxane solution has part A as the polymer and part B as the cross-linking agent.

[0032] The present invention has the following beneficial effects:

[0033] Aiming at the problems of poor durability and low anti-icing stability of some polymer-based anti-icing coatings in the prior art, the present invention specifically combines a porous metal skeleton, an oil liquid with phase change characteristics, and a polymer anti-icing material. With a porous Ni mesh skeleton as the sample substrate, taking advantage of the large specific surface area of the aerogel powder to fully absorb the phase change oil liquid, and using the polymer material PDMS in combination. Through the design and regulation of its structure, using the porous metal skeleton to support the surrounding PDMS polymer coating and the solid state presented by the phase change liquid in the freezing temperature range, its mechanical durability and anti-icing stability are improved. And actively using the latent heat of phase change released during the freezing process of the phase change oily liquid to delay the freezing process can effectively improve the anti-icing and de-icing efficiency of this anti-icing coating. The preparation method is simple and feasible and can be mass-produced.

[0034] The present invention adopts a method combining vacuum impregnation + spin coating. The operation method is simple and clear, and it is relatively easy to realize the preparation of a high-durability anti-icing structure.

[0035] The objective of the present invention is to construct an anti-icing coating by introducing a porous metal skeleton and combining it with an oil-based material and aerogel powder with phase change characteristics. The porous metal skeleton and aerogel powder are used to significantly reduce the leakage of the injected oil-based fluid. By replacing the oil-based fluid with a liquid having phase change characteristics, it can be in a solid state within the icing temperature range, reducing the loss of the oil-based fluid. Meanwhile, the phase change heat released during the phase change process of icing can be utilized to delay the formation of interfacial ice.

[0036] The present invention can improve durability: The present invention improves durability from the following aspects. Firstly, the metal mesh skeleton with a porous structure can be combined with the cured polymer. Compared with a pure polymer coating, it can form a skeleton-like network structure, effectively increasing the impact resistance of the polymer. Secondly, the aerogel powder used has a large specific surface area and can effectively store the injected phase change oil-based liquid, reducing the previous oil-based liquid loss. Thirdly, the oil-based liquid with phase change properties is used, and the selected phase change temperature range of the oil-based liquid is from the freezing point to room temperature. In this way, during service, when the external temperature drops to near the freezing point, the injected oil-based liquid will change from a liquid state to a solid state, thus ensuring a reduction in the loss of the oil-based liquid under intense service conditions.

[0037] The aerogel has good porosity and strong adsorption capacity. Its main function is to adsorb and store the oil-based liquid. There is a synergistic effect between the aerogel, the oil-based injection liquid, and PDMS. After combination, a three-dimensional cross-linked pore structure can be formed, effectively improving the storage stability of the oil-based injection liquid in the system and also slowing down the loss of the oil-based injection liquid. Meanwhile, the aerogel not filled with the oil-based injection liquid also serves as the gas phase component in the system, jointly forming a multiphase composite system with the oil-based injection liquid (liquid phase) and PDMS (solid phase), enhancing the deformation incoordination in the local area and improving the mechanical de-icing ability.

[0038] During the curing process, it can be considered that the PDMS polymer forms a polymer network with a regular matrix. After injecting a phase change liquid such as peanut oil or coconut oil, part of it volatilizes during the curing process to form internal pores, and part reacts with PDMS and remains in the PDMS matrix. In addition, the participation of the oil-based injection liquid in the reaction also brings a certain softening effect to the whole sample, reducing the hardness (Shore hardness) of the whole sample. The decrease in hardness (Shore hardness) can improve the de-icing ability because the softening effect causes the Shore hardness to decrease, and the Shore hardness can reflect the elastic modulus of the anti-icing structure. Therefore, the decrease in the Shore hardness also means a decrease in the elastic modulus of the whole structure, which can also increase the difference in elastic modulus between different phases in the whole system. In this way, under the action of external force for de-icing, the ice adhesion strength decreases, making the de-icing difficulty decrease.

[0039] The present invention can enhance the anti-icing ability: Compared with the existing PDMS coating, the surface free energy of the PDMS coating modified by the phase change liquid in the present invention significantly increases the energy barrier that needs to be overcome for heterogeneous ice nucleation on its surface, thereby greatly increasing the ice formation time of droplets on the coating surface and significantly enhancing its anti-icing ability. At the same time, the introduction of the oil-based injection liquid and the aerogel creates certain pores inside the coating, including the solid phase, liquid phase, and gas phase, which can further increase the mismatch between different parts of the entire coating material.

[0040] The elastic modulus difference between the PDMS coating modified by the phase change liquid and the metal skeleton therein is very large. During the de-icing process, even when the same force is applied, it will cause different small deformations, thereby triggering the formation mechanism of microcracks at the solid-ice interface, reducing the ice adhesion strength and the difficulty of de-icing; subsequently, the surface of the coating prepared by the spin coating method is smooth and flat, which can effectively reduce the formation of mechanically locked ice and reduce the ice adhesion strength; the phase change oil-based liquid will release a certain amount of latent heat of phase change during the ice formation process, which can increase the temperature at the water-coating interface, delay the ice formation process, and effectively improve the anti-icing and de-icing efficiency of the coating. Brief Description of the Drawings

[0041] Figure 1 It is a partially enlarged optical photograph of the finished product of the present invention;

[0042] Figure 2 It is an SEM photograph of the finished product of the present invention;

[0043] Figure 3 It is a graph of the time delay of supercooled droplets from ice formation of the present invention;

[0044] Figure 4 It is a graph of the ice adhesion strength of the present invention;

[0045] Figure 5 It is a graph of the mass change during 50 ice formation / de-icing cycles of the present invention;

[0046] Figure 6 It is a schematic diagram of the synergistic effect among the phase change oil-based injection liquid, PDMS, and aerogel powder of the present invention. Detailed Description of the Invention

[0047] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0048] Characterization and testing methods:

[0049] (1) Optical microscope analysis:

[0050] The surface morphology of the prepared anti-icing coating was characterized by a Nikon Microscope (optical microscope).

[0051] (2)Scanning electron microscope analysis:

[0052] The surface microstructure of the prepared anti-icing coating was characterized by a JEOL-6490LV SEM scanning electron microscope. The scanning voltage was 20 kV, and the working distance was maintained at 10 mm. Since the surface of the coating is non-conductive, it is necessary to perform platinum spraying treatment before taking pictures to add a layer of platinum (Pt) layer to the coating to make the coating conductive.

[0053] (3)Static water contact angle test:

[0054] The surface wettability of the coating was tested using a fully automatic optical contact angle measuring instrument (FTA200, First TenAngstroms) from the United States. The test solvent was deionized water, the volume of the test droplet was 5 μL, the release rate was 1 μL / s, and 5 positions were selected for testing for each sample, and the average value was calculated.

[0055] (4)Ice adhesion strength test:

[0056] In an environmental chamber at a temperature of -20 °C, it was measured using a horizontal shear test system. The pre-prepared sample / ice block was adhered to the sample surface. The shear test system mainly consisted of a force probe, a motion controller, and a prefabricated ice block adhered to the sample to be tested. The pre-prepared ice block / substrate sample was tested in a uniform horizontal motion form, and the force probe pushed the ice / sample at a speed of 0.1 mm / min. As the horizontal shear force gradually increased, the ice block would overcome the shear strength and finally separate from the sample surface. By measuring the horizontal shear force and the sample contact area, the ice adhesion strength of the sample itself could be calculated.

[0057] (5)Durability and anti-icing stability test of the anti-icing coating

[0058] The prepared samples were repeatedly subjected to ice adhesion strength test cycles. The test interval for each time was 3 hours, and the total number of freezing / de-icing cycles was 50 times. And the mass change and ice adhesion strength change of the coating samples for each time were recorded.

[0059] (6)The measurement standard used in the process of measuring Shore hardness is Shore A hardness.

[0060] Example 1

[0061] A preparation method of a porous oil-injected anti-icing material supported by a metal skeleton, comprising the following steps:

[0062] 1. Prepare a porous nickel mesh substrate sample with dimensions of 50 mm × 20 mm × 0.3 mm. Its internal porosity is calculated to be about 89%. Subsequently, perform ultrasonic cleaning. The method of ultrasonic cleaning is as follows: Clean it separately with deionized water and absolute ethanol. Each time, the ultrasonic power is 180 W and the ultrasonic time is 50 min. Then dry it for later use. Cover the bottom surface of the sample with a high-temperature resistant tape. The high-temperature resistant tape is a Teflon tape (Kafuwell TE3499, fiberglass cloth). The main purpose is to prevent PDMS from remaining at the bottom of the sample (causing adhesion) during the subsequent PDMS impregnation process;

[0063] 2. Prepare 2 g of peanut oil and 0.3 g of Aluminiumoxid C aerogel powder. Add the two to a beaker in sequence for uniform mixing, and continuously stir magnetically. Control the stirring speed at about 300 rpm and the stirring time at about 2 hours;

[0064] 3. After stirring the peanut oil and Aluminiumoxid C aerogel powder evenly, transfer the above mixed solution into a vacuum furnace for vacuum treatment at room temperature without heating. Control the vacuum degree at 0.05 atmospheres and the treatment time at 12 hours to allow the Aluminiumoxid C aerogel powder to fully absorb the injected peanut oil, and then leave it for later use;

[0065] 4. Prepare a polydimethylsiloxane (Dow Corning, Sylgard 184) solution. Weigh its part A and part B according to a mass ratio of 10:1, where part A is 7 g and part B is 0.7 g, using an electronic balance. Place them in a glass beaker in sequence and carefully stir with a magnetic rotor. Control the stirring speed at 200 rpm and the stirring time at about 3 hours, and leave it for later use;

[0066] 5. Mix the peanut oil - aerogel mixture (with a mass of 2.3 g) and the PDMS solution (with a mass of 7.7 g) in a beaker. The mass percentage between the two is 23:77. After mixing, continue to stir magnetically. Control the stirring time at 3 hours and keep the magnetic stirring rate at 350 rpm.

[0067] 6. Slowly place the porous nickel mesh substrate into the mixed solution obtained in step 5) and allow it to be fully wetted. After 10 minutes of placement, take it out. Prepare another polytetrafluoroethylene plate with a size of 500mm×300mm and spray a rubber release agent (manufacturer: Dow Corning PDMS 184 special release agent) on the polytetrafluoroethylene plate; place the metal skeleton substrate with a porous structure filled with the filling solution on the polytetrafluoroethylene plate, and use a squeegee to remove the excess filling solution around the sample. Then transfer the polytetrafluoroethylene plate and the sample together to a vacuum furnace; perform vacuum pumping, control the vacuum degree at 0.1 atmospheric pressure, and remove the gas existing in the porous nickel mesh substrate. At the same time, raise the temperature, keep the heating temperature at 40°C (the purpose is to ensure that the injected peanut oil is in a liquid state), and the first-stage heating treatment time is 30 minutes to enable the mixed solution to fully fill the voids in the porous skeleton structure.

[0068] 7. Further raise the temperature of the vacuum furnace to 85°C. At this time, the vacuum degree is maintained at 0.1 atmospheric pressure, and the heating treatment time is 360 minutes to cause cross-linking on the surface of the impregnated polydimethylsiloxane to complete curing. After the heating time reaches, take out the sample. During the process of taking out the sample, the vacuum needs to be slowly released. The entire air intake process should last for 4 minutes, and ensure that the rotation amplitude of the vacuum degree pointer does not exceed a certain range, and the rotation speed is maintained at 40° / min. The purpose of such an operation is to prevent the air intake speed from being too fast, so as to avoid the internal and external pressure difference from squeezing out the already infiltrated oily substance, and then leave it for standby.

[0069] 8. Use the spin coating method to evenly coat the mixed solution obtained in step 5) on the surface of the sample. The spin coating process parameters are 1500rpm, the spin coating time for each time is controlled at 45 seconds, and the number of spin coating times is 5 times. After the spin coating operation is completed, transfer the sample to an ordinary oven for secondary curing, heat-treat at 40°C for 30 minutes, then raise the temperature to 85°C and treat for 360 minutes, and cool with the furnace. Take out the sample and carefully remove the high-temperature glue attached to the back to obtain the finished product. The final thickness of the coating on the finished product is about 60μm.

[0070] The filling solution obtained in step 5) is continuously magnetically stirred during the processes of step 6) and step 8), and the magnetic stirring rate is maintained at 350rpm; that is, during the wetting operation in step 6) and the spin coating operation in step 8), the filling solution needs to be magnetically stirred to prevent stratification or aggregation.

[0071] The porous oil-injected anti-icing material supported by a metal skeleton obtained in this embodiment includes a metal skeleton substrate with a porous structure. The inside of the substrate is filled with a polymer composed of polydimethylsiloxane, an oily injection liquid, and an aerogel material. The percentage of the oily injection liquid in the total mass of the polymer is 20%, and the percentage of the aerogel material in the total mass of the polymer is 3%; the surface of the substrate is coated with a coating of the polymer.

[0072] Application of the porous oil-injected anti-icing material supported by a metal skeleton obtained in this embodiment on the surface of engineering components, where the engineering components include energy equipment and / or communication equipment, the energy equipment includes wind turbines and / or transmission lines; the communication equipment includes radios and / or communication towers.

[0073] After measurement, the Shore A hardness of the finished product obtained in this embodiment is 13.7 ± 1.0 (Shore A hardness).

[0074] Figure 1 A partially enlarged optical photograph of this embodiment is given, as Figure 1 shown in (a), it can be seen that the porous nickel mesh skeleton is wrapped by the PDMS matrix, and there are some black substances on the surface, which are actually the peanut oil diffused and penetrated. And Figure 1 (b) is a sample without adding aerogel powder, and it can be found that there is more peanut oil diffused and penetrated on the surface. The two pictures can reflect the role of aerogel powder in improving the storage efficiency of oil.

[0075] In addition, during the curing process, the PDMS polymer forms a polymer network with a regular matrix. After the peanut oil phase change liquid is injected, part of the peanut oil volatilizes during the curing process, forming internal pores as shown in Figure 1 (a), and part of the peanut oil reacts with PDMS to crosslink and remains in the PDMS matrix. The existence of internal pores makes there be certain pores inside the coating of the present invention, including solid phase, liquid phase and gas phase, jointly forming a multiphase composite system, enhancing the deformation incoordination of local areas and improving the mechanical de-icing ability.

[0076] Figure 2 An SEM photograph of the finished product of this embodiment is given. As can be seen from Figure 2 (a), the surface is relatively smooth and flat, with a small number of black dots, corresponding to the optical photograph in Figure 1 (a); as can be seen from Figure 2 (b), the cross-sectional morphology of this embodiment can be seen, and there are irregularly distributed holes inside the finished product, and the formed internal hole size is about 5 to 10 µm.

[0077] Figure 3The anti-icing materials of Example 1 - Example 2 and Comparative Example 1 - Comparative Example 2 are given. For the time graph of delaying the icing of supercooled droplets on them, it can be found that the delaying time of Comparative Example 2 without adding aerogel powder is about 49 s. After adding a small amount of aerogel, the delaying effect of Comparative Example 1 reaches 68 s. For Example 1, after having an oily injection liquid and appropriate aerogel powder, its delaying effect reaches 93 s. For Example 2, after adding an excessive amount of aerogel powder, its delaying icing effect is similar to that of Example 1, with a slight increase, being 95 s. This shows that adding an excessive amount of aerogel powder to obtain a multiphase composite system, namely a gas-phase - liquid-phase - solid-phase multiphase composite system, can significantly delay the icing time of supercooled droplets.

[0078] Figure 4 The ice adhesion strength of this example during 50 icing / de-icing processes is given. It can be seen that the data of the ice adhesion strength in the initial state is 15.16 ± 1.32 kPa, with a relatively low value, reflecting the good de-icing ability of the coating. As the number of icing / de-icing cycles increases, the ice adhesion strength increases slightly, rising to 18.92 ± 1.34 kPa at the 15th time and gradually remaining stable. When the 50 icing / de-icing cycles end, the ice adhesion strength is still only 19.83 ± 1.65 kPa, demonstrating good anti-icing stability performance.

[0079] Figure 5 The mass change situations of Example 1 - Example 2 and Comparative Example 1 - Comparative Example 2 during 50 icing / de-icing cycles are given. It can be seen that the coating of Example 1 shows good mechanical durability. After 50 cycles, the entire coating system still retains 99.86% of its mass, reflecting the ability of the coating sample to maintain structural stability. The injected peanut oil can be well protected and will not be quickly depleted and lost under intense service conditions. This increases its mechanical stability and enables the coating to serve for a long time. For Comparative Example 1, after adding a small amount of aerogel, due to the relatively small content of the added aerogel powder, there is a certain loss, and the remaining mass is 99.3%. For Example 2, it is 99.84%, and for Comparative Example 2 without adding aerogel powder, the remaining mass is 98.57%.

[0080] As Figure 6 shown, there is a synergistic effect between the aerogel, the oily injection liquid, and PDMS. After combination, a three-dimensional cross-linked pore structure is formed, which can effectively improve the storage stability of the oily injection liquid in the system and also slow down the loss of the oily injection liquid. At the same time, the aerogel not filled with the oily injection liquid also serves as the gas-phase component in the system, jointly forming a multiphase composite system with the oily injection liquid (liquid phase) and PDMS (solid phase), enhancing the deformation incoordination in the local area and improving the mechanical de-icing ability.

[0081] Example 2

[0082] The difference between this embodiment and Embodiment 1 is only that: the mass of the added peanut oil is 1.9 g, and the mass of the added Aluminiumoxid C aerogel powder is 0.4 g, aiming to keep the Aluminiumoxid C aerogel powder in excess, and the mass ratio of the peanut oil-aerogel mixture to the PDMS mass is 23:77.

[0083] Example 3

[0084] A preparation method of a porous oil-injected anti-icing material supported by a metal skeleton includes the following steps:

[0085] 1. Prepare an aluminum foam sample with dimensions of 200 mm × 50 mm × 0.2 mm, and its internal porosity is calculated to be about 85%. Subsequently, perform ultrasonic cleaning. The method of ultrasonic cleaning is: clean it separately with deionized water and absolute ethanol. The ultrasonic power is 180 W each time, and the ultrasonic time is 40 min each time. Then dry it for later use, and cover the bottom surface of the sample with a high-temperature resistant tape. The high-temperature resistant tape is a Teflon tape (Kafwell TE3499, fiberglass cloth). The main purpose is to prevent PDMS from remaining at the bottom of the sample (causing adhesion) during the subsequent PDMS impregnation process;

[0086] 2. Prepare 2.2 g of coconut oil and 0.1 g of silica aerogel powder, add the two to a beaker in sequence for uniform mixing, and continuously stir magnetically. The stirring speed is controlled at about 400 rpm, and the stirring time is controlled at about 3 hours;

[0087] 3. After stirring the coconut oil and silica aerogel powder evenly, transfer the above mixed solution into a vacuum furnace for vacuum treatment at room temperature without heating. The vacuum degree is controlled at 0.03 atmospheres, and the treatment time is 8 hours to allow the silica aerogel powder to fully absorb the injected coconut oil, and then leave it for later use;

[0088] 4. Prepare a polydimethylsiloxane (Dow Corning, Sylgard 184) solution. Weigh its Part A and Part B according to a mass ratio of 10:1, where Part A is 7 g and Part B is 0.7 g. Use an electronic balance for weighing, place them in a glass beaker in sequence, and carefully stir with a magnetic rotor. The stirring speed is controlled at 300 rpm, and the stirring time is controlled at about 2 hours, and leave it for later use;

[0089] 5. Mix the coconut oil-aerogel mixture (with a mass of 2.3 g) and the PDMS solution (with a mass of 7.7 g) in a beaker. The mass percentage between the two is 23:77. After mixing, continue to stir magnetically. The stirring time is controlled at 2 hours, and the magnetic stirring rate is maintained at 300 rpm.

[0090] 6. Slowly place the aluminum foam substrate into the mixed solution obtained in step 5) and allow it to be fully wetted. After 15 minutes of placement, take it out. Prepare another polytetrafluoroethylene plate with a size of 500 mm × 300 mm, and spray a rubber release agent (manufacturer: Dow Corning PDMS 184 special release agent) on the polytetrafluoroethylene plate. Place the metal skeleton substrate with a porous structure filled with the filling solution on the polytetrafluoroethylene plate, and use a scraper to remove the excess filling solution around the sample. Then transfer the polytetrafluoroethylene plate and the sample together to a vacuum furnace. Conduct a vacuum treatment, control the vacuum degree at 0.08 atmospheres, and expel the gas existing in the aluminum foam substrate. At the same time, raise the temperature, keep the heating temperature at 38 °C (the purpose is to ensure that the injected coconut oil is in a liquid state), and the first-stage heating treatment time is 28 minutes, so that the mixed solution can fully fill the voids in the porous skeleton structure.

[0091] 7. Further raise the temperature of the vacuum furnace to 83 °C. At this time, the vacuum degree is maintained at 0.08 atmospheres, and the heating treatment time is 350 minutes to cause cross-linking on the surface of the impregnated polydimethylsiloxane to complete curing. After the heating time reaches, take out the sample. During the process of taking out the sample, the vacuum needs to be slowly released. The entire air intake process should last for 3 minutes, and ensure that the rotation amplitude of the vacuum degree pointer does not exceed a certain range, and the rotation speed is maintained at 30° / min. The purpose of such an operation is to prevent the air intake speed from being too fast, so as to avoid the internal and external pressure difference from squeezing out the infiltrated oily substance, and then leave it for standby.

[0092] 8. Use the spin coating method to evenly apply the mixed solution obtained in step 5) to the surface of the sample. The spin coating process parameters are 2000 rpm, the spin coating time for each time is controlled at 30 seconds, and the number of spin coating times is 3 times. After the spin coating operation is completed, transfer the sample to an ordinary oven for secondary curing. Heat-treat at 38 °C for 28 minutes, then raise the temperature to 83 °C and treat for 350 minutes, and cool with the furnace. Take out the sample and carefully remove the high-temperature adhesive attached to the back to obtain the finished product. The final thickness of the coating on the finished product is about 70 μm.

[0093] The filling solution obtained in step 5) is continuously magnetically stirred during the processes of step 6) and step 8), and the magnetic stirring rate is maintained at 300 rpm; that is, during the wetting operation in step 6) and the spin coating operation in step 8), the filling solution needs to be magnetically stirred to prevent stratification or agglomeration.

[0094] The porous oil-injected anti-icing material supported by a metal skeleton obtained in this embodiment includes a metal skeleton substrate with a porous structure. The inside of the substrate is filled with a polymer composed of polydimethylsiloxane, an oily injection liquid, and an aerogel substance. The percentage of the oily injection liquid in the total mass of the polymer is 22%, and the percentage of the aerogel substance in the total mass of the polymer is 1%; a coating of the polymer is coated on the surface of the substrate.

[0095] Application of the porous oil-injected anti-icing material supported by a metal skeleton obtained in this embodiment on the surface of engineering components, where the engineering components include energy equipment and / or communication equipment, the energy equipment includes wind turbines and / or transmission lines; the communication equipment includes radios and / or communication towers.

[0096] Example 4

[0097] A preparation method of a porous oil-injected anti-icing material supported by a metal skeleton, comprising the following steps:

[0098] 1. Prepare a porous nickel mesh sample with dimensions of 100 mm × 150 mm × 1.5 mm, whose internal porosity is calculated to be about 90%. Subsequently, perform ultrasonic cleaning. The method of ultrasonic cleaning is as follows: Clean with deionized water and anhydrous ethanol respectively. The ultrasonic power is 180 W each time, and the ultrasonic time is 60 min each time. Then dry it for later use, and cover the bottom surface of the sample with a high-temperature resistant tape. The high-temperature resistant tape is a Teflon tape (Kafuwell TE3499, fiberglass cloth). The main purpose is to prevent PDMS from remaining at the bottom of the sample (causing adhesion) during the subsequent PDMS impregnation process;

[0099] 2. Prepare 1.7 g of silicone oil and 0.6 g of silica aerogel powder. Add the two to a beaker in sequence for uniform mixing, and continuously stir magnetically. The stirring speed is controlled at about 350 rpm, and the stirring time is controlled at about 2.5 hours;

[0100] 3. After stirring the silicone oil and silica aerogel powder evenly, transfer the above mixed solution into a vacuum furnace for vacuum treatment at room temperature without heating. The vacuum degree is controlled at 0.05 atmospheres, and the treatment time is 10 hours to allow the silica aerogel powder to fully absorb the injected silicone oil, and then leave it for later use;

[0101] 4. Prepare a polydimethylsiloxane (Dow Corning, Sylgard 184) solution. Weigh its part A and part B according to a mass ratio of 10:1, where part A is 7 g and part B is 0.7 g. Use an electronic balance for weighing, place them in a glass beaker in sequence, and carefully stir with a magnetic rotor. The stirring speed is controlled at 250 rpm, and the stirring time is controlled at about 4 hours, and leave it for later use;

[0102] 5. Mix the silicone oil-aerogel mixture (with a mass of 2.3 g) and the PDMS solution (with a mass of 7.7 g) in a beaker. The mass percentage between the two is 23:77. After mixing, continue to stir magnetically. The stirring time is controlled at 2.5 hours, and the magnetic stirring rate is maintained at 400 rpm.

[0103] 6. Slowly place the porous nickel mesh substrate into the mixed solution obtained in step 5) and allow it to be fully wetted. After 12 minutes of placement, take it out. Prepare another polytetrafluoroethylene plate with a size of 500 mm × 300 mm and spray a rubber release agent (manufacturer: Dow Corning PDMS 184 special release agent) on the polytetrafluoroethylene plate. Place the metal skeleton substrate with a porous structure filled with the filling solution on the polytetrafluoroethylene plate, and use a scraper to remove the excess filling solution around the sample. Then transfer the polytetrafluoroethylene plate and the sample together to a vacuum furnace. Conduct a vacuum treatment, control the vacuum degree at 0.12 atmospheres, and expel the gas existing in the porous nickel mesh substrate. At the same time, raise the temperature, keep the heating temperature at 42 °C (the purpose is to ensure that the injected silicone oil is in a liquid state), and the first-stage heating treatment time is 32 minutes to enable the mixed solution to fully fill the voids in the porous skeleton structure.

[0104] 7. Further raise the temperature of the vacuum furnace to 87 °C. At this time, the vacuum degree is maintained at 0.12 atmospheres, and the heating treatment time is 380 minutes to cause cross-linking on the surface of the impregnated polydimethylsiloxane to complete curing. After the heating time reaches, take out the sample. During the process of taking out the sample, the vacuum needs to be slowly released. The entire air intake process should last for 5 minutes, and ensure that the rotation amplitude of the vacuum degree pointer does not exceed a certain range, and the rotation speed is kept at 50° / min. The purpose of such an operation is to prevent the air intake speed from being too fast, so as to avoid the internal and external pressure difference from squeezing out the already infiltrated oily substance, and then leave it for standby.

[0105] 8. Use the spin coating method to evenly apply the mixed solution obtained in step 5) to the surface of the sample. The spin coating process parameters are 1600 rpm, the spin coating time for each time is controlled at 60 seconds, and the number of spin coating times is 5 times. After the spin coating operation is completed, transfer the sample to a common oven for secondary curing. Heat-treat at 42 °C for 32 minutes, then raise the temperature to 87 °C and treat for 380 minutes, and cool with the furnace. Take out the sample and carefully remove the high-temperature adhesive attached to the back to obtain the finished product. The final thickness of the coating on the finished product is about 100 μm.

[0106] The filling solution obtained in step 5) is continuously magnetically stirred during the processes of step 6) and step 8). The magnetic stirring rate is kept at 400 rpm; that is, during the wetting operation in step 6) and the spin coating operation in step 8), the filling solution needs to be magnetically stirred to prevent stratification or agglomeration.

[0107] The porous oil-injected anti-icing material supported by the metal skeleton obtained in this embodiment includes a metal skeleton substrate with a porous structure. The inside of the substrate is filled with a polymer composed of polydimethylsiloxane, oily injection liquid and aerogel material. The percentage of the oily injection liquid in the total mass of the polymer is 17%, and the percentage of the aerogel material in the total mass of the polymer is 6%. The surface of the substrate is coated with a coating of the polymer.

[0108] Application of the porous oil-injected anti-icing material supported by a metal skeleton obtained in this embodiment on the surface of engineering components, where the engineering components include energy equipment and / or communication equipment, the energy equipment includes a wind turbine and / or a transmission line; the communication equipment includes a radio and / or a communication tower.

[0109] Comparative Example 1

[0110] The difference between this comparative example and Example 1 is only that: 2.25 g of peanut oil and 0.05 g of Aluminiumoxid C aerogel powder are added. The purpose of this comparative example is to keep the amount of Aluminiumoxid C aerogel powder insufficient, that is, a small amount of aerogel is added, and a multiphase composite system cannot be formed, and the deformation incoordination of the local area cannot be enhanced, and thus the mechanical de-icing ability cannot be significantly improved.

[0111] Comparative Example 2

[0112] The difference between this comparative example and Example 1 is only that: the mass of the added peanut oil is 2.3 g, and no Aluminiumoxid C aerogel powder is added.

[0113] Comparative Example 3

[0114] The difference between this comparative example and Example 1 is only that: no peanut oil is added, and no oily injection liquid is added. The Shore hardness data of the finally obtained finished product is 37.6 ± 1.1 (Shore A hardness). Explanation: The oily injection liquid participates in the reaction and brings a certain softening effect to the whole sample, reducing the hardness (Shore hardness) of the whole sample. The decrease in hardness (Shore hardness) can improve the de-icing ability. Because the softening effect causes the Shore hardness to decrease, and the Shore hardness can reflect the elastic modulus of the anti-icing structure, so the decrease in the Shore hardness also means that the elastic modulus of the whole structure decreases, which can also increase the elastic modulus difference between different phases in the whole system. Under the action of external force de-icing, the ice adhesion strength decreases, making the de-icing difficulty decrease.

[0115] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art of this industry should understand that the present invention is not limited by the above embodiments. What is described in the above embodiments and the specification only illustrates the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

1. A porous oil-injected anti-icing material supported by a metal skeleton, characterized in that: it includes a metal skeleton substrate with a porous structure, and the interior of the substrate is filled with a polymer composed of polydimethylsiloxane, an oil-based injection liquid, and an aerogel substance. The percentage of the oil-based injection liquid in the total mass of the polymer is 17% to 22%, and the percentage of the aerogel substance in the total mass of the polymer is 1% to 6%; a coating of the polymer is coated on the surface of the substrate; the oil-based injection liquid includes peanut oil, coconut oil, or silicone oil.

2. The porous oil-injected anti-icing material supported by a metal skeleton according to claim 1, characterized in that: the metal skeleton substrate with a porous structure has a length and a width both between 20 and 500 mm and a thickness between 0.2 and 1.5 mm, and includes a porous nickel mesh or aluminum foam.

3. The porous oil-injected anti-icing material supported by a metal skeleton according to claim 1, characterized in that: the aerogel substance includes Aluminiumoxid C aerogel powder or silica aerogel powder.

4. The porous oil-injected anti-icing material supported by a metal skeleton according to claim 1, characterized in that: the thickness of the coating is 60 to 100 μm.

5. A preparation method of the porous oil-injected anti-icing material supported by a metal skeleton according to any one of claims 1 to 4, characterized in that: it includes the following steps: Step 1: Prepare the sample, cut it, ultrasonically clean it, dry it for standby, and cover the bottom surface of the sample with a high-temperature resistant tape to obtain a metal skeleton substrate with a porous structure; Step 2: Prepare the oil-based injection liquid and the aerogel substance, mix the aerogel substance and the oil-based injection liquid, wherein the added mass ratio of the oil-based injection liquid to the aerogel substance is between 22:1 and 17:6, and continuously stir magnetically, the stirring speed is controlled at 300 to 400 rpm, and the stirring time is controlled at 2 to 3 hours; Step 3: After the oil-based injection liquid and the aerogel substance are stirred evenly, obtain a mixed solution, transfer the mixed solution into a vacuum furnace, perform vacuum treatment at room temperature without heating treatment, the vacuum degree is controlled at 0.03 to 0.05 atmospheric pressure, and the treatment time is 8 to 12 hours to enable the aerogel substance to fully absorb the injected oil-based injection liquid to obtain an aerogel-oil liquid mixture, and then leave it for standby; Step 4: Prepare a polydimethylsiloxane solution, place the A part and the B part of Dow Corning Sylgard 184 in a beaker in a mass ratio of 10:1 in sequence, add a magnetic rotor and stir thoroughly, the stirring speed is controlled at 200 to 300 rpm, and the stirring time is controlled at 2 to 4 hours to obtain a polydimethylsiloxane solution, and leave it for standby; Step Five: Mix the aerogel-oil mixture obtained in Step Three and the polydimethylsiloxane solution obtained in Step Four in a beaker. The mass percentage of the aerogel-oil mixture to the polydimethylsiloxane solution is 23:

77. Ensure that the percentage of the added oil-based injection liquid in the total mass is 17 - 22%, and the percentage of the added aerogel material in the total mass is 1 - 6%. After mixing, continue magnetic stirring. The stirring speed is maintained at 300 - 400 rpm, and the stirring time is controlled within 2 - 3 hours to obtain a filling solution. Step Six: Immerse the metal skeleton substrate with a porous structure obtained in Step One into the filling solution obtained in Step Five. Take it out after at least 10 minutes of immersion. Prepare another polytetrafluoroethylene plate and spray a release agent on it. Place the metal skeleton substrate with a porous structure filled with the filling solution on the polytetrafluoroethylene plate, and use a scraper to remove the excess filling solution around the sample. Then transfer the polytetrafluoroethylene plate and the sample together to a vacuum furnace. Conduct a vacuum treatment. The vacuum degree is controlled at 0.08 - 0.12 atmospheres. At the same time, raise the temperature. The heating temperature is maintained at 38 - 42 °C, which is the temperature to keep the oil-based injection liquid in a liquid state. The heating treatment time is 28 - 32 minutes to make the filling solution fully fill the pores of the metal skeleton substrate with a porous structure. Step Seven: Further raise the temperature of the vacuum furnace to 83 - 87 °C. At this time, the vacuum degree is maintained at 0.08 - 0.12 atmospheres, and the heating treatment time is 350 - 380 minutes to fully cure the sample. After the heating time reaches, take out the sample. During the process of taking out the sample, slowly release the vacuum. The entire air intake process lasts for 3 - 5 minutes, and ensure that the rotation speed of the vacuum degree pointer is maintained at 30 - 50 ° / min. Step Eight: Use the spin coating method to evenly coat the filling solution obtained in Step Five on the surface of the sample obtained in Step Seven. The spin coating process parameters are 1500 - 2000 rpm. Each spin coating time is controlled within 30 - 60 seconds, and the number of spin coating times is 3 - 5 times. After the spin coating operation is completed, transfer the sample to an oven for secondary curing. Conduct heat treatment at 38 - 42 °C for 28 - 32 minutes, then raise the temperature to 83 - 87 °C for 350 - 380 minutes, and cool it in the furnace. Take out the sample and remove the high-temperature resistant tape attached to the back to obtain the finished product.

6. The preparation method of the porous oil-injected anti-icing material supported by a metal skeleton according to Claim 5, characterized in that: In Step One, the high-temperature resistant tape is a Teflon tape.

7. The preparation method of the porous oil-injected anti-icing material supported by a metal skeleton according to Claim 5, characterized in that: In Step One, the method of ultrasonic cleaning is: clean with deionized water and absolute ethanol respectively. The power used for each ultrasonic cleaning is 180 W, and the ultrasonic time is 40 - 60 min.

8. The preparation method of the porous oil-injected anti-icing material supported by a metal skeleton according to Claim 5, characterized in that: The filling solution obtained in Step Five is continuously magnetically stirred during Step Six and Step Eight, and the magnetic stirring rate is maintained at 300 - 400 rpm; that is, during the infiltration operation in Step Six and the spin-coating operation in Step Eight, the filling solution needs to be magnetically stirred to prevent stratification or agglomeration.

9. Application of the porous oil-injected anti-icing material supported by a metal skeleton according to any one of claims 1 to 4 on the surface of engineering components, characterized in that: the engineering components include energy equipment and / or communication equipment, the energy equipment includes wind turbines and / or transmission lines; the communication equipment includes radios and / or communication towers.

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