Electronic ceramic element and preparation method thereof
By incorporating sacrificial elements with high oxygen affinity into the copper electrode material, the problem of insufficient bonding force between the copper electrode layer and the ceramic core is solved, resulting in better bonding strength and conductivity, and improving the stability and oxidation resistance of electronic ceramic components.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-03-03
- Publication Date
- 2026-04-07
AI Technical Summary
In the existing technology, the bonding force between the copper electrode layer and the ceramic core is insufficient, and it is prone to oxidation during high-temperature sintering or long-term operation, which leads to a decrease in interfacial adhesion and affects the conductivity and stability of electronic ceramic components.
Sacrificial elements such as nickel, tin, silicon, sulfur, selenium, tellurium, titanium, phosphorus, manganese, and aluminum are incorporated into copper electrode materials. These elements react with oxygen to form stable oxides, which enhance the bonding strength between the electrode layer and the ceramic core. The mechanical locking effect and interface wetting effect also improve the bonding force, while alleviating stress concentration caused by differences in thermal expansion coefficients.
It effectively improves the bonding force between the copper electrode and the ceramic core, enhances the density and conductivity stability of the electrode layer, strengthens the oxidation resistance and thermal shock resistance, and improves the long-term reliability of electronic ceramic components.
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Abstract
Description
Technical Field
[0001] This application relates to the field of metal alloy technology, and in particular to an electronic ceramic element and its preparation method. Background Technology
[0002] Electronic ceramic components are a class of electronic devices that primarily use ceramic materials and leverage their electrical properties to achieve sensing or protection functions. They are commonly used in temperature measurement, overcurrent protection, circuit compensation, and voltage suppression. Electronic ceramic components can be positive temperature coefficient thermistors (PTC), negative temperature coefficient thermistors (NTC), or varistors, etc. These components typically contain a ceramic core sintered at high temperatures, which possesses stable and repeatable electrical characteristics. To ensure reliable conduction between the electronic ceramic component and external circuits, electrode layers are usually formed at both ends or on the surface of the ceramic core.
[0003] In existing technologies, metal electrode layers can be prepared by electroplating, electroless plating, spraying, sputtering, or screen printing and sintering, with copper being a common electrode material. In addition to providing good electrical conductivity and mechanical adhesion, this metal electrode layer also has thermal conductivity, facilitating the rapid transfer of heat or electrical signals to the ceramic core, thereby improving the responsiveness and stability of electronic ceramic components.
[0004] In existing processes, insufficient bonding strength between the copper electrode and the ceramic core is a major technical bottleneck. This is due to the significant difference in their coefficients of thermal expansion, coupled with the tendency for copper to oxidize during high-temperature sintering, welding, or long-term operation, forming a copper oxide layer that reduces the interfacial adhesion between the metal and ceramic. Particularly in thermal spraying, copper rapidly melts under arc or flame heating and is sprayed at high speed onto the ceramic substrate surface to form a coating. This process involves a transient high-energy state and a rapid cooling and solidification mechanism. Molten copper particles rapidly spread and solidify upon impact with the substrate, forming a dense or semi-dense metallic layer structure. During this process, the arc region is in a high-energy state. Although the deposited layer dissipates heat rapidly after formation, and the substrate as a whole is not continuously exposed to a high-temperature environment, the atmospheric conditions in the spraying environment can still affect the degree of oxidation of the copper particles. Under these conditions, copper may react with oxygen to form Cu₂O or CuO, leading to reduced conductivity, increased internal porosity, and insufficient adhesion in the coating.
[0005] To address these issues, existing technologies have proposed introducing inert gases as carrier or protective gases during metal spraying, such as nitrogen as the spraying medium, to reduce the risk of metal oxidation during the spraying process. However, such inert gas spraying methods typically require additional gas supply and safety monitoring systems, increasing equipment complexity and manufacturing costs. Furthermore, limitations remain in process management and long-term stability under mass production conditions. Therefore, considering the needs for process simplification, cost control, and large-scale production, atmospheric spraying technology remains a common process for preparing electrode layers in electronic ceramic components. Summary of the Invention
[0006] In order to improve the bonding effect between the copper electrode layer and the ceramic core, and at the same time suppress oxidation, this application provides an electronic ceramic element and its preparation method.
[0007] In a first aspect, this application provides an electronic ceramic component, which adopts the following technical solution: An electronic ceramic component includes a ceramic core and electrode layers respectively disposed on both sides of the ceramic core. The electrode layer material contains copper and a sacrificial element, wherein the sacrificial element is at least two of nickel, tin, silicon, sulfur, selenium, tellurium, titanium, phosphorus, manganese and aluminum. The weight percentage of each sacrificial element in the electrode layer material is 0.5%-2.0%.
[0008] By employing the above-mentioned technical solution, sacrificial elements such as nickel, tin, silicon, sulfur, selenium, tellurium, titanium, phosphorus, manganese, and aluminum, which have high oxygen affinity, are incorporated into the copper electrode material. Firstly, during the spraying process, these elements preferentially react with oxygen to form stable oxides, thereby inhibiting copper oxidation and maintaining a localized liquid state and good wettability on the electrode surface, enhancing the bonding strength between the electrode layer and the ceramic core. The molten copper alloy can penetrate into the micropores or recessed areas of the ceramic core surface, generating a mechanical locking effect, significantly improving the interfacial adhesion strength between the metal and ceramic, and enhancing the density and conductivity stability of the electrode layer. The sacrificial elements of nickel, tin, silicon, sulfur, selenium, tellurium, titanium, phosphorus, manganese, and aluminum can form a transition zone between the copper and ceramic core, alleviating stress concentration caused by differences in thermal expansion coefficients, thus improving the component's thermal shock resistance and long-term reliability. Therefore, through the dual effects of sacrificial elements, copper alloying, and interfacial wetting, the bonding force between the copper electrode and the ceramic core is effectively improved, while simultaneously maintaining good conductivity and oxidation resistance.
[0009] Preferably, the weight percentage of each sacrificial element in the electrode layer is 0.5%-1.5%.
[0010] Preferably, the total weight of the sacrificial elements accounts for 1.5%-2.5% of the total weight of the electrode layer.
[0011] Preferably, the electrode layer contains at least three sacrificial elements, including silicon and two other sacrificial elements. The other two sacrificial elements are any two of nickel, tin, sulfur, selenium, tellurium, titanium, phosphorus, manganese and aluminum. The total weight ratio of silicon to the other two sacrificial elements is 0.15%-0.45%.
[0012] Preferably, the weight ratio between the other two sacrificial elements is 0.5%-1.5%.
[0013] Preferably, the electrode layer contains at least three sacrificial elements, namely silicon, tin and manganese.
[0014] By adopting the above technical solution, the combination of silicon, manganese, and tin can balance the glass phase and oxide structure in the electrode layer, further reducing the brittleness of the electrode layer and improving its strength.
[0015] Preferably, the total weight of tin and manganese accounts for 1.3%-2.0% of the total weight of the electrode layer.
[0016] By adopting the above technical solution and controlling the content of manganese and tin within a reasonable range, a continuous electrode film can be formed, which has both good film strength and brittleness, while reducing the probability of increased oxidation and reducing the phenomenon of brittle and easily cracked electrode film.
[0017] Preferably, the electrode layer material further includes oxygen, and the weight percentage of oxygen in the electrode layer is 2.0%-3.5%.
[0018] Preferably, the total weight of oxygen and other sacrificial elements accounts for 1.5%-2.2% of the total weight of the electrode layer material.
[0019] Preferably, the ceramic core comprises raw materials in the following weight percentages: 60-90 wt% manganese oxide, 5-30 wt% nickel oxide, and 1-30 wt% copper oxide; the total content of each component in the raw materials of the ceramic core is 100 wt%.
[0020] By adopting the above technical solution, manganese oxide, copper oxide, and nickel oxide are combined. The three oxides have similar sintering activity, and after sintering, they form a dense and solid ceramic body, reducing the chemical reaction with copper and enabling the sintering of a defect-free ceramic core.
[0021] Secondly, this application provides a method for preparing an electronic ceramic component, which adopts the following technical solution: A method for preparing an electronic ceramic component includes the following specific steps: cleaning and drying the ceramic core; depositing electrode layer materials composed of elements such as silicon, manganese, tin, and copper onto both ends of the ceramic core through thermal spraying; and allowing it to cool statically to form an electrode layer, thereby obtaining the electronic ceramic component.
[0022] By adopting the above technical solution, copper electrode layers are formed on both ends of the ceramic core. During the subsequent heating process, silicon, manganese, and tin in the electrode layer raw materials preferentially react with oxygen, inhibiting copper oxidation and generating a localized liquid phase. This liquid phase penetrates into the micropores and grooves on the ceramic surface and forms a transition reaction layer with the oxide. After cooling and solidification, a stable composite interface is formed between the metal electrode layer and the ceramic core. During heating, silicon, manganese, and tin react with oxygen to generate composite oxides, located at the interface between the copper electrode layer and the ceramic core, forming a reaction layer with adhesive and chemical bonding properties. This layer combines mechanical locking and chemical bridging functions, effectively enhancing the bonding strength between the ceramic core and the electrode layer. The ceramic grain surface contains microporous structures partially infiltrated by the liquid alloy, forming metal-infiltrated wedges and creating a three-way interface of metal-oxide-ceramic, further improving the adhesion strength between the electrode layer and the ceramic core.
[0023] In summary, this application has the following beneficial effects: 1. This application incorporates sacrificial elements such as nickel, tin, silicon, sulfur, selenium, tellurium, titanium, phosphorus, manganese, and aluminum, which have high oxygen affinity, into the copper electrode material. These sacrificial elements have high oxygen affinity and can preferentially react with oxygen during heating, thereby inhibiting copper oxidation to a certain extent and helping to form a local liquid phase. The liquid phase penetrates into the micropores and grooves on the ceramic surface and forms a transition reaction layer with the oxide. After cooling and solidification, a stable composite interface is formed between the metal electrode layer and the ceramic core, effectively improving the bonding force between the electrode layer and the ceramic core, while maintaining good conductivity and oxidation resistance.
[0024] 2. In this application, raw materials such as manganese trioxide, copper oxide, and nickel trioxide are combined, granulated by ball milling to form granulated powder, and then dry-pressed and debinded to obtain a ceramic core. The three oxides have similar melting points and sintering activities, and after sintering, a dense and solid ceramic body is formed, which reduces the chemical reaction with copper. Detailed Implementation
[0025] The present application will be further described in detail below with reference to the embodiments.
[0026] All raw materials used in the examples are commercially available. Example Example 1
[0027] This embodiment provides an electronic ceramic component, including a ceramic core and electrodes respectively disposed on both sides of the ceramic core; the ceramic core comprises the following raw materials by weight percentage: 62% manganese oxide, 11% copper oxide, and 27% nickel oxide.
[0028] The raw material element composition used to form the electrode layer includes the following weight percentages: oxygen 0.7%, silicon 0.36%, manganese 0.15%, tin 0.39%, with the balance being copper.
[0029] The preparation method of electronic ceramic components includes the following specific steps: manganese trioxide, copper oxide, and nickel trioxide are mixed and granulated by ball milling to form granulated powder, which is then dry-pressed and sintered at 1140℃ for 25 hours to obtain a ceramic core; electrode layer raw materials composed of elements such as silicon, manganese, tin, and copper are deposited on both ends of the ceramic core through a thermal spraying process to form an electrode layer; in the thermal spraying process, by adjusting the voltage and current parameters of the spraying equipment, the copper material is melted under the action of an electric arc and sprayed onto the surface of the ceramic core under the action of a high-speed airflow to complete the deposition. The molten copper particles spread rapidly after impacting the substrate and cool and solidify. After the deposition layer is formed, the actual surface temperature is about 55℃. After static cooling, a copper electrode layer is formed, and the electronic ceramic component is obtained.
[0030] Example 2
[0031] The difference between Example 2 and Example 1 is that the electrode layer comprises the following raw materials by weight percentage: 0.48% oxygen, 0.40% silicon, 0.40% manganese, 0.72% tin, with the balance being copper.
[0032] Example 3 The difference between Example 3 and Example 1 is that the ceramic core includes the following raw materials by weight percentage: 75% manganese oxide, 10% copper oxide, and 15% nickel oxide.
[0033] Example 4 The difference between Example 4 and Example 1 is that the ceramic core includes the following raw materials by weight percentage: 68% manganese oxide, 12% copper oxide, and 20% nickel oxide.
[0034] Comparative Example Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the copper electrode layer is made of copper.
[0035] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the electrode layer comprises the following raw materials by weight percentage: 0.15% silicon, 0.18% manganese, 0.38% tin, 0.43% oxygen, with the balance being copper.
[0036] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the electrode layer comprises the following raw materials by weight percentage: silicon 0.32%, manganese 0.39%, tin 0.71%, iron 0.1%, oxygen 1.06%, and the balance being copper.
[0037] Performance testing The electronic ceramic components provided in Examples 1-4 and Comparative Examples 1-3 of this application were subjected to the following performance tests, and the specific test results are shown in the table below.
[0038] Detection methods 1. Electrode layer content detection: Detect the element content in the electrode layer of the electronic ceramic component product prepared in this application.
[0039] Table 1: Weight percentage of elements in the electrode layer (wt%)
[0040] 2. Appearance inspection: Visually inspect 36 electrode layers sprayed at one time, and record the number of peeling parts after spraying.
[0041] 3. Tensile test: In each embodiment, the electronic ceramic component prepared in this application is used as a sample. Six groups are taken as tensile test samples and the average value is taken. The two wires of the electronic ceramic component are bent at 90° at the lower edge of the body in opposite directions perpendicular to the plane of the body. Then the wires are broken on the tensile tester and the tensile force value is recorded.
[0042] Table 2: Performance Test Results Data Table
[0043] The performance test results show that the electronic ceramic components prepared in this application have good structural stability and adhesion. A comparison of Comparative Examples 1-3 and Example 1 shows that changing any raw material in the electrode layer prepared in this application can affect the adhesion of the electrode layer. Furthermore, silicon, manganese, and tin preferentially react with oxygen during the spraying process, enhancing the bonding strength between the copper electrode layer and the ceramic core.
[0044] As can be seen from Examples 1-2, by using a suitable ratio of sacrificial elements, the prepared electrode layer has good tensile strength and adhesion, and the copper electrode layer prepared by the sacrificial elements used in Example 1 has better overall performance.
[0045] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.
Claims
1. An electronic ceramic component, characterized in that, The device includes a ceramic core and electrode layers respectively disposed on both sides of the ceramic core. The electrode layer material contains copper and sacrificial elements. The sacrificial elements are at least two of nickel, tin, silicon, sulfur, selenium, tellurium, titanium, phosphorus, manganese and aluminum. The weight percentage of each sacrificial element in the electrode layer material is 0.5%-2.0%.
2. The electronic ceramic component according to claim 1, characterized in that, The weight percentage of each sacrificial element in the electrode layer is 0.5%-1.5%.
3. The electronic ceramic component according to claim 2, characterized in that, The total weight of the sacrificial elements accounts for 1.5%-2.5% of the total weight of the electrode layer.
4. The electronic ceramic component according to claim 1, characterized in that, The electrode layer contains at least three sacrificial elements, including silicon and two other sacrificial elements. The other two sacrificial elements are any two of nickel, tin, sulfur, selenium, tellurium, titanium, phosphorus, manganese and aluminum. The total weight ratio of silicon to the other two sacrificial elements is 0.15%-0.45%.
5. The electronic ceramic component according to claim 4, characterized in that, The weight ratio between the other two sacrificial elements is 0.5%-1.5%.
6. The electronic ceramic component according to claim 4, characterized in that, The electrode layer contains at least three sacrificial elements, namely silicon, tin and manganese.
7. The electronic ceramic component according to claim 6, characterized in that, The total weight of tin and manganese accounts for 1.3%-2.0% of the total weight of the electrode layer.
8. The electronic ceramic component according to claim 1, characterized in that, The electrode layer material also includes oxygen, and the weight percentage of oxygen in the electrode layer is 2.0%-3.5%.
9. The electronic ceramic component according to claim 8, characterized in that, The total weight of oxygen and other sacrificial elements accounts for 1.5%-2.2% of the total weight of the electrode layer material.
10. A method for preparing an electronic ceramic component as described in any one of claims 1-9, characterized in that, The specific steps include: cleaning and drying the ceramic core; depositing electrode layer materials composed of elements such as silicon, manganese, tin, and copper onto both ends of the ceramic core through thermal spraying; allowing it to cool and stand to form the electrode layer, thus producing the electronic ceramic component.