Preparation method of non-symmetrical surfactant yttrium-based ceramic corrosion-resistant slurry
Patent Information
- Application Number
- CN202610949176.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-29
- Publication Date
- 2026-10-09
AI Technical Summary
本发明通过合成非对称两性表面活性剂并协同超声—球磨工艺，显著降低了浆料的平均粒度、改善了陶瓷颗粒的分散性，所制涂层表面硬度高达1650—1700HV，接触角达136—139°，同时摩擦系数低至0.62—0.66、磨损率仅2.34×10—6~3.26×10-6mm3/N·m，从而兼具高硬度、强疏水、低摩擦、耐磨损和抗腐蚀等综合性能，既解决了陶瓷粉体团聚问题、提升了浆料稳定性，又形成了疏水防护屏障，显著增强耐蚀能力，且合成与制备工艺条件温和、参数可控，可为动力电池箱底板等易受腐蚀磨损的关键构件，提供长效耐磨耐蚀一体化防护方案。
Smart Images
Figure CN122878792A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of reinforced ceramic coating products, specifically a method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry. Background Technology
[0002] When engineering equipment operates under harsh conditions such as marine environments and industrial atmospheres, the synergistic effect of corrosion and wear can significantly accelerate material failure. This coupled damage manifests as follows: friction damages the protective film on the material surface (such as passivation film and coating), causing fresh metal to be continuously exposed to the corrosive medium. At the same time, the loose layer formed by corrosion products exacerbates abrasive wear. Related studies have shown that the material loss rate under the synergistic effect of corrosion and wear can be 3 to 10 times that under the action of a single factor, seriously threatening the long-term service reliability of key aerospace components and marine engineering equipment.
[0003] Surface coating technology provides an effective way to solve the engineering problem of corrosion-wear synergistic damage. By constructing a coating with specific functional properties on the substrate surface, it is possible not only to significantly improve the surface hardness of the material, which can typically be 2-5 times that of the substrate, but more importantly, it can form a dense protective barrier, effectively blocking the penetration of corrosive media and reducing the corrosion current density by 1-3 orders of magnitude. The breakthrough of this technology lies in the synergistic optimization of wear resistance and corrosion resistance, which can simultaneously take into account the mechanical properties and chemical stability of the coating. Based on this, a method for preparing asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry is now provided, which can eliminate the drawbacks of existing devices. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing a yttrium-based ceramic corrosion-resistant slurry with an asymmetric surfactant, so as to solve the problems in the background art.
[0005] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing an asymmetric surfactant-based yttrium-based ceramic corrosion-resistant slurry includes the following steps: Step 1: Preparation of tetradecylphenol glycidyl ether: Using tetrabutylammonium bromide as a catalyst, weigh a certain amount of 4-tetradecylphenol and tetrabutylammonium bromide into a 250ml three-necked flask, use petroleum ether as the reaction solvent, stir and mix thoroughly, then add epichlorohydrin, and react in an environment with a certain temperature. After the reaction, slowly add a certain amount of sodium hydroxide aqueous solution. After the addition is complete, continue the reaction. After the reaction is complete, filter under reduced pressure, wash the filtrate with distilled water until neutral, collect the organic phase with a separatory funnel, and obtain tetradecylphenol glycidyl ether by rotary evaporation. Step 2: Preparation of cationic surfactant: Take a measured amount of ethanol solution of dodecyl dimethyl tertiary amine and place it in a 250 ml three-necked flask equipped with a reflux condenser. Then add ammonium chloride catalyst. Under a certain temperature environment, while stirring, slowly add a measured amount of tetradecylphenol glycidyl ether dropwise using a dropping funnel. After the reaction is completed, cool to room temperature and use a rotary evaporator to remove excess tertiary amine and ethanol to obtain {N-[(4-tetradecylphenoxy-2-hydroxy)propyl]-N-alkyl-N-dimethyl}ammonium chloride; Step 3: Preparation of the mixed solution: Prepare 100 ml of a water-alcohol mixed solvent, then add {N-[(4-tetradecylphenoxy-2-hydroxy)propyl]-N-alkyl-N-dimethyl}ammonium chloride, , , Benzyl dimethylamine was deagglomerated using a high-energy ultrasonic cell disruptor. Step 4: Ball milling and pH adjustment: After deagglomerating the mixed solution in Step 3, transfer it to a ball mill jar and then to a planetary ball mill. After ball milling, pour out the mixed slurry, add ammonia water and stir to adjust the pH of the solution to 6, and obtain the ceramic corrosion-resistant coating slurry.
[0006] Based on the above technical solutions, the present invention also provides the following optional technical solutions: In one alternative: in step one, the amount of petroleum ether used is 100 ml, the amount of 4-tetradecylphenol used is 290 g / L, the amount of tetrabutylammonium bromide used is 8-10 g / L, the amount of epichlorohydrin used is 100-110 g / L, and the amount of sodium hydroxide aqueous solution used is 20-25 ml / L.
[0007] In one alternative: the reaction temperature in step one is 60℃, the reaction time before addition is 3h, the addition rate is 3ml / min, and the reaction time after addition is 3h.
[0008] In one alternative: in step two, the amount of tetradecylphenol glycidyl ether used is 380 g / L, the amount of ethanol solution of dodecyl dimethyl tertiary amine used is 230 g / L, and the amount of ammonium chloride used is 2.1 g / L.
[0009] In one alternative: the stirring temperature in step two is 80°C, and the reaction time is 7 hours.
[0010] In one alternative: the ratio of water to alcohol mixed solvent in step three is water: anhydrous ethanol = 80 mL: 20 mL, and the amount of {N-[(4-tetradecylphenoxy-2-hydroxy)propyl]-N-alkyl-N-dimethyl} ammonium chloride is 1 g. The dosage is 1g. The dosage is 12g. The dosage is 1g, and the dosage of benzyl dimethylamine is 3g.
[0011] In one alternative: the high-energy ultrasonic cell disruptor in step three is model JY92-IIN, with an output power of 80W and a duration of 10 minutes.
[0012] In one alternative: the planetary ball mill in step four is model QM-SP, with a rotation speed of 300 r·min-1, and the time is 30 minutes of forward rotation followed by 30 minutes of reverse rotation at the same speed.
[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention, through the synthesis of asymmetric amphoteric surfactants and the synergistic use of ultrasonic-ball milling, significantly reduces the average particle size of the slurry and improves the dispersibility of ceramic particles. The resulting coating exhibits a surface hardness of 1650-1700 HV, a contact angle of 136-139°, and simultaneously a low coefficient of friction of 0.62-0.66 and a wear rate of only 2.34 × 10⁻⁶. 6 ~3.26×10 -6 mm 3 / N·m, thus possessing comprehensive properties such as high hardness, strong hydrophobicity, low friction, wear resistance and corrosion resistance. It not only solves the problem of ceramic powder agglomeration and improves the stability of slurry, but also forms a hydrophobic protective barrier, significantly enhancing corrosion resistance. Moreover, the synthesis and preparation process conditions are mild and the parameters are controllable, which can provide a long-lasting wear-resistant and corrosion-resistant integrated protection solution for key components such as the bottom plate of power battery boxes that are susceptible to corrosion and wear. Attached Figure Description
[0014] Figure 1 This is a schematic diagram of the process steps of the present invention.
[0015] Figure 2 This is a schematic diagram of the reaction formula for tetradecylphenol glycidyl ether of the present invention.
[0016] Figure 3 This is a schematic diagram of the ammonium chloride reaction formula of the present invention. Detailed Implementation
[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments.
[0018] Example 1 A method for preparing an asymmetric surfactant-based yttrium-based ceramic corrosion-resistant slurry includes the following steps: Example 2 A method for preparing an asymmetric surfactant-based yttrium-based ceramic corrosion-resistant slurry includes the following steps: The coatings in the above embodiments were applied and dried before being measured. (1) Hardness: The microhardness of the above-mentioned examples was determined by Vickers microhardness test, wherein the load was 50g, the indenter was a conical indenter, and the holding time was 10s. (2) Contact angle: The contact angle of the sample surface was measured using a contact angle measuring instrument, and the droplet volume was 5 μL; (3) Friction coefficient and wear rate: The friction and wear test of the reinforced layer was carried out according to ASTM G133. The reciprocating friction method was adopted, the friction test temperature was room temperature, the load was set to 80N, the reciprocating length was 5mm, the running speed was 800t / min, and the wear time was 10min. The ceramic surfaces prepared in Examples 1-2 were subjected to relevant performance tests, and the test results are shown in Table 1: Table 1 As shown in Table 1, the coating properties obtained in Examples 1-2 of this invention are within the performance standard range. Therefore, the method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry provided by this invention involves synthesizing tetrabutylammonium bromide as a catalyst to synthesize tetradecylphenol glycidyl ether, and then reacting it with dodecyl dimethyl tertiary amine (MW=213) under ammonium chloride catalysis to obtain {N-[(4-tetradecylphenoxy-2-hydroxy)propyl]-N-alkyl-N-dimethyl} ammonium chloride asymmetric amphoteric surfactant. Then, this surfactant is sequentially added to a water-alcohol mixed solvent. , , The mixture was subjected to ultrasonic deagglomeration and planetary ball milling with benzyl dimethylamine, and finally adjusted to pH=6 with ammonia water to obtain the finished slurry. This method utilizes asymmetric amphoteric surfactants to effectively reduce the average particle size of the slurry and improve its dispersibility. The resulting coating has a surface hardness of 1650–1700 HV, a contact angle of 136–139°, a coefficient of friction of 0.62–0.66, and a wear rate as low as 2.34 × 10⁻⁶. -6 mm 3 / (N·m), which combines high hardness, high hydrophobicity and excellent wear and corrosion resistance, its key technical points include a two-step synthesis route of specific structure surfactants, precise formulation of yttrium-based ceramic slurry and ultrasonic-ball milling synergistic preparation process, which can protect the corresponding surfactant synthesis method, ceramic slurry formulation and preparation process. The process is controllable and easy to scale up, and can provide long-term wear and corrosion protection for components such as the bottom plate of power battery box; It should be noted that {N-[(4-tetradecylphenoxy-2-hydroxy)propyl]-N-alkyl-N-dimethyl} ammonium chloride is a quaternary ammonium salt cationic surfactant with a molecule consisting of a long-chain hydrophobic tail (4-tetradecylphenoxy), a hydroxyl-containing linker arm (2-hydroxypropyl), and a positively charged hydrophilic head (N-alkyl-N-dimethylammonium). It is readily soluble in water and ethanol, stable over a wide pH range, and possesses excellent bactericidal, bacteriostatic, antistatic, emulsifying, and softening properties. It has low irritation and should not be mixed with anionic surfactants. The sodium hydroxide (50% mass concentration, W / W) aqueous solution indicates that every 100 grams of this solution contains 50 grams of sodium hydroxide and 50 grams of water.
[0019] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.
Claims
1. A method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry, characterized in that, Includes the following steps: Step 1: Preparation of tetradecylphenol glycidyl ether: Using tetrabutylammonium bromide as a catalyst, weigh a certain amount of 4-tetradecylphenol and tetrabutylammonium bromide into a 250ml three-necked flask, use petroleum ether as the reaction solvent, stir and mix thoroughly, then add epichlorohydrin, and react in an environment with a certain temperature. After the reaction, slowly add a certain amount of sodium hydroxide aqueous solution. After the addition is complete, continue the reaction. After the reaction is complete, filter under reduced pressure, wash the filtrate with distilled water until neutral, collect the organic phase with a separatory funnel, and obtain tetradecylphenol glycidyl ether by rotary evaporation. Step 2: Preparation of cationic surfactant: Take a measured amount of ethanol solution of dodecyl dimethyl tertiary amine and place it in a 250 ml three-necked flask equipped with a reflux condenser. Then add ammonium chloride catalyst. Under a certain temperature environment, while stirring, slowly add a measured amount of tetradecylphenol glycidyl ether dropwise using a dropping funnel. After the reaction is completed, cool to room temperature and use a rotary evaporator to remove excess tertiary amine and ethanol to obtain {N-[(4-tetradecylphenoxy-2-hydroxy)propyl]-N-alkyl-N-dimethyl}ammonium chloride; Step 3: Preparation of the mixed solution: Prepare 100 ml of a water-alcohol mixed solvent, then add {N-[(4-tetradecylphenoxy-2-hydroxy)propyl]-N-alkyl-N-dimethyl}ammonium chloride, , , Benzyl dimethylamine was deagglomerated using a high-energy ultrasonic cell disruptor. Step 4: Ball milling and pH adjustment: After deagglomerating the mixed solution in Step 3, transfer it to a ball mill jar and then to a planetary ball mill. After ball milling, pour out the mixed slurry, add ammonia water and stir to adjust the pH of the solution to 6, and obtain the ceramic corrosion-resistant coating slurry.
2. The method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry according to claim 1, characterized in that, In step one, the amount of petroleum ether used is 100 ml, the amount of 4-tetradecylphenol used is 290 g / L, the amount of tetrabutylammonium bromide used is 8-10 g / L, the amount of epichlorohydrin used is 100-110 g / L, and the amount of sodium hydroxide aqueous solution used is 20-25 ml / L.
3. The method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry according to claim 1, characterized in that, In step one, the reaction temperature is 60℃, the reaction time before addition is 3 hours, the addition rate is 3 ml / min, and the reaction time after addition is 3 hours.
4. The method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry according to claim 1, characterized in that, In step two, the amount of tetradecylphenol glycidyl ether used is 380 g / L, the amount of ethanol solution of dodecyl dimethyl tertiary amine used is 230 g / L, and the amount of ammonium chloride used is 2.1 g / L.
5. The method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry according to claim 1, characterized in that, In step two, the stirring temperature is 80℃ and the reaction time is 7 hours.
6. The method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry according to claim 1, characterized in that, In step three, the ratio of the water-ethanol mixed solvent is water: anhydrous ethanol = 80 mL: 20 mL, and the amount of {N-[(4-tetradecylphenoxy-2-hydroxy)propyl]-N-alkyl-N-dimethyl} ammonium chloride is 1 g. The dosage is 1g. The dosage is 12g. The dosage is 1g, and the dosage of benzyl dimethylamine is 3g.
7. The method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry according to claim 1, characterized in that, In step three, the high-energy ultrasonic cell disruptor is model JY92-IIN, with an output power of 80W and a duration of 10 minutes.
8. The method for preparing an asymmetric surfactant yttrium-based ceramic corrosion-resistant slurry according to claim 1, characterized in that, In step four, the planetary ball mill is model QM-SP, with a rotation speed of 300 r·min-1, and the time is 30 minutes of forward rotation followed by 30 minutes of reverse rotation at the same speed.