Self-sealing high-temperature-resistant electronic ink, preparation method and application thereof

Abstract

The application provides a self-sealing high-temperature-resistant electronic ink, characterized by comprising the following raw material components: 100 parts of metal nano powder, 50-100 parts of silicon-based ceramic precursor polymer and 10-30 parts of organic dilution solvent. An application method of the self-sealing high-temperature-resistant electronic ink comprises the following steps: S1, printing the self-sealing high-temperature-resistant electronic ink into a sensitive film; and S2, annealing the sensitive film in a high-temperature air environment at 700-1400 DEG C, so that a high-temperature-resistant conductive film can be prepared after cooling.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high-temperature conductive materials, and particularly relates to self-packaging high-temperature-resistant electronic ink and a preparation method and application thereof. BACKGROUND

[0002] The design optimization and ground testing of aerospace equipment (including aircraft engines and hypersonic aircraft) require accurate collection of operating parameters. Real-time monitoring of the surface state of these complex curved surfaces in extreme environments is a highly challenging task. Existing discrete and wire sensors may encounter flow field interference and potential damage to structural integrity, thus being difficult to meet the requirements of accurate monitoring of the operating state of aerospace equipment in the field. However, traditional physical vapor deposition (PVD) thin film sensors face challenges such as complex surface configuration difficulties, high cost, and limited temperature resistance. The conformal printing technology provides a novel solution that is simple, flexible, cost-effective, and compatible with various materials. It can be used for rapid, large-scale, and customized manufacturing of high-temperature-resistant conformal thin film sensors. However, the internal temperature of an aircraft engine and the temperature peak of an aircraft stagnation point exceed 1300℃, and the temperature resistance of existing printed inks is <1000℃, which cannot meet the application requirements of such high-temperature environments. At the same time, the synthesis process of existing inks is complex, or requires a complex heat treatment process, such as inert atmosphere pyrolysis, which is not conducive to practical application. Therefore, it is a formidable challenge to develop an ink that is easy to synthesize, has high electrical conductivity, has a simple post-processing process, and also maintains high temperature resistance. SUMMARY

[0003] To solve the above problems, the application provides a self-packaging high-temperature-resistant electronic ink and a preparation method and application thereof.

[0004] The object of the application is achieved by the following technical solutions:

[0005] The self-packaging high-temperature-resistant electronic ink comprises the following raw material components: 100 parts of metal nano powder, 50-100 parts of silicon-based ceramic precursor polymer, and 10-30 parts of organic dilution solvent.

[0006] In some embodiments, the silicon-based ceramic precursor polymer is selected from one or more of polysiloxane, polysilazane, polyborosiloxane, polyaluminosiloxane, polyborosilazane, polyaluminosilazane, and perhydropolysilazane.

[0007] In some embodiments, the organic dilution solvent is selected from one or more of xylene, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether.

[0008] In some embodiments, the metal nano powder is selected from one or more of silver-palladium nano powder, palladium nano powder, platinum nano powder, and platinum-rhodium nano powder.

[0009] In some embodiments, 10-20 parts of titanium carbide nano-powder is further included.

[0010] In some embodiments, 5-10 parts of melamine is further included.

[0011] An application method of the self-packaged high-temperature-resistant electronic ink, comprising the following steps:

[0012] S1, printing the self-packaged high-temperature-resistant electronic ink into a sensitive film;

[0013] S2, annealing the sensitive film in a high-temperature air environment of 700-1400 DEG C, and after cooling, a high-temperature-resistant conductive film is prepared.

[0014] In some embodiments, step S2 is: annealing the sensitive film in a high-temperature nitrogen environment of 800 DEG C first, and then annealing in a high-temperature air environment of 800-1300 DEG C.

[0015] A method for preparing a high-temperature conformal film sensor by using the self-packaged high-temperature-resistant electronic ink, comprising the following steps:

[0016] S1, performing plasma treatment on an engine blade substrate with a thermal barrier coating;

[0017] S2, direct writing printing the self-packaged high-temperature-resistant electronic ink on the surface of the engine blade treated in step S1, to obtain an engine blade with a 5-20 micron thin film sensor sensitive grid pattern attached;

[0018] S3, annealing the engine blade with the thin film sensor sensitive grid pattern attached obtained in step S2 in a high-temperature air environment of 700-1400 DEG C.

[0019] In some embodiments, the plasma treatment time is 1-20 min.

[0020] The present application has the following advantages:

[0021] The present application uses a non-sacrificial organic solvent silicon-based ceramic precursor polymer to synthesize a high-temperature-resistant ink. After the ink is annealed at high temperature, the silicon-based ceramic precursor polymer forms an amorphous ceramic phase, which wraps the mutually connected conductive metal nanoparticles with amorphous ceramic, on the one hand, isolating oxygen, and on the other hand, improving the anti-sintering performance of the nanoparticles, thereby improving the stability of platinum particles in a high-temperature environment. The film made of the ink synthesized by using metal platinum nanoparticles has an air environment application temperature of up to 1600 DEG C or above, which is the highest temperature resistance performance reported so far, and is used to make an ink for making a high-temperature-resistant functional conductive film.

[0022] The application applies the metal carrier interaction mechanism to the development of high-temperature ink, forms a double-layer structure of outer amorphous ceramic physical coating and inner metal carrier chemical coating, which is beneficial to the improvement of the oxidation stability of metal nanoparticles and the improvement of the electromigration resistance. Therefore, the conductive ink configured by the method has good stability, and the conductive sensitive pattern printed on the high-temperature running part has good conductivity and adhesion.

[0023] The preparation method and post-processing process of the self-packaged high-temperature-resistant electronic ink are simple, easy to operate and beneficial to practical application. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The self-packaged high-temperature-resistant electronic ink provided for the embodiment 1 of the application is shown in the manufacturing process schematic diagram.

[0025] Figure 2 The rheological property diagram of the self-packaged high-temperature-resistant electronic ink provided for the embodiment 1 of the application is shown.

[0026] Figure 3 The TEM diagram of the self-packaged high-temperature-resistant electronic ink provided for the embodiment 1 of the application after 1300 DEG C annealing is shown.

[0027] Figure 4 The resistance change curve with temperature of the self-packaged high-temperature-resistant electronic ink provided for the embodiment 1 of the application after high-temperature annealing is shown.

[0028] Figure 5 The temperature resistance test result of the high-temperature-resistant film made of the self-packaged high-temperature-resistant electronic ink provided for the embodiment 1 of the application is shown.

[0029] Figure 6 The SEM comparison diagram of the platinum composite material film provided for the embodiment 1 and the comparative example 1-2 of the application after keeping at 1300 DEG C for 100 hours is shown.

[0030] Figure 7 The schematic diagram of the self-packaged high-temperature-resistant electronic ink provided for the application example 1 for printing a conformal film sensor is shown.

[0031] Figure 8 The comparison diagram of the thermocouple signal and the resistance change signal of the blade base conformal film temperature sensor provided for the application example 1 and the conversion of the resistance change into a temperature signal are shown. DETAILED DESCRIPTION

[0032] In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative effort belong to the protection scope of the present application.

[0033] In a first aspect, the embodiments of the present application provide a self-sealing high-temperature-resistant electronic ink, which comprises the following raw material components: 100 parts of metal nano powder, 50-100 parts of silicon-based ceramic precursor polymer, and 10-30 parts of organic diluent solvent.

[0034] In the embodiments of the present application, the silicon-based ceramic precursor polymer and the organic diluent solvent are not particularly limited, and the silicon-based ceramic precursor polymer can be selected from polysiloxane, polysilazane, polyborosiloxane, polyaluminosiloxane, polyborosilazane, polyaluminosilazane, and perhydropolysilazane, etc. The metal nano powder can be selected from silver palladium, palladium, platinum, platinum rhodium, etc. The particle size of the metal nano powder can be selected in the range of 2 nm-50 nm.

[0035] In some embodiments, the self-sealing high-temperature-resistant electronic ink further comprises 10-20 parts of titanium carbide nano powder.

[0036] In some embodiments, the self-sealing high-temperature-resistant electronic ink further comprises 5-10 parts of melamine.

[0037] The preparation method of the self-sealing high-temperature-resistant electronic ink is as follows: the silicon-based ceramic precursor solution is placed in a container, the metal nano particles and the organic diluent are added, and then the mixture is prepared by magnetic stirring and ultrasonic treatment until it is uniformly mixed.

[0038] In some embodiments, titanium carbide nano powder and / or melamine are further added, and the mixture is prepared again by magnetic stirring and ultrasonic treatment until it is uniformly mixed.

[0039] In a second aspect, the embodiments of the present application provide an application method of the above self-sealing high-temperature-resistant electronic ink, which comprises the following steps:

[0040] S1, printing the self-sealing high-temperature-resistant electronic ink into a sensitive film; the printing substrate can be an insulating coating or the surface of an object, such as silicate, alumina, silicon nitride, and silicon oxide.

[0041] S2, annealing the sensitive film in a high-temperature air environment at 700-1400℃, and then preparing a high-temperature-resistant conductive film after cooling. The high-temperature air environment can be a high-temperature furnace, laser, flame, etc.

[0042] In some embodiments, step S2 is: annealing the sensitive film in a high-temperature nitrogen environment at 800 DEG C for 1 hour, and then annealing in a high-temperature air environment at 800-1300 DEG C for 1 hour.

[0043] The self-sealing high-temperature-resistant electronic ink is not conductive in normal temperature state due to insufficient solid content to form a conductive network and the isolation of the silicon-based precursor polymer. The process of high-temperature air annealing can achieve conductivity. During the annealing process, the volume of the ink shrinks, and at the same time, the metal nanocrystals increase in size to achieve the connection between the particles, showing a metal-like conductivity.

[0044] One of the most important features of the embodiments of the present application is to use a silicon-based ceramic precursor polymer as an organic solvent, and its characteristics of being converted into an amorphous ceramic after high-temperature annealing. This is completely different from the route of using a sacrificial organic solvent in most current inks or commercial slurries, and then removing the organic solvent by high-temperature annealing. Such a sacrificial organic solvent ink or slurry is difficult to overcome the inherent properties of the solute material itself. For example, a platinum thin film obtained by sintering a commercial platinum slurry will form volatile platinum oxide in a high-temperature air environment, resulting in the volatilization and failure of the platinum thin film in a high-temperature environment.

[0045] In order to overcome this limitation, the embodiments of the present application design a preparation method of a self-sealing high-temperature-resistant electronic ink. The core of this method is to use a non-sacrificial organic solvent, a silicon-based ceramic precursor polymer. After the ink is annealed at high temperature, the silicon-based ceramic precursor polymer forms an amorphous ceramic phase, which wraps the conductive metal nanoparticles connected to each other, on the one hand, to isolate oxygen, and on the other hand, to improve the anti-sintering performance of the nanoparticles, thereby improving the stability of the metal particles in a high-temperature environment.

[0046] In order to improve the stability and anti-sintering performance of the composite material formed after the self-sealing high-temperature-resistant electronic ink is annealed at high temperature, in some embodiments of the present application, an enhanced component of 15 parts of titanium carbide nano powder is also included. The particle size of the titanium carbide powder is preferably not higher than 50 nm to ensure a large specific surface area. In the embodiments of the present application, the free carbon formed by the silicon-based ceramic precursor polymer at high temperature will enhance the Fermi level of the metal nanoparticles, which is helpful for the formation of a strong metal-support interaction of titanium carbide in a high-temperature oxidation environment. Through the strong interaction between titanium carbide and metal nanoclusters, the titanium carbide carrier firmly anchors the metal nanoparticles, induces the encapsulation of the metal carrier, and ensures the stability of the conductive nanoparticles at high temperature. Thus, a two-layer coating structure is realized, that is, an outer amorphous ceramic physical coating and an inner metal carrier interaction coating. Therefore, the stability of the metal nanoparticles at high temperature can be significantly improved, which not only inhibits the oxidation and volatilization behavior of the metal nanoparticles at high temperature, but also improves the anti-sintering performance of the metal nanoparticles.

[0047] In a third aspect, the embodiments of the present application provide a method for applying self-sealing high-temperature-resistant ink to a high-temperature conformal film sensor, specifically comprising:

[0048] Step a, processing the substrate: plasma treating the engine blade substrate with a thermal barrier coating to remove impurities on the surface; the material of the thermal barrier coating is generally zirconium oxide, which serves as an insulating layer;

[0049] Step b, printing the ink: directly printing the self-sealing high-temperature-resistant ink on the engine blade surface treated in step a to obtain an engine blade with a 5-20 μm thin film sensor sensitive grid pattern attached;

[0050] Step c, annealing treatment: placing the engine blade with the thin film sensor sensitive grid pattern attached obtained in step b into a high-temperature furnace or performing annealing treatment by laser.

[0051] In some embodiments, in step a, the plasma treatment of the engine blade substrate is performed for 1-20 min; in step c, the annealing temperature is not lower than 700℃, and is preferably 700-1300℃.

[0052] Example 1

[0053] In this example, a preparation and application method of self-sealing high-temperature-resistant ink is provided, specifically comprising the following steps:

[0054] 1) Prepare self-sealing high-temperature-resistant electronic ink: weigh 1 g of polysilazane solution into a container, add 1.5 g of platinum nanoparticles, and prepare a uniformly mixed self-sealing high-temperature-resistant electronic ink by ultrasonic treatment for 30 min and magnetic stirring for 1 h, as shown in Figure 1 .

[0055] 2) Add reinforcing components: take 0.225 g of titanium carbide nano powder from the self-sealing high-temperature-resistant electronic ink obtained in step (1), and prepare a uniformly mixed self-sealing high-temperature-resistant electronic ink by magnetic stirring and ultrasonic treatment again.

[0056] 3) Print the ink: the self-sealing high-temperature-resistant electronic ink obtained through the above steps can be used to print a designed 5-20 μm sensitive thin film on an alumina temperature-resistant substrate by ink direct writing.

[0057] 4) Annealing treatment method: place the platinum composite film printed by direct writing in a high-temperature air environment high-temperature furnace and anneal at 1300℃ for 1 h, and after cooling, the high-temperature-resistant conductive platinum composite film can be manufactured.

[0058] The rheological properties of the self-sealing high-temperature-resistant electronic ink prepared in step 1) of Example 1 are characterized and analyzed, as shown in Figure 2As shown in FIG. 6, it can be seen that the ink exhibits shear thinning phenomenon.

[0059] TEM analysis was performed on the platinum composite film after high-temperature annealing, as shown in FIG. 7, it can be seen that the platinum is obviously coated by amorphous ceramic. Figure 3

[0060] The platinum self-packaging high-temperature-resistant electronic ink after high-temperature annealing was analyzed for the change trend of annealing temperature and conductivity, as shown in FIG. 8, it can be seen that the conductivity is increasing with the increase of temperature, and the conductivity of the platinum self-packaging high-temperature-resistant electronic ink after annealing at 1300℃ is close to the conductivity of platinum metal, showing metallic conductivity. Figure 4

[0061] The long-term resistance drift rate of the platinum composite film obtained in this example at 1300℃ for 100 hours is shown in Table 1, and the resistance drift rate is obtained by real-time monitoring of the change of film resistivity by digital acquisition instrument.

[0062] In addition, the resistance drift rate of the platinum composite film after being kept at 1600℃ for 40 minutes was also tested, as shown in FIG. 9, the abscissa is the cooling time, which takes 25h, and the resistance change rate is only 3.9% / h in the short-term air environment at 1600℃, which is the highest temperature-resistant film reported in the air environment at present. Figure 5

[0063] Example 2

[0064] The difference between this example and Example 1 is only that:

[0065] In step 1) of this example, the self-packaging high-temperature-resistant electronic ink was configured: 1g of polysilazane solution was weighed into a container, 1.25g of platinum nanoparticles was added, and the mixture was uniformly prepared by ultrasonic treatment for 30 minutes and magnetic stirring for 1 hour.

[0066] Example 3

[0067] The difference between this example and Example 1 is only that:

[0068] In step 1) of this example, the self-packaging high-temperature-resistant electronic ink was configured: 1g of polysilazane solution was weighed into a container, 1g of platinum nanoparticles was added, and the mixture was uniformly prepared by ultrasonic treatment for 30 minutes and magnetic stirring for 1 hour.

[0069] Comparative Example 1

[0070] The difference between this example and Example 1 is that no reinforcing component titanium carbide is added in the configuration of the self-packaging high-temperature-resistant electronic ink.

[0071] ​​​The resistance drift rate of the platinum composite film obtained from the comparative example at 1300°C for 100 hours is shown in Table 1.

[0072] Comparative Example 2

[0073] The difference from Example 1 is that a commercially purchased platinum paste (Shenzhen Saiya Platinum Paste 1803D) is used as the printing ink after being diluted 1:1.1, and the high-temperature-resistant conductive platinum film can be realized after being annealed at 1300°C for 1 hour and then cooled.

[0074] The resistance drift rate of the platinum composite film obtained from the comparative example at 1300°C for 100 hours is shown in Table 1.

[0075] Comparative Example 3

[0076] The difference from Example 1 is that the annealing temperature is 500°C.

[0077] Comparative Example 4

[0078] The difference from Example 1 is that the annealing temperature is 1800°C.

[0079] Table 1 Long-term resistance drift rate of platinum composite film of each example and comparative example at 1300°C for 100 hours

[0080] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Resistance drift 6％ / 100h 8％ / 100h 9％ / 100h 10％ / 100h 122％ / 100h

[0081] As can be seen from Table 1, the high-temperature resistance of the platinum composite film of Example 1 is obviously better than that of Comparative Examples 1 and 2.

[0082] The contact angle of the ink in Examples 1-3 and Comparative Examples 1-4 is measured, and the conductivity of the ink after being annealed at 1300°C is tested. The contact angle measurement uses the titration method: a liquid drop is dropped on the surface of the solid, a high-resolution camera is used to take the shape of the liquid drop from the side, and then the angle of contact between the liquid drop and the surface is measured through image analysis software. The conductivity is measured by the four-probe test method by sequentially placing four parallel probes on the surface of the material, applying current through the two outer probes and measuring the voltage difference through the two inner probes to accurately calculate the conductivity or resistivity of the material. The results are shown in Table 2.

[0083] Table 2

[0084] Contact angle size Room temperature conductivity after annealing Example 1 about 40° 6.1 x 10 6 S / m]] Example 2 about 33° 2.9 x 10 6 S / m]] Example 3 about 25° 7.8 x 10 5 S / m]] Comparative Example 1 about 38° 6.3 x 10 6 S / m]] Comparative Example 2 about 35° 6.5 x 10 6 S / m]] Comparative Example 3 about 40° < 10 -6 S / m <!-- 5 -->]]> Comparative Example 4 about 40° < 10 -6 S / m]]

[0085] As can be seen from Table 2, the conductivity of the ink of Examples 1-3 and Comparative Examples 1-2 is of the same order of magnitude, with little difference, but the conductivity of Comparative Examples 3-4 is much smaller than that of Examples 1-3, indicating that the annealing temperature is very critical, and a suitable annealing temperature can improve the conductivity of the ink.

[0086] SEM comparison of platinum composite thin films obtained in Example 1 and Comparative Examples 1-2 after being kept at 1300°C for 100 hours is shown in FIG. 1. Both Example 1 and Comparative Example 1 show the effect of encapsulating platinum nanoparticles, and the platinum nanoparticle size in Example 1 is relatively smaller than that in Comparative Example 1. In Comparative Example 2, the Pt nanoparticles are completely sintered, and without the outer encapsulation, the Pt nanoparticles show poorer durability at high temperatures. Figure 6

[0087] Application Example 1

[0088] In this example, the application of the self-encapsulated high-temperature-resistant ink in the field of high-temperature conformal thin film sensor is provided, and specifically includes the following steps:

[0089] 1) Pretreatment: The nickel-based alloy blade with thermal barrier coating is subjected to plasma treatment for 20 min.

[0090] 2) Printing ink: The self-encapsulated high-temperature-resistant electronic ink prepared in step 2) of Example 1 is directly printed on the engine blade surface treated in step 1) to obtain an engine blade with a thin film temperature sensor sensitive grid pattern attached.

[0091] Step c, annealing treatment: The engine blade with a thin film temperature sensor sensitive grid pattern attached obtained in step b is placed in a high-temperature furnace and subjected to 900°C air environment annealing treatment.

[0092] The blade-based conformal thin film temperature sensor is prepared as shown in FIG. 4. The conformal thin film sensor has obvious advantages over the current wire-made thermocouple temperature measurement method. It can be manufactured in situ by printing, and the structure itself will not be damaged. In addition, the temperature measurement is more accurate, Figure 7 Figure 7 In this example, the application of the self-encapsulated high-temperature-resistant ink in the field of high-temperature conformal thin film sensor is provided, and specifically includes the following steps: Figure 8

[0093] ​​​The above examples are only used to illustrate the technical solutions of the present application, and are not intended to limit the present application; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced by equivalent features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A self-encapsulated high-temperature resistant electronic ink, characterized in that, The raw material components include: 100 parts metal nanopowder, 50-100 parts silicon-based ceramic precursor polymer, 10-30 parts organic diluent solvent, and 10-20 parts titanium carbide nanopowder; The metal nanopowder is selected from one or more of silver-palladium nanopowder, palladium nanopowder, platinum nanopowder, and platinum-rhodium nanopowder.

2. The self-encapsulated high-temperature resistant electronic ink according to claim 1, characterized in that, The silicon-based ceramic precursor polymer is selected from one or more of polysiloxane, polysilazane, polyboronsiloxane, polyaluminumsiloxane, polyboronsilazane, polyaluminumsilazane, and perhydropolysilazane.

3. The self-encapsulated high-temperature resistant electronic ink according to claim 1, characterized in that, The organic diluent is selected from one or more of xylene, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether.

4. The self-encapsulated high-temperature resistant electronic ink according to claim 1, characterized in that, It also includes 5 to 10 parts of melamine.

5. A method for applying the self-encapsulated high-temperature resistant electronic ink according to any one of claims 1 to 4, characterized in that, The process includes the following steps: printing self-encapsulated high-temperature resistant electronic ink into a sensitive film, annealing the sensitive film in a high-temperature air environment of 700~1400℃, and cooling it to achieve the preparation of a high-temperature resistant conductive film.

6. The application method according to claim 5, characterized in that, The process includes annealing the sensitive film in a high-temperature air environment before annealing it in a nitrogen environment at 800°C.

7. A method for fabricating a high-temperature conformal thin-film sensor using the self-encapsulated high-temperature resistant electronic ink according to any one of claims 1 to 4, comprising the following steps: S1, Plasma treatment is performed on the engine blade substrate with thermal barrier coating; S2, the self-encapsulated high-temperature electronic ink is directly written onto the surface of the engine blade after step S1 to obtain an engine blade with a 5~20μm thin film sensor sensitive grid pattern attached. S3, the engine blade with the attached thin film sensor sensitive grid pattern obtained in step S2 is annealed in a high-temperature air environment of 700~1400℃.

8. The application method according to claim 7, characterized in that, The plasma treatment time is 1~20 min.

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