A method of building a ceramic shell on a ceramifiable silicone rubber surface and a ceramic silicone rubber part

Abstract

The application discloses a method for constructing a ceramic shell on a ceramifiable silicone rubber surface and a ceramic silicone rubber part, and belongs to the technical field of surface modification of high polymer composite materials. The method aims to solve the problems of mechanical performance decline and poor surface coating combination caused by overall ceramic in the prior art. The method comprises the following steps: preparing a ceramifiable silicone rubber preform comprising a silicone rubber matrix, a ceramic-forming filler and a fluxing agent; and irradiating a predetermined surface area of the preform by using a high-energy laser beam, so that the material of the surface area is converted into a ceramic layer in situ. The application further discloses a ceramic silicone rubber part which comprises a ceramifiable silicone rubber matrix and a ceramic shell on the surface, and a gradient transition layer exists between the two. The application can rapidly generate a ceramic protective layer in situ on the surface without sacrificing the mechanical performance of the matrix, and realizes the structure of "soft inside and hard outside".

Description

Technical Field

[0002] This invention relates to the field of surface modification technology for polymer composite materials, and in particular to a method for constructing a ceramic shell on a ceramicizable silicone rubber surface and a ceramic silicone rubber component. Background Technology

[0003] In fields such as new energy vehicles, energy storage power stations, and aerospace, increasingly stringent requirements are being placed on the fire safety performance of polymer elastomer materials. For example, thermal runaway of power batteries can instantly generate flames and molten metal particles exceeding 1000°C. Ceramizable silicone rubber, a composite material that maintains flexibility at room temperature and transforms into a hard ceramic body at high temperatures, is considered a key material for addressing such challenges.

[0004] Existing technologies typically employ a monolithic ceramization method, which involves incorporating a large amount of ceramic filler and flux into a silicone rubber matrix, followed by molding and vulcanization to create components. When exposed to high temperatures such as flames, this material undergoes a monolithic ceramization transformation, forming a protective barrier. However, this approach has inherent drawbacks: First, to achieve effective monolithic ceramization, the amount of inorganic filler added is usually very high, severely sacrificing the excellent mechanical properties of silicone rubber (such as elasticity and elongation at break) and worsening its processing flowability. Second, this ceramization process is passively triggered, relying on slow heat conduction from an external heat source, resulting in a slow response. Under instantaneous high-temperature impacts, the material may be burned through or destroyed before achieving full ceramization. Furthermore, other techniques that coat the silicone rubber surface with ceramic slurry are prone to cracking and peeling under high-temperature impacts due to the significant difference in thermal expansion coefficients between the coating and the flexible substrate, and the inherent physical bonding between the coating and the substrate, leading to premature failure of the protective function. Summary of the Invention

[0005] The purpose of this invention is to provide a method for constructing a ceramic shell on the surface of ceramizable silicone rubber and a ceramic silicone rubber component. This invention aims to solve the technical problems in the prior art, where the addition of fillers to achieve ceramization leads to a decrease in the mechanical properties of silicone rubber, poor processability, slow thermal response, and the ceramic coating layer on the surface has poor adhesion to the substrate and is easy to peel off.

[0006] To achieve the above objectives, the present invention provides a method for constructing a ceramic shell on a ceramicizable silicone rubber surface, comprising the following steps: Prepare a ceramizable silicone rubber preform, wherein the ceramizable silicone rubber comprises: a silicone rubber matrix, a ceramic filler, and a flux; A predetermined surface area of ​​the ceramicizable silicone rubber preform is irradiated with a high-energy laser beam; The energy and duration of the irradiation are sufficient to transform the material in the predetermined surface area into a ceramic layer in situ.

[0007] Optionally, the ceramizable silicone rubber further comprises reinforcing fillers.

[0008] Optionally, based on 100 parts by weight of the silicone rubber matrix, the amount of the ceramic filler is 50-150 parts by weight, and the amount of the flux is 5-30 parts by weight.

[0009] Optionally, the ceramic filler is selected from at least one of wollastonite, mica powder, kaolin, or talc powder.

[0010] Optionally, the flux is selected from at least one of low-melting-point glass powder, zinc borate, or borax.

[0011] Optionally, the high-energy laser beam is selected from carbon dioxide lasers, fiber lasers, ultraviolet lasers, or excimer lasers.

[0012] Optionally, the energy density of the irradiation is from 10 J / cm² to 200 J / cm².

[0013] Optionally, the irradiation is achieved by scanning the predetermined surface area at a scanning speed of 10 mm / s to 5000 mm / s.

[0014] The present invention also provides a ceramic silicone rubber component, comprising: A matrix made of ceramizable silicone rubber; and a ceramic shell disposed on the surface of the substrate; There is a gradient transition layer with a gradual change in composition or structure from the substrate to the ceramic shell.

[0015] Optionally, the surface of the ceramic shell has a micro-nano rough structure.

[0016] Compared with the prior art, the present invention has the following beneficial effects: By irradiating the surface of ceramicizable silicone rubber preforms with a high-energy laser beam, a high-hardness, high-density ceramic shell is generated in situ only on the surface without affecting the overall flexibility, elasticity, and mechanical properties of the matrix material. This structure, with a hard outer layer and a flexible interior, solves the problem of severely degraded material mechanical and processing properties caused by the addition of large amounts of inorganic fillers in existing technologies.

[0017] The ceramic-silicone rubber component prepared by the method of this invention forms a gradient transition layer with gradually changing composition or structure between the ceramic shell and the silicone rubber matrix through an in-situ transformation process. This gradient transition layer can effectively alleviate the thermal and mechanical stress between the hard ceramic layer and the flexible substrate, achieving a strong interfacial bond and effectively avoiding the defects of traditional surface coating technology, such as cracking and peeling due to mismatch in thermal expansion coefficients.

[0018] Leveraging the non-contact, high-energy-density, and rapid heating characteristics of lasers, the ceramicization process has been shortened from tens of minutes in traditional heat treatment to milliseconds, significantly improving production efficiency and reducing energy consumption. Simultaneously, laser processing is easily digitally controlled, enabling precise, localized processing of complex-shaped workpieces. It offers high flexibility and design freedom, solving the problems of slow response and inability to perform localized strengthening in traditional overall heat treatment.

[0019] By adjusting the laser process parameters, a micro-nano rough structure can be formed on the surface of the ceramic shell, giving the component additional functionality, such as hydrophobicity and self-cleaning properties, thereby further improving the overall performance of the product. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a schematic flowchart of a method for constructing a ceramic shell on a ceramicizable silicone rubber surface according to an embodiment of the present invention.

[0022] Figure 2 This is a schematic diagram of the laser in-situ ceramization process according to an embodiment of the present invention.

[0023] Figure 3 This is a schematic cross-sectional view of a ceramic-silicone rubber component prepared according to an embodiment of the present invention.

[0024] Figure 4 This is an application diagram illustrating the machining of complex curved surface workpieces according to an embodiment of the present invention.

[0025] In the diagram: 10-Laser processing head; 20-Laser beam; 30-Ceramicizable silicone rubber preform; 31-Silicone rubber matrix; 40-In-situ formed ceramic layer; 41-Ceramic shell; 42-Gradient transition layer; 50-O-ring seal; 60-Laser scanning trajectory; 70-Area where the ceramic layer has been formed. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this application clearer, the application will be further described in detail below with reference to the accompanying drawings. The described embodiments should not be considered as limitations on this application. All other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this application. Unless otherwise defined, all technical and scientific terms used in the embodiments of this application have the same meaning as commonly understood by those skilled in the art. The terminology used in the embodiments of this application is for the purpose of describing the embodiments of this application only and is not intended to limit this application. Before further detailed description of the embodiments of this application, some nouns and terms involved in the embodiments of this application are explained, and the nouns and terms involved in the embodiments of this application are subject to the following interpretations.

[0027] (1) Ceramizable silicone rubber: refers to a composite material containing a silicone rubber matrix, ceramic filler and flux, characterized by exhibiting an elastomer at room temperature, but its surface or the whole can be transformed into a hard structure with a ceramic phase under laser irradiation or high temperature. This material aims to combine the flexibility of silicone rubber with the high temperature resistance and high hardness of ceramics.

[0028] (2) In-situ transformation: refers to the process in which physical and chemical changes (such as pyrolysis, melting, reaction, and solidification) are directly induced in the original location of the material through the input of external energy (such as laser), thereby forming a new phase or structure, rather than through the addition or coating of external materials. In this application, it specifically refers to the process of directly transforming the surface material of ceramizable silicone rubber into a ceramic layer.

[0029] (3) Gradient transition layer: refers to the interface region between the ceramic shell and the silicone rubber substrate, in which the chemical composition, phase composition or microstructure changes continuously from one side to the other. This region ensures stress relief and firm bonding between the hard ceramic layer and the flexible substrate, which is a key structural feature that distinguishes it from traditional physical coating technology.

[0030] (4) Micro-nano rough structures: These refer to the uneven morphology formed on the surface of ceramic shells with dimensions in the micrometer and / or nanometer range, such as mesh or columnar arrays. Such structures can endow the surface with special physicochemical properties, such as hydrophobicity, self-cleaning properties, or enhanced thermal insulation.

[0031] Please see Figures 1 to 3This application aims to provide a method for constructing a ceramic shell on the surface of ceramizable silicone rubber and a ceramic silicone rubber component obtained by this method. Its core objective is to solve the technical problems in the prior art, such as the severe degradation of the mechanical properties of silicone rubber due to the overall addition of fillers to achieve fire resistance, or the poor adhesion and easy peeling failure of surface coating technology at high temperatures. The technical solution of this application achieves the formation of a robust, high-temperature resistant, and firmly bonded ceramic protective layer only on the surface while maintaining the flexibility of the silicone rubber matrix through a precise and rapid surface treatment method.

[0032] The method provided in this application is based on the core idea of ​​using a high-energy laser beam to treat the surface of a specially formulated ceramicizable silicone rubber. First, a ceramicizable silicone rubber preform needs to be prepared. The purpose of this step (S101) is to obtain a matrix material with a specific chemical composition. This material is a stable flexible body at room temperature but contains the potential to transform into ceramic at high temperatures. This design fundamentally differs from the approach of coating ordinary silicone rubber; instead, it embeds the transformation capability within the material itself, laying the material basis for subsequent in-situ transformation.

[0033] Next, a predetermined surface area of ​​the ceramizable silicone rubber preform is irradiated with a high-energy laser beam (S102). This step is crucial to this technical solution. Unlike traditional oven heating methods that rely on slow heat conduction, high-energy laser beams can precisely project extremely high energy density onto tiny surface areas of the material in a non-contact manner within a very short time. This process is designed to overcome the shortcomings of traditional heat treatment, such as slow response, low efficiency, and high energy waste. By precisely controlling the laser path and energy, selective and localized treatment of the workpiece surface can be achieved without causing unnecessary thermal effects on untreated areas or the interior of the material, thereby protecting the macroscopic properties of the base material.

[0034] Finally, the energy and duration of the irradiation are sufficient to transform the material in the predetermined surface area into a ceramic layer in situ (S103). This is the direct technical effect achieved by the aforementioned steps. Under the excitation of laser energy, the surface material undergoes drastic physicochemical changes, including the pyrolysis of the silicone rubber matrix, the melting of the ceramic filler and flux, and chemical reactions between the components. After the laser beam sweeps across, the high-temperature molten region undergoes an extremely rapid cooling process (rapid cooling), thereby solidifying to form a new, dense ceramic phase. Through this "in-situ transformation," there is no physical interface between the newly grown ceramic layer and the underlying substrate; instead, a continuous transition is formed, fundamentally solving the peeling problem caused by the mismatch in thermal expansion coefficients of traditional coatings and achieving a robust metallurgical-grade bond.

[0035] Furthermore, in a preferred embodiment, the ceramizable silicone rubber further comprises reinforcing fillers. These reinforcing fillers, such as fumed silica, are designed to enhance the fundamental mechanical properties of the silicone rubber matrix itself. Before laser treatment, these fillers significantly improve the tensile strength, tear strength, and abrasion resistance of the material through their high specific surface area and interaction with the silicone rubber molecular chains. The technical effect of this feature is that it not only makes the matrix portion of the final product more robust and durable but also provides a stronger supporting foundation for the subsequently formed ceramic layer, thereby improving the overall mechanical properties and reliability of the entire composite component.

[0036] In another preferred embodiment, the proportions of the core components of the material are defined. Based on 100 parts by weight of the silicone rubber matrix, the amount of the ceramic filler is 50-150 parts by weight, and the amount of the flux is 5-30 parts by weight. This ratio range is a balanced result obtained through extensive experimental optimization. Its design aims to ensure sufficient ceramic components in the system to form a continuous, dense ceramic layer, while avoiding a sharp decline in the processability (such as flowability) of the preform during the molding and vulcanization stage due to excessive filler. By controlling the component content within this range, good processability of the material can be maintained while ensuring the final ceramicization effect, resolving the contradiction between performance and processability caused by high filler content in the prior art.

[0037] In one alternative embodiment, the ceramic filler can be selected from a range of proven materials, such as at least one of wollastonite, mica powder, kaolin, or talc. These inorganic mineral fillers share the common characteristic of containing significant amounts of ceramic-forming elements such as silicon, aluminum, and calcium, and are chemically stable at high temperatures, serving as a primary source for forming the ceramic framework. The advantage of providing multiple options is that the most suitable filler or combination thereof can be flexibly selected based on cost, material availability, and requirements for specific properties of the final ceramic layer (such as dielectric properties and coefficient of thermal expansion).

[0038] Similarly, in another alternative embodiment, the flux may be selected from at least one of low-melting-point glass powder, zinc borate, or borax. The flux is designed in this system to melt first during the laser-induced rapid heating process, forming a liquid phase that wets and encapsulates the solid-phase ceramic filler particles. The presence of this liquid phase significantly accelerates mass migration and chemical reaction rates. By selecting these specific fluxes, the ceramic transformation temperature of the entire system can be effectively reduced, allowing for a dense sintering process to be completed within the limited laser action time, thus achieving the technical effect of obtaining a high-quality ceramic layer within a wider process window.

[0039] Furthermore, the type of high-energy laser beam—the energy source for this method—is further refined. The high-energy laser beam can be selected from carbon dioxide lasers, fiber lasers, ultraviolet lasers, or excimer lasers. Different types of lasers emit different wavelengths, beam qualities, and operating modes (continuous or pulsed), and their absorption rates vary for different materials. For example, carbon dioxide lasers (wavelength 10.6 μm) have excellent absorption for silicate materials, making them suitable for macroscopic heat treatment; while ultraviolet lasers (such as 355 nm), due to their high photon energy and small heat-affected zone, are more suitable for fine processing. The technical advantage of this solution, which encompasses multiple laser types, is that it is not limited to a specific type of equipment, enhancing the method's versatility and allowing users to choose the most suitable technical path based on processing requirements and existing equipment conditions.

[0040] In a preferred embodiment, key process parameters for laser processing are defined, with the irradiation energy density ranging from 10 J / cm² to 200 J / cm². Energy density, a function of laser power and spot area, directly determines the energy absorbed per unit area of ​​material. Its design aims to precisely control the degree of ceramization reaction. If the energy density is below 10 J / cm², it may be insufficient to reach the temperature for complete melting and reaction, resulting in a porous and weak ceramic layer. If it exceeds 200 J / cm², it may cause excessive ablation and vaporization of the material, damaging the surface smoothness and integrity. Therefore, by controlling the energy density within this optimized range, a dense, uniform ceramic layer free of macroscopic defects can be stably obtained.

[0041] In another preferred embodiment, the irradiation is achieved by scanning the predetermined surface area at a scanning speed of 10 mm / s to 5000 mm / s. The scanning speed determines the residence time of the laser beam at a point in the material, which, together with the laser power, determines the total energy input. This is designed to work in conjunction with energy density to create a broad and stable process window. At lower scanning speeds, the material interacts with the laser for a longer time, allowing for more complete thermal penetration and reaction, suitable for preparing thicker ceramic layers; while at higher scanning speeds, extremely high processing efficiency can be achieved, suitable for rapid processing of large areas or thin layers. This broad speed range gives this method extremely high flexibility and production efficiency, capable of adapting to diverse needs ranging from fine marking to large-area surface strengthening.

[0042] Please see Figure 3This application also provides a ceramic-silicone rubber component prepared by the above method. This component is structurally innovative, comprising a substrate 31 made of ceramizable silicone rubber and a ceramic shell 41 disposed on the surface of the substrate 31. Its core distinguishing feature is the presence of a gradient transition layer 42 with a gradual change in composition or structure from the substrate 31 to the ceramic shell 41. This gradient transition layer 42 is not a separate, clearly separable layer, but rather a bridge connecting the ceramic and the rubber. Its design principle stems from the physical nature of the in-situ conversion process: the absorption of laser energy and heat conduction in the material are themselves gradient-distributed, with the highest energy and most complete reaction at the point closest to the surface, forming a pure ceramic phase; further inward, the energy gradually weakens, the degree of reaction decreases, and the ceramic phase coexists with the unreacted silicone rubber component, gradually transitioning until it smoothly connects to the completely unaffected silicone rubber substrate 31. This structure completely eliminates stress concentration points between the hard layer and the flexible substrate, making them appear as a naturally grown whole, thereby achieving excellent bonding strength and resistance to thermal shock and mechanical peeling.

[0043] Furthermore, in a preferred embodiment, the surface of the ceramic shell 41 may have a micro / nano rough structure. This structure is naturally formed or controlled by specific process parameters under the synergistic effect of complex physical phenomena such as rapid melting and plasma impact during laser-material interaction. Its design aims to endow the component with additional surface functions. For example, specific micro / nano structures can significantly reduce surface energy, allowing water droplets to exhibit a high contact angle, thereby achieving excellent hydrophobic and self-cleaning properties; or, this rough structure can increase the specific surface area, acting as an effective thermal radiation barrier at high temperatures, further enhancing the thermal insulation effect. Through this feature, the fabricated component not only possesses basic fire protection capabilities but also integrates more high-value-added functions.

[0044] To better understand the present invention, a specific embodiment will be described in detail below with reference to the accompanying drawings. Figure 1 and Figure 2 As shown, this embodiment provides a method for constructing a ceramic shell on a ceramicizable silicone rubber surface. The method first requires performing step S101, which involves preparing a ceramicizable silicone rubber preform 30. This preform 30 macroscopically presents as a flexible elastomer with a specific shape, such as a sheet, gasket, or sealing ring. Its internal components include a silicone rubber matrix as a continuous phase, and ceramic fillers and fluxes uniformly dispersed therein. These fillers and fluxes are the material basis for subsequent functional transformation, but at this stage, they exist only as inert fillers, and the preform 30 as a whole retains the mechanical properties of silicone rubber.

[0045] Subsequently, step S102 is performed, in which a high-energy laser beam 20 is used to irradiate a predetermined surface area of ​​the preform 30. Specifically, as shown in step S102... Figure 2 As shown, a laser processing head 10 is positioned above the preform 30. Its internal optical system focuses the laser beam generated by the laser source to form a laser beam 20 with a specific diameter and energy distribution, which is then projected onto the surface of the preform 30. The laser processing head 10 can be mounted on a CNC machine tool or a robotic arm, thereby enabling precise control of the movement trajectory, scanning speed, and area of ​​the laser beam 20 on the surface of the preform 30 according to a preset program.

[0046] Under the irradiation of laser beam 20, the material in the irradiated area undergoes in-situ transformation to form a ceramic layer, i.e., step S103. The high-density photon energy carried by laser beam 20 is absorbed by the material surface (typically at a depth of micrometers) within picoseconds to nanoseconds and is rapidly converted into heat energy, causing the temperature in this area to rise sharply to over 800°C within milliseconds. At this high temperature, the silicone rubber matrix undergoes thermal decomposition, while the flux rapidly melts into a liquid state and encapsulates the solid ceramic filler particles. In the liquid phase environment, the ceramic filler decomposes, reorganizes, and undergoes complex physicochemical reactions with the pyrolysis products of silicone rubber (such as reactive silica). As laser beam 20 moves away with the scan, the high-temperature molten area is exposed to a lower temperature environment and experiences an extremely high cooling rate, causing the melt to solidify before it has time to crystallize or only partially crystallize, forming a dense ceramic layer 40 with an amorphous or microcrystalline structure. The entire process only occurs on the surface layer that has been laser-scanned, while the temperature of most of the main body of the preform 30 does not rise significantly, thus preserving its original flexibility and elasticity.

[0047] Accordingly, this invention also provides a ceramic-silicone rubber component prepared by the above method. Please refer to [link / reference]. Figure 3 The cross-sectional structure of this component clearly demonstrates its "flexible interior and rigid exterior" characteristics. The main body of the component is made of ceramicizable silicone rubber, with the unconverted portion being the silicone rubber matrix 31 shown in the figure. This matrix occupies the majority of the component's volume and determines its overall flexibility, elasticity, and sealing performance. A ceramic shell 41, generated through in-situ laser conversion, covers the surface of the matrix 31. This ceramic shell 41 is hard and dense, giving the component surface excellent high-temperature resistance, wear resistance, and chemical corrosion resistance.

[0048] The most critical structural feature of this component lies in the presence of a gradient transition layer 42 between the ceramic shell 41 and the silicone rubber substrate 31, exhibiting a continuous change in both composition and structure. This gradient transition layer 42 is not a clear interface, but rather a region. Within this region, the composition and microstructure of the material gradually change from the side closer to the ceramic shell 41 to the side closer to the silicone rubber substrate 31: the content of the ceramic phase gradually decreases, while the content of the silicone rubber phase gradually increases, and simultaneously, the hardness and modulus of the material smoothly decrease. This gradient structure is an inevitable product of the laser thermal field gradient distribution and in-situ reaction process, making the rigid ceramic shell 41 appear as if it "grows" from the flexible silicone rubber substrate 31, forming a strong metallurgical bond between the two. It is precisely the existence of this gradient transition layer 42 that effectively alleviates the interfacial stress caused by the incoordination of deformation between the hard layer and the soft substrate when subjected to external forces or temperature changes, fundamentally avoiding the cracking, blistering, and peeling problems common in traditional coatings, thus endowing the component with extremely high reliability and durability.

[0049] In a preferred embodiment, based on the above embodiments, the materials used to prepare the ceramizable silicone rubber preform 30 include, in addition to the silicone rubber matrix, ceramic filler, and flux, reinforcing filler is added. The reinforcing filler (such as fumed silica or precipitated silica), through its nanoscale size and large specific surface area, forms a strong physical and chemical adsorption effect with the silicone rubber molecular chains, constituting a "filler-polymer" network structure. The technical effect of this structure is that it significantly improves the mechanical properties of the silicone rubber matrix 31 itself, including tensile strength, tear strength, and tensile stress, making the matrix portion, which is the main body of the component, more robust. When the component is subjected to external forces, a more robust matrix can better disperse stress, providing more stable support for the ceramic shell 41 on the surface, thereby improving the structural integrity and fatigue resistance of the entire component under complex working conditions.

[0050] Furthermore, in a more specific embodiment, the material formulation is optimized. Using 100 parts by weight of methyl vinyl silicone rubber as the silicone rubber matrix, 50 to 150 parts by weight of ceramic-forming filler and 5 to 30 parts by weight of flux are added. The technical advantage of this formulation range is that it achieves a good balance between ceramicization performance and processing performance. When the amount of ceramic-forming filler is less than 50 parts, a continuous and dense ceramic layer may not be formed after laser treatment; while when it is greater than 150 parts, the viscosity of the compound is too high, resulting in poor flowability, making molding or extrusion difficult, and the untreated matrix itself may also be too hard and lose some flexibility. Similarly, the amount of flux is also crucial; less than 5 parts, the fluxing effect is not obvious, and the required ceramicization temperature is too high; more than 30 parts, although beneficial for ceramicization, may reduce the refractoriness and high-temperature strength of the final ceramic layer. Therefore, this formulation limits a core formulation space for achieving efficient in-situ ceramicization and good matrix performance.

[0051] In another alternative embodiment, specific materials can be selected to achieve the above formulation. For example, the ceramic filler can be wollastonite, which is chemically stable, inexpensive, and an ideal source of ceramic framework. The flux can be low-melting-point glass powder, which softens at relatively low temperatures, providing an excellent liquid phase environment for the ceramicization reaction. By selecting these specific and proven material combinations, the technical effects of the present invention can be stably and reliably reproduced, reducing the threshold and uncertainty of technical implementation.

[0052] Furthermore, the laser process used is refined. The high-energy laser beam 20 can be generated by various lasers. For example, in applications requiring rapid processing of large areas and prioritizing cost-effectiveness, high-power carbon dioxide lasers or fiber lasers can be selected. When fine patterning or micro-area processing is required, ultraviolet lasers with better beam quality and smaller heat-affected zones can be used. This flexibility allows the method to adapt to various needs, from large-scale industrial production to high-precision customized processing. In addition, by strictly controlling the laser energy density within the range of 10 J / cm² to 200 J / cm², and adjusting the scanning speed from 10 mm / s to 5000 mm / s, the total energy input to the material surface can be precisely controlled. This parameter combination constitutes a wide and stable process window, allowing operators to precisely control the thickness, density, surface roughness, and even microstructure of the final ceramic shell 41 by adjusting specific parameters within this window.

[0053] In another preferred embodiment, the surface of the ceramic shell 41 of the prepared ceramic-silicone rubber component can be further formed with micro-nano rough structures possessing specific functions. This structure can be achieved by controlling parameters such as the pulse width, frequency, and polarization state of the laser during laser processing, or it can be the result of the self-organizing behavior of a specific material system during ultrafast melting and solidification. For example, the formed micron-scale pits and nano-scale villous composite structure can effectively trap air, forming a stable air cushion, thereby giving the surface superhydrophobic properties. This functionalized surface not only enhances the added value of the component but also expands its application scenarios, such as for outdoor seals requiring anti-fouling and self-cleaning properties, or for electronic device housings requiring enhanced hydrophobicity.

[0054] The technical solution of this invention will be illustrated below through a specific application example. Please refer to [link / reference]. Figure 4 This example demonstrates localized surface reinforcement of an O-ring 50 for a power battery pack in a new energy vehicle. Under normal operating conditions, the O-ring 50 needs to provide a reliable seal, therefore its body must maintain excellent elasticity and compression set performance. However, in extreme situations such as thermal runaway of the battery, the side exposed to the outside of the battery pack may face direct impact from high-temperature flames and molten material jets. Traditional silicone rubber would rapidly burn under such conditions, losing its sealing function and allowing the flames to spread.

[0055] To solve this problem, the technical solution of this invention is adopted. First, an O-ring 50 preform made of ceramicizable silicone rubber is prepared by injection molding. Then, it is mounted on a rotatable fixture and placed in a five-axis fiber laser processing center. Based on the three-dimensional digital model of the O-ring 50, a laser scanning trajectory 60 is pre-programmed and set. This trajectory precisely covers the outer half-circumferential surface of the O-ring 50 that may be exposed to danger, while keeping the inner surface, which plays a major sealing role within the groove, untreated.

[0056] At the start of processing, the fixture rotates the O-ring 50 at a set speed, while the laser processing head 10 moves axially and radially in coordination, ensuring that the laser beam 20 always irradiates the O-ring surface at a vertical or near-vertical angle along a preset laser scanning trajectory 60. Laser parameters (e.g., power 180W, average linear velocity 500mm / s) are optimized to ensure uniform energy density during dynamic scanning. In the area swept by the laser beam, the surface material instantly undergoes in-situ ceramization, forming a ceramic layer region 70.

[0057] After processing, a composite O-ring seal is obtained. Its outer surface forms a seamless, dense, and robust ceramic shell, effectively resisting flame erosion exceeding 1000°C and the scouring of molten metal droplets, providing a crucial fire barrier for the battery pack and delaying the spread of thermal runaway. Meanwhile, its inner surface and the sealing surface in contact with the flange fully retain the original flexibility and elasticity of silicone rubber, ensuring its IP67 rating or even higher sealing performance under normal operating conditions. This example demonstrates the digital precision manufacturing capabilities of this invention, and its unique advantage of endowing components with extreme protective capabilities without sacrificing their original core functions.

[0058] To demonstrate a preferred technical effect achievable by combining multiple technical features of the present invention, a comprehensive embodiment is provided below. This embodiment aims to prepare a ceramic-silicone rubber component that combines excellent fire resistance, superior mechanical properties, and high reliability.

[0059] First, the materials are prefabricated. 100 parts by weight of high-performance methyl vinyl silicone rubber is selected as the matrix. Based on this, 30 parts by weight of fumed silica is added as a reinforcing filler to construct a strong and tough matrix 31. Next, 120 parts by weight of micron-sized wollastonite powder is added as the main ceramic-forming filler, supplemented with 20 parts by weight of low-melting-point borosilicate glass powder as a flux. All the above components are thoroughly mixed in an internal mixer to ensure that all powder materials are uniformly dispersed in the silicone rubber matrix. Then, a compression molding and vulcanization process is used to produce a ceramicizable silicone rubber preform 30 of the desired shape.

[0060] Next, in-situ laser ceramicization is performed. A continuous-wave carbon dioxide laser is used, whose emitted laser beam 20 with a wavelength of 10.6 μm has a good absorption rate on the material. The laser beam 20 is focused by an optical system, and the laser power and scanning speed are set so that the energy density acting on the material surface is stabilized at about 100 J / cm², and the scanning speed is controlled at about 600 mm / s. A computer numerical control system controls the laser processing head 10 to perform area-filling scanning on the surface of the preform 30 according to a preset path.

[0061] In the complete workflow, when the laser beam 20 irradiates the surface of the preform 30, the surface material absorbs energy and heats up to approximately 1200°C within milliseconds. Low-melting-point glass powder melts first, forming a molten environment encapsulating wollastonite particles. Simultaneously, the silicone rubber matrix pyrolyzes to produce highly reactive silica nanoparticles. In the high-temperature liquid phase, rapid eutectic and sintering reactions occur among the components. As the laser beam 20 moves, the region cools rapidly, solidifying on the surface to form a dense ceramic layer 40 with a thickness of approximately 50-100 micrometers. Due to the gradient distribution of laser energy and heat along the material's depth, a gradient transition layer 42 with continuously varying composition and hardness is naturally formed between the surface pure ceramic layer 40 and the internal silicone rubber matrix 31. Furthermore, specific micro / nano rough structures are formed on the surface during the rapid melting and solidification process.

[0062] Through the above-described scheme combining all features, the final ceramic-silicone rubber component achieved optimized overall performance. Its comprehensive technical benefits are reflected in: Excellent protective performance: Thanks to optimized material ratios and precise laser process control, the resulting ceramic shell 41 is extremely dense and firmly bonded to the substrate. Compared to implementing only the basic solution, its resistance to flame erosion can be extended by more than 3 times, effectively resisting the long-term erosion of high-temperature molten metal droplets without being damaged.

[0063] Excellent mechanical reliability: The addition of reinforcing filler makes the silicone rubber matrix 31 stronger and tougher, while the presence of gradient transition layer 42 eliminates interfacial stress, making the ceramic layer less prone to cracking or peeling when the component is subjected to repeated bending, stretching or vibration, exhibiting extremely high structural reliability.

[0064] Additional functional value: The micro-nano rough structure formed on the surface endows the component with excellent hydrophobicity, and its static water contact angle can reach more than 140°, giving it self-cleaning ability in humid or dusty environments and extending its service life.

[0065] Highly efficient and flexible manufacturing: The laser process and parameter combination achieve a balance between production efficiency and processing quality. Compared with the traditional integral sintering process, energy consumption is reduced by more than 90%, and local strengthening of any complex surface can be achieved without molds, resulting in extremely high production flexibility.

[0066] It is evident that the synergistic effect of the various technical features of this invention ultimately enables the preparation of a high-performance composite material component that integrates flexibility, high strength, high fire resistance, and functionalized surface, solving a long-standing technical problem in this field.

[0067] The technical solution provided by this invention has broad application prospects and can offer innovative solutions for many fields that have stringent requirements for materials to possess both flexibility and tolerance to extreme environments. In the field of new energy vehicles, this technology can be used to manufacture fireproof sealing gaskets for power battery packs, O-rings 50, insulating sheaths for high-voltage cables, and heat-insulating buffer pads between battery cells. By performing in-situ ceramic treatment on the fire-facing surfaces of these components, a critical line of defense against the spread of thermal runaway can be constructed without affecting their normal sealing, insulation, and buffering functions, greatly improving the safety of electric vehicles.

[0068] In the field of construction engineering, this technology can be used to produce high-performance fire-stopping materials. For example, flexible fire-resistant sealing rings or fire-resistant putty for cable and pipe penetrations in walls and floors. These materials need to remain flexible under normal conditions to accommodate minor displacements and thermal expansion and contraction of buildings, while in the event of a fire, their fire-facing surfaces can quickly form a hard ceramic layer, effectively sealing flames and toxic fumes, buying valuable time for evacuation and rescue.

[0069] In the aerospace field, there are extremely high requirements for lightweight materials and their resistance to extreme environments. This technology can be used to manufacture fireproof seals for aircraft engine compartments, protective sleeves for hydraulic lines, and thermal insulation gaskets for rocket fuel tanks. This method allows the construction of a ceramic protective layer on a lightweight silicone rubber matrix that can withstand high temperatures and high-speed airflow, resulting in significant weight reduction compared to traditional metal or monolithic ceramic solutions.

[0070] Furthermore, in fields such as rail transportation, power communication, high-end equipment manufacturing, and even consumer electronics, wherever flexible materials are required to perform functions such as sealing, shock absorption, and insulation, while simultaneously facing potential risks such as fire, high temperatures, and wear, the technical solution of this invention can provide an efficient solution. For example, fireproof door and window sealing strips used in subway vehicles, insulator sleeves in substations, and wear-resistant shock-absorbing pads for precision instruments can all achieve significant performance improvements through this technology. The flexibility and digital manufacturing characteristics of this invention enable it to quickly respond to customized needs in different industries and scenarios.

Claims

1. A method for constructing a ceramic shell on a ceramizable silicone rubber surface, characterized in that, Includes the following steps: Prepare a ceramizable silicone rubber preform, wherein the ceramizable silicone rubber comprises: a silicone rubber matrix, a ceramic filler, and a flux; A predetermined surface area of ​​the ceramicizable silicone rubber preform is irradiated with a high-energy laser beam; The energy and duration of the irradiation are sufficient to transform the material in the predetermined surface area into a ceramic layer in situ.

2. The method according to claim 1, characterized in that, The ceramizable silicone rubber also contains reinforcing fillers.

3. The method according to claim 1 or claim 2, characterized in that, Based on 100 parts by weight of the silicone rubber matrix, the amount of the ceramic filler is 50-150 parts by weight, and the amount of the flux is 5-30 parts by weight.

4. The method according to claim 1, characterized in that, The ceramic filler is selected from at least one of wollastonite, mica powder, kaolin, or talc powder.

5. The method according to claim 1, characterized in that, The flux is selected from at least one of low-melting-point glass powder, zinc borate, or borax.

6. The method according to claim 1, characterized in that, The high-energy laser beam is selected from carbon dioxide lasers, fiber lasers, ultraviolet lasers, or excimer lasers.

7. The method according to claim 1, characterized in that, The energy density of the irradiation is from 10 J / cm² to 200 J / cm².

8. The method according to claim 1, characterized in that, The irradiation is achieved by scanning the predetermined surface area at a scanning speed of 10 mm / s to 5000 mm / s.

9. A ceramic silicone rubber component, characterized in that, include: A matrix made of ceramizable silicone rubber; And a ceramic shell disposed on the surface of the substrate; wherein, there is a gradient transition layer with a gradual change in composition or structure from the substrate to the ceramic shell.

10. The component according to claim 9, characterized in that, The surface of the ceramic shell has a micro-nano rough structure.

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