技术领域Technical field
本发明属于稀土金属技术领域，具体涉及有机抗氧化组合物及稀土金属或稀土合金表面抗氧化方法。The invention belongs to the technical field of rare earth metals, and specifically relates to organic antioxidant compositions and rare earth metal or rare earth alloy surface antioxidant methods.
背景技术Background technique
稀土金属主要用于生产高性能稀土永磁材料，是电子信息、新能源汽车、新材料等领域重要基础原料。稀土金属的生产工艺主要以熔盐电解法为主。该工艺以氟化稀土-氟化锂-氧化稀土为电解质体系RE2O3-REF3-LiF，该体系由于电流效率高，且稀土氧化物不易受潮吸水等优点，是熔盐电解法生产稀土金属或者合金的首选。Rare earth metals are mainly used to produce high-performance rare earth permanent magnet materials and are important basic raw materials in fields such as electronic information, new energy vehicles, and new materials. The production process of rare earth metals is mainly based on molten salt electrolysis. This process uses rare earth fluoride-lithium fluoride-rare earth oxide as the electrolyte system RE2 O3 -REF3 -LiF. This system has the advantages of high current efficiency and the rare earth oxide is not susceptible to moisture and water absorption. It is the best method for producing rare earth by molten salt electrolysis. Metals or alloys are preferred.
稀土金属化学性质活泼，容易和空气中的氧气发生化学反应，生成稀土氧化物。尤其是在熔盐电解过程中，由于生成稀土金属环节不在真空条件下进行，稀土金属或者合金在高温条件下和空气中的氧气或者氮气发生氧化或者氮化反应剧烈。过一段时间后，由于受潮和电化学腐蚀等原因，造成稀土金属或者合金表面氧化现象非常严重，给下游的磁性材料制备企业带来危害。Rare earth metals are chemically active and easily react chemically with oxygen in the air to form rare earth oxides. Especially in the molten salt electrolysis process, since the generation of rare earth metals is not carried out under vacuum conditions, the rare earth metals or alloys undergo violent oxidation or nitridation reactions with oxygen or nitrogen in the air under high temperature conditions. After a period of time, due to factors such as moisture and electrochemical corrosion, the surface oxidation of rare earth metals or alloys is very serious, causing harm to downstream magnetic material preparation companies.
发明内容Contents of the invention
本发明的目的在于提供有机抗氧化组合物及稀土金属或稀土合金表面抗氧化方法，本发明提供的有机抗氧化组合物能阻隔稀土金属或者合金和空气的直接接触，减少了稀土金属或者合金的表面氧化。The object of the present invention is to provide an organic antioxidant composition and a rare earth metal or rare earth alloy surface antioxidant method. The organic antioxidant composition provided by the invention can block the direct contact between the rare earth metal or alloy and the air, reducing the risk of rare earth metal or alloy Surface oxidation.
为了实现上述目的，本发明提供如下技术方案：In order to achieve the above objects, the present invention provides the following technical solutions:
本发明提供了一种用于稀土金属或稀土合金表面抗氧化的有机抗氧化组合物，包括以下质量百分含量的组分：叔十二硫醇0.5~1%，树脂粘结剂1~3%，有机稀释剂96~98.5%。The invention provides an organic antioxidant composition for rare earth metal or rare earth alloy surface antioxidant, including the following mass percentage components: tert-dodecanethiol 0.5~1%, resin binder 1~3 %, organic diluent 96~98.5%.
优选的，所述树脂粘结剂为环氧树脂粘结剂。Preferably, the resin adhesive is an epoxy resin adhesive.
优选的，所述有机稀释剂由丙三酮和/或乙醇组成。Preferably, the organic diluent consists of glycerol and/or ethanol.
优选的，所述有机稀释剂包括丙三酮和乙醇时，所述丙三酮和乙醇的体积比为（3~4）：1。Preferably, when the organic diluent includes glycerol and ethanol, the volume ratio of glycerin and ethanol is (3~4):1.
本发明提供了一种稀土金属或稀土合金表面抗氧化的方法，包括以下步骤：The invention provides a method for surface oxidation resistance of rare earth metals or rare earth alloys, which includes the following steps:
将所述稀土金属或稀土合金进行预处理，所述预处理包括：将稀土金属或稀土合金浸泡在热水中，取出后干燥；然后在稀土金属或稀土合金表面涂覆上述技术方案所述的有机抗氧化组合物；然后挥发去除稀土金属或稀土合金表面的有机稀释剂。The rare earth metal or rare earth alloy is pretreated, and the pretreatment includes: soaking the rare earth metal or rare earth alloy in hot water, taking it out and drying it; and then coating the surface of the rare earth metal or rare earth alloy with the method described in the above technical solution. Organic antioxidant composition; and then evaporate the organic diluent on the surface of the rare earth metal or rare earth alloy.
优选的，所述热水的温度为80~90℃，所述热水浸泡的时间为10~20min。Preferably, the temperature of the hot water is 80~90°C, and the soaking time in the hot water is 10~20 minutes.
优选的，所述稀土金属包括钕金属；所述稀土合金包括镨钕合金或铈镨钕合金。Preferably, the rare earth metal includes neodymium metal; the rare earth alloy includes praseodymium and neodymium alloy or cerium praseodymium and neodymium alloy.
优选的，所述镨钕合金中镨元素的质量百分含量为25%，钕元素的质量百分含量为75%。Preferably, the mass percentage of praseodymium element in the praseodymium and neodymium alloy is 25%, and the mass percentage of neodymium element is 75%.
优选的，所述铈镨钕合金中铈元素的质量百分含量为8%，镨元素的质量百分含量为20~24%，余量为钕。Preferably, the mass percentage content of the cerium element in the cerium-praseodymium-neodymium alloy is 8%, the mass percentage content of the praseodymium element is 20-24%, and the balance is neodymium.
本发明提供了一种用于稀土金属或稀土合金表面抗氧化的有机抗氧化组合物，包括以下质量百分含量的组分：叔十二硫醇0.5~1%，树脂粘结剂1~3%，有机稀释剂96~98.5%。本发明按照所述有机抗氧化组合物中：以叔十二硫醇和树脂粘结剂为活性组分，同时控制三种组分的质量百分含量，应用于稀土金属或稀土合金表面时，所述有机抗氧化组合物能在稀土金属或者稀土合金表面形成一层有机膜，阻隔了稀土金属或者稀土合金和空气的直接接触，减少了稀土金属或者稀土合金的表面氧化。由实施例的结果表明，本发明提供的经过有机抗氧化组合物处理的稀土金属或者稀土合金可以放置3~4个月仍然具有金属光泽而不变颜色。The invention provides an organic antioxidant composition for rare earth metal or rare earth alloy surface antioxidant, including the following mass percentage components: tert-dodecanethiol 0.5~1%, resin binder 1~3 %, organic diluent 96~98.5%. According to the organic antioxidant composition of the present invention, tert-dodecyl mercaptan and resin binder are used as active components, and the mass percentages of the three components are controlled at the same time. When applied to the surface of rare earth metal or rare earth alloy, the result is The organic antioxidant composition can form an organic film on the surface of the rare earth metal or rare earth alloy, blocking direct contact between the rare earth metal or rare earth alloy and air, and reducing surface oxidation of the rare earth metal or rare earth alloy. The results of the examples show that the rare earth metal or rare earth alloy treated with the organic antioxidant composition provided by the present invention can still have a metallic luster without changing color after being left for 3 to 4 months.
附图说明Description of the drawings
图1为本发明实施例1的测试结果；Figure 1 is the test results of Example 1 of the present invention;
图2为本发明实施例2的测试结果；Figure 2 is the test result of Example 2 of the present invention;
图3为本发明实施例3的测试结果；Figure 3 is the test results of Example 3 of the present invention;
图4为本发明对比例1的测试结果；Figure 4 is the test result of Comparative Example 1 of the present invention;
图5为本发明对比例2的测试结果；Figure 5 is the test result of Comparative Example 2 of the present invention;
图6为本发明对比例3的测试结果；Figure 6 is the test result of Comparative Example 3 of the present invention;
图7为本发明对比例4的测试结果；Figure 7 is the test result of Comparative Example 4 of the present invention;
图8为本发明实施例4的测试结果。Figure 8 shows the test results of Example 4 of the present invention.
具体实施方式Detailed ways
本发明提供了一种用于稀土金属或稀土合金表面抗氧化的有机抗氧化组合物，包括以下质量百分含量的组分：叔十二硫醇0.5~1%，树脂粘结剂1~3%，有机稀释剂96~98.5%。The invention provides an organic antioxidant composition for rare earth metal or rare earth alloy surface antioxidant, including the following mass percentage components: tert-dodecanethiol 0.5~1%, resin binder 1~3 %, organic diluent 96~98.5%.
在本发明中，若无特殊说明，所有制备原料/组分均为本领域技术人员熟知的市售产品。In the present invention, unless otherwise specified, all preparation raw materials/components are commercially available products well known to those skilled in the art.
以质量百分含量计，本发明提供的用于稀土金属或稀土合金表面抗氧化的有机抗氧化组合物包括叔十二硫醇0.5~1%，优选为0.6~0.8%。In terms of mass percentage, the organic antioxidant composition for surface antioxidant of rare earth metals or rare earth alloys provided by the present invention includes 0.5 to 1% of tert-dodecanethiol, preferably 0.6 to 0.8%.
以质量百分含量计，本发明提供的用于稀土金属或稀土合金表面抗氧化的有机抗氧化组合物包括树脂粘结剂1~3%，优选为1.5~2.5%。在本发明中，所述树脂粘结剂优选为环氧树脂粘结剂。所述环氧树脂粘结剂优选为凤凰牌环氧树脂E44。In terms of mass percentage, the organic antioxidant composition provided by the present invention for surface antioxidant of rare earth metals or rare earth alloys includes 1 to 3% of resin binder, preferably 1.5 to 2.5%. In the present invention, the resin adhesive is preferably an epoxy resin adhesive. The epoxy resin adhesive is preferably Phoenix brand epoxy resin E44.
以质量百分含量计，本发明提供的用于稀土金属或稀土合金表面抗氧化的有机抗氧化组合物包括有机稀释剂96~98.5%，优选为96.5~98%。在本发明中，所述有机稀释剂优选由丙三酮和/或乙醇组成，更优选由丙三酮和乙醇组成。在本发明中，所述有机稀释剂中含有丙三酮，所述丙三酮具有比乙醇干好的稳定性和安全性，且兼顾乙醇对高分子有机物的溶解性强的特点，本发明优选丙三酮和乙醇的混合物作为所述有机稀释剂。所述有机稀释剂优选由丙三酮和乙醇组成时，所述丙三酮和乙醇的体积比优选为（3~4）：1。In terms of mass percentage, the organic antioxidant composition for rare earth metal or rare earth alloy surface antioxidant provided by the present invention includes 96 to 98.5% of organic diluent, preferably 96.5 to 98%. In the present invention, the organic diluent is preferably composed of glycerol and/or ethanol, more preferably composed of glycerol and ethanol. In the present invention, the organic diluent contains glycerol, which has better stability and safety than ethanol, and takes into account the strong solubility of ethanol to high molecular organic matter. This invention is preferred A mixture of glycerol and ethanol was used as the organic diluent. When the organic diluent is preferably composed of glycerin and ethanol, the volume ratio of glycerin and ethanol is preferably (3~4):1.
在本发明中，所述有机抗氧化组合物的制备方法优选包括：将有机稀释剂和树脂粘结剂预混，得到预混溶液；将所述预混溶液和所述叔十二硫醇混合。本发明对所述预混和混合的具体实施过程没有特殊要求，确保所述有机稀释剂、树脂粘结剂和所述叔十二硫醇混合均匀即可。In the present invention, the preparation method of the organic antioxidant composition preferably includes: premixing an organic diluent and a resin binder to obtain a premixed solution; mixing the premixed solution and the tert-dodecanethiol . The present invention has no special requirements for the specific implementation process of premixing and mixing, as long as it is ensured that the organic diluent, resin binder and tert-dodecyl mercaptan are evenly mixed.
本发明提供了一种稀土金属或稀土合金表面抗氧化的方法，包括以下步骤：The invention provides a method for surface oxidation resistance of rare earth metals or rare earth alloys, which includes the following steps:
在稀土金属或稀土合金表面涂覆上述技术方案所述的有机抗氧化组合物；然后挥发去除稀土金属或稀土合金表面的有机稀释剂。The organic antioxidant composition described in the above technical solution is coated on the surface of the rare earth metal or rare earth alloy; and then the organic diluent on the surface of the rare earth metal or rare earth alloy is volatilized and removed.
在本发明中，所述稀土金属优选包括钕金属。所述稀土合金优选包括镨钕合金或铈镨钕合金。所述镨钕合金中镨元素的质量百分含量优选为25%，钕元素的质量百分含量优选为75%。所述铈镨钕合金中铈元素的质量百分含量优选为8%，镨元素的质量百分含量优选为20~24%，余量为钕。本发明对所述稀土金属或者稀土合金的制备方法没有特殊要求，采用本领域技术人员熟知的熔盐电解制备即可。In the present invention, the rare earth metal preferably includes neodymium metal. The rare earth alloy preferably includes a praseodymium-neodymium alloy or a cerium-praseodymium-neodymium alloy. The mass percentage content of the praseodymium element in the praseodymium-neodymium alloy is preferably 25%, and the mass percentage content of the neodymium element is preferably 75%. The mass percentage content of the cerium element in the cerium praseodymium and neodymium alloy is preferably 8%, the mass percentage content of the praseodymium element is preferably 20 to 24%, and the balance is neodymium. The present invention has no special requirements for the preparation method of the rare earth metal or rare earth alloy, and it can be prepared by molten salt electrolysis, which is well known to those skilled in the art.
在本发明中，在稀土金属或稀土合金表面涂覆上述技术方案所述的有机抗氧化组合物之前，本发明优选还包括：将所述稀土金属或稀土合金进行预处理，所述预处理优选包括：将稀土金属或稀土合金浸泡在热水中，取出后干燥。在本发明中，所述稀土金属或稀土合金浸泡在热水中之前，本发明优选对所述稀土金属或者稀土合金的表面进行打磨抛光。本发明对所述打磨抛光的具体实施方式没有特殊要求，将所述稀土金属或者稀土合金表面的夹杂杂质或电解质去掉即可。所述热水的温度优选为80~90℃，所述热水浸泡的时间优选为10~20min。所述干燥优选为风干或吹干，所述风干优选将热水浸泡后的稀土金属或稀土合金放置在通风位置进行风干。所述吹干优选采用吹风机吹干，所述吹风机吹干的时间优选≥20min。In the present invention, before the surface of the rare earth metal or rare earth alloy is coated with the organic antioxidant composition described in the above technical solution, the present invention preferably further includes: pre-treating the rare earth metal or rare earth alloy, and the pre-treatment preferably Including: soaking rare earth metal or rare earth alloy in hot water, taking it out and drying it. In the present invention, before the rare earth metal or rare earth alloy is immersed in hot water, the surface of the rare earth metal or rare earth alloy is preferably ground and polished. The present invention has no special requirements for the specific implementation of the grinding and polishing. It is enough to remove the impurities or electrolytes on the surface of the rare earth metal or rare earth alloy. The temperature of the hot water is preferably 80~90°C, and the soaking time in the hot water is preferably 10~20 minutes. The drying is preferably air drying or blow drying. The air drying is preferably done by placing the rare earth metal or rare earth alloy soaked in hot water in a ventilated position for air drying. The drying is preferably carried out with a hair dryer, and the drying time of the hair dryer is preferably ≥20 minutes.
在本发明中，所述涂覆的温度优选为室温，所述涂覆的具体实施方式优选为浸涂、刮涂或刷涂，更优选为浸涂。本发明对所述浸涂、刮涂或刷涂的具体实施方式以及实施时间没有特殊要求，确保所述稀土金属或者稀土合金的每一个表面均沾满所述有机抗氧化组合物即可。在本发明中，挥发去除稀土金属或稀土合金表面的有机稀释剂室温具体实施方式优选为风干或吹干，所述风干优选将有机抗氧化组合物涂覆后的稀土金属或稀土合金放置在通风位置进行风干。所述吹干优选采用吹风机吹干，所述吹风机吹干的时间优选≥10min。In the present invention, the temperature of the coating is preferably room temperature, and the specific implementation method of the coating is preferably dip coating, blade coating, or brush coating, and more preferably, dip coating. The present invention has no special requirements on the specific implementation method and implementation time of dipping, scraping or brushing, as long as it is ensured that every surface of the rare earth metal or rare earth alloy is covered with the organic antioxidant composition. In the present invention, the room temperature specific implementation method for volatilizing and removing the organic diluent on the surface of the rare earth metal or rare earth alloy is preferably air drying or blow drying. The air drying is preferably done by placing the rare earth metal or rare earth alloy coated with the organic antioxidant composition in a ventilated place. Position to dry. The drying is preferably carried out with a hair dryer, and the drying time of the hair dryer is preferably ≥10 minutes.
本发明通过上述技术方案所述的有机抗氧化组合物对稀土金属或稀土合金进行表面抗氧化处理后，得到表面具有抗氧化涂层的稀土金属或稀土合金，能够阻隔稀土金属或者合金和空气的直接接触，减少了稀土金属或者合金的表面氧化。当表面具有抗氧化涂层的稀土金属或稀土合金需要进行下一道处理工序时，在表面具有抗氧化涂层的稀土金属或稀土合金进行高温熔炼时，稀土金属或稀土合金的表面抗氧化涂层（叔十二硫醇和树脂粘结剂）在高温环境中分解，对熔炼得到的熔融态稀土金属或者熔融态稀土合金的纯度不会造成不利影响。The present invention uses the organic antioxidant composition described in the above technical solution to perform surface antioxidant treatment on the rare earth metal or rare earth alloy, thereby obtaining the rare earth metal or rare earth alloy with an antioxidant coating on the surface, which can block the interaction between the rare earth metal or alloy and the air. Direct contact reduces surface oxidation of rare earth metals or alloys. When the rare earth metal or rare earth alloy with an anti-oxidation coating on the surface needs to undergo the next processing step, when the rare earth metal or rare earth alloy with an anti-oxidation coating on the surface is smelted at high temperature, the surface anti-oxidation coating of the rare earth metal or rare earth alloy (tert-dodecyl mercaptan and resin binder) decompose in a high-temperature environment and will not adversely affect the purity of the molten rare earth metal or molten rare earth alloy obtained by smelting.
为了进一步说明本发明，下面结合实施例对本发明提供的技术方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with the examples, but they should not be understood as limiting the protection scope of the present invention.
实施例1Example 1
取两块熔盐电解制备的镨钕合金锭，每块镨钕合金锭重量约7kg，打磨抛光去掉表面的夹杂物和电解质。Take two praseodymium and neodymium alloy ingots prepared by molten salt electrolysis. Each praseodymium and neodymium alloy ingot weighs about 7kg, and polish them to remove surface inclusions and electrolytes.
取丙三酮300mL，乙醇100mL，放置在一个容量瓶中混合均匀。取环氧树脂8mL，放入丙三酮和乙醇组成的稀释剂中搅拌溶解均匀。取叔十二硫醇4mL，加入前面配置好的稀释剂和环氧树脂中搅拌溶解均匀，得到有机抗氧化组合物。Take 300mL of glycerol and 100mL of ethanol, place them in a volumetric flask and mix evenly. Take 8 mL of epoxy resin, put it into a diluent composed of glycerin and ethanol, stir and dissolve evenly. Take 4 mL of tert-dodecyl mercaptan, add it to the previously prepared diluent and epoxy resin, stir and dissolve evenly to obtain an organic antioxidant composition.
将打磨抛光后的镨钕合金锭放置于85℃纯水中，水温保持85℃±5℃，持续15min后取出，放置于通风处风干，确保表面无水分。将镨钕合金锭放入有机抗氧化组合物中浸泡，确保每个面都沾有抗氧化剂。取出后放置于通风处风干。用铁桶内衬塑料，扎紧密封后保存放置3个月，图1为本实施例经过抗氧化处理后的镨钕合金锭放置3个月后的实物照片，其中图1中标号为“128”的样品（其中128是工厂里标注的序号）为没有经过实施例1处理的镨钕合金锭，图1中标号为“128”的样品下方以及右侧贴有标签纸的样品为经过实施例1抗氧化处理后的镨钕合金锭。由图1可知，没有经过实施例1处理的标号为“128”的样品表面氧化严重，表面失去金属光泽，而经过实施例1提供的有机抗氧化组合物浸泡后的镨钕合金锭放置3个月后合金表面仍然具有金属光泽。Place the polished praseodymium and neodymium alloy ingots in 85°C pure water, keep the water temperature at 85°C ± 5°C, take it out after 15 minutes, and place it in a ventilated place to air dry to ensure that there is no moisture on the surface. Soak the praseodymium and neodymium alloy ingots in the organic antioxidant composition to ensure that every surface is covered with antioxidants. Take it out and place it in a ventilated place to dry. Lining an iron bucket with plastic, sealing it tightly and storing it for 3 months. Figure 1 is a photo of the praseodymium and neodymium alloy ingot after anti-oxidation treatment in this embodiment after being stored for 3 months. The number in Figure 1 is "128" "The sample (128 is the serial number marked in the factory) is a praseodymium and neodymium alloy ingot that has not been processed in Example 1. The sample with label paper below and on the right side of the sample numbered "128" in Figure 1 is a sample that has been processed in Example 1. 1Praseodymium and neodymium alloy ingots after anti-oxidation treatment. As can be seen from Figure 1, the surface of the sample labeled "128" that has not been treated in Example 1 is severely oxidized and the surface has lost its metallic luster. However, the praseodymium and neodymium alloy ingots soaked in the organic antioxidant composition provided in Example 1 are placed on 3 After months, the alloy surface still has a metallic luster.
实施例2Example 2
取一块熔盐电解制备的钕金属锭，锭重量约6kg，打磨抛光去掉表面的夹杂物和电解质等。Take a neodymium metal ingot prepared by molten salt electrolysis. The ingot weighs about 6kg and is polished to remove surface inclusions and electrolytes.
取丙三酮200mL，乙醇50mL，放置在一个容量瓶中混合均匀。取环氧树脂5mL，放入丙三酮和乙醇组成的稀释剂中搅拌溶解均匀。取叔十二硫醇3mL，加入前面配置好的稀释剂和环氧树脂中搅拌溶解均匀，得到有机抗氧化组合物。Take 200mL of glycerol and 50mL of ethanol, place them in a volumetric flask and mix evenly. Take 5 mL of epoxy resin, put it into a diluent composed of glycerin and ethanol, stir and dissolve evenly. Take 3 mL of tert-dodecyl mercaptan, add it to the previously prepared diluent and epoxy resin, stir and dissolve evenly to obtain an organic antioxidant composition.
将镨钕合金锭放置于90℃纯水中，水温保持85℃±5℃，持续10min后取出，用风机吹20min，确保表面无水分。将钕金属锭放入有机抗氧化组合物中浸泡，确保每个面都沾有抗氧化剂。取出后用风机吹10min。用铁桶内衬塑料，扎紧密封后保存放置4个月，图2为本实施例经过抗氧化处理后的钕金属锭放置4个月后的实物照片，其中图2中标号为“12802”的样品（其中12802是工厂里标注的序号）为没有经过实施例2处理的镨钕合金锭，图2中贴有标签纸的样品为经过实施例2抗氧化处理后的镨钕合金锭。由图2可知，没有经过实施例2处理的标号为“12802”的样品表面氧化严重，表面失去了金属光泽，而经过实施例2提供的有机抗氧化组合物浸泡后的钕金属锭放置4个月后该合金表面仍然具有金属光泽。Place the praseodymium and neodymium alloy ingot in 90°C pure water, keep the water temperature at 85°C ± 5°C, take it out after 10 minutes, and blow it with a fan for 20 minutes to ensure that there is no moisture on the surface. Soak the neodymium metal ingot in the organic antioxidant composition, making sure every side is coated with the antioxidant. After taking it out, blow it with a fan for 10 minutes. Lining an iron bucket with plastic, sealing it tightly and storing it for 4 months. Figure 2 is a photo of the neodymium metal ingot after anti-oxidation treatment in this embodiment after being stored for 4 months. The number in Figure 2 is "12802" The sample (12802 is the serial number marked in the factory) is a praseodymium and neodymium alloy ingot that has not been treated in Example 2. The sample with label paper in Figure 2 is a praseodymium and neodymium alloy ingot that has been treated by the antioxidant treatment in Example 2. As can be seen from Figure 2, the surface of the sample labeled "12802" that has not been treated in Example 2 is severely oxidized and the surface has lost its metallic luster. However, the neodymium metal ingot soaked in the organic antioxidant composition provided in Example 2 is placed on 4 The surface of the alloy still has a metallic luster after several months.
实施例3Example 3
取一块熔盐电解制备的铈镨钕合金锭，铈含量为8%，镨钕含量为92%，镨含量为22%，钕含量为70%，锭重量约6kg，打磨抛光去掉表面的夹杂物和电解质等。Take a piece of cerium, praseodymium and neodymium alloy ingot prepared by molten salt electrolysis. The cerium content is 8%, the praseodymium and neodymium content is 92%, the praseodymium content is 22%, and the neodymium content is 70%. The ingot weighs about 6kg. Polish it to remove the inclusions on the surface. and electrolytes, etc.
取丙三酮200mL，乙醇50mL，放置在一个容量瓶中混合均匀。取环氧树脂4mL，放入丙三酮和乙醇组成的稀释剂中搅拌溶解均匀。取叔十二硫醇3mL，加入前面配置好的稀释剂和环氧树脂中搅拌溶解均匀，得到有机抗氧化组合物。Take 200mL of glycerol and 50mL of ethanol, place them in a volumetric flask and mix evenly. Take 4 mL of epoxy resin, put it into a diluent composed of glycerin and ethanol, stir and dissolve evenly. Take 3 mL of tert-dodecyl mercaptan, add it to the previously prepared diluent and epoxy resin, stir and dissolve evenly to obtain an organic antioxidant composition.
将镨钕合金锭放置于90℃纯水中，水温保持85℃±5℃，持续20min后取出，放置于通风处风干，确保表面无水分。将铈镨钕合金锭放入，得到有机抗氧化组合物中浸泡，确保每个面都沾有抗氧化剂。取出后放置于通风处风干。用铁桶内衬塑料，扎紧密封后保存放置3个月，图3为本实施例经过抗氧化处理后的铈镨钕合金锭放置3个月后的实物照片，其中图3中标号为“128”的样品（其中128是工厂里标注的序号）为没有经过实施例3处理的镨钕合金锭，图3中贴有标签纸的样品为经过实施例3抗氧化处理后的镨钕合金锭。由图3可知，没有经过实施例3处理的标号为“128”的样品表面氧化严重，表面失去金属光泽，而经过实施例3提供的有机抗氧化组合物浸泡后的铈镨钕合金锭放置3个月后该合金表面仍然具有金属光泽。Place the praseodymium and neodymium alloy ingot in 90°C pure water, keep the water temperature at 85°C ± 5°C, take it out after 20 minutes, and place it in a ventilated place to air dry to ensure that there is no moisture on the surface. Put the cerium praseodymium and neodymium alloy ingot and soak it in the organic antioxidant composition to ensure that every surface is covered with antioxidants. Take it out and place it in a ventilated place to dry. Lining an iron bucket with plastic, sealing it tightly and storing it for 3 months. Figure 3 is a photo of the cerium praseodymium and neodymium alloy ingot after anti-oxidation treatment in this embodiment after being stored for 3 months. The number in Figure 3 is " The 128" sample (where 128 is the serial number marked in the factory) is a praseodymium and neodymium alloy ingot that has not been treated in Example 3. The sample with label paper in Figure 3 is a praseodymium and neodymium alloy ingot that has undergone the anti-oxidation treatment in Example 3. . As can be seen from Figure 3, the surface of the sample labeled "128" that has not been treated in Example 3 is severely oxidized and the surface has lost its metallic luster. However, the cerium, praseodymium and neodymium alloy ingot soaked in the organic antioxidant composition provided in Example 3 is placed 3 The surface of the alloy still has a metallic luster after several months.
实施例4Example 4
取两块熔盐电解制备的镨钕合金锭，每块镨钕合金锭重量约7kg，打磨抛光去掉表面的夹杂物和电解质。Take two praseodymium and neodymium alloy ingots prepared by molten salt electrolysis. Each praseodymium and neodymium alloy ingot weighs about 7kg, and polish them to remove surface inclusions and electrolytes.
取乙醇，400mL，放置在一个容量瓶中作为稀释剂。取环氧树脂8mL，放入稀释剂中搅拌溶解均匀。取叔十二硫醇4mL，加入前面配置好的稀释剂和环氧树脂中搅拌溶解均匀，得到有机抗氧化组合物。Take 400mL of ethanol and place it in a volumetric flask as a diluent. Take 8mL of epoxy resin, put it into the diluent and stir to dissolve evenly. Take 4 mL of tert-dodecyl mercaptan, add it to the previously prepared diluent and epoxy resin, stir and dissolve evenly to obtain an organic antioxidant composition.
将打磨抛光后的镨钕合金锭放置于85℃纯水中，水温保持85℃±5℃，持续15min后取出，放置于通风处风干，确保表面无水分。将镨钕合金锭放入有机抗氧化组合物中浸泡，确保每个面都沾有抗氧化剂。取出后放置于通风处风干。用铁桶内衬塑料，扎紧密封后保存放置3个月。图8的左侧图为采用实施例4提供的有机抗氧化组合物处理后放置3个月的镨钕合金的表面照片（颜色浅），图8的右侧图为没有实施例4提供的有机抗氧化组合物处理的镨钕合金放置3个月的表面照片（颜色深），由图8可知，左侧图经过实施例4的有机抗氧化剂处理后，镨钕合金放置3个月仍具有金属光泽（颜色浅），而图8的右侧图没有经过处理的样品放置3个月表面氧化严重，表面失去金属光泽（颜色深）。Place the polished praseodymium and neodymium alloy ingots in 85°C pure water, keep the water temperature at 85°C ± 5°C, take it out after 15 minutes, and place it in a ventilated place to air dry to ensure that there is no moisture on the surface. Soak the praseodymium and neodymium alloy ingots in the organic antioxidant composition to ensure that every surface is covered with antioxidants. Take it out and place it in a ventilated place to dry. Line the iron bucket with plastic, seal it tightly and store it for 3 months. The left side picture of Figure 8 is a surface photo (light color) of praseodymium and neodymium alloy treated with the organic antioxidant composition provided in Example 4 and left for 3 months. The right side picture of Figure 8 is a picture without the organic antioxidant composition provided in Example 4. Surface photos (dark color) of the praseodymium and neodymium alloy treated with the antioxidant composition after being left for 3 months. As can be seen from Figure 8, in the left picture after being treated with the organic antioxidant in Example 4, the praseodymium and neodymium alloy still has metal properties after being left for 3 months. gloss (light color), while the untreated sample on the right side of Figure 8 has been left seriously oxidized for 3 months, and the surface has lost its metallic luster (dark color).
对比例1Comparative example 1
与实施例1的提供的方法基本相同，不同之处在于：有机抗氧化组合物的配置方法为：取丙三酮300mL，乙醇100mL，放置在一个容量瓶中混合均匀。取叔十二硫醇4mL，加入前面配置好的稀释剂中搅拌溶解均匀，得到有机抗氧化组合物。The method is basically the same as that provided in Example 1, except that the preparation method of the organic antioxidant composition is: take 300 mL of glycerol and 100 mL of ethanol, place them in a volumetric flask and mix them evenly. Take 4 mL of tert-dodecanethiol, add it to the diluent prepared previously, stir and dissolve evenly to obtain an organic antioxidant composition.
图4中的左图为新制备得到的未氧化的镨钕合金锭（颜色浅），图4中的右图为经过对比例1的有机抗氧化组合物处理后的镨钕合金锭保存3个月的照片。The left picture in Figure 4 shows a newly prepared unoxidized praseodymium and neodymium alloy ingot (light color), and the right picture in Figure 4 shows three preserved praseodymium and neodymium alloy ingots after being treated with the organic antioxidant composition of Comparative Example 1. Photos of the month.
由图4可知：采用对比例1提供的有机抗氧化组合物处理的镨钕合金锭，虽然经过了对比例1的有机抗氧化组合物处理，但是与新制备得到的未氧化的镨钕合金锭相比，表面失去金属光泽，表明氧化比较严重（样品颜色变深）。与实施例1相比较，对比例1中有机抗氧化组合物中省略环氧树脂，图4中的右图的样品也失去了金属光泽，说明氧化严重，效果变差。It can be seen from Figure 4 that although the praseodymium and neodymium alloy ingots treated with the organic antioxidant composition provided in Comparative Example 1 are different from the newly prepared unoxidized praseodymium and neodymium alloy ingots, In comparison, the surface loses its metallic luster, indicating serious oxidation (the color of the sample becomes darker). Compared with Example 1, the epoxy resin was omitted from the organic antioxidant composition in Comparative Example 1, and the sample on the right in Figure 4 also lost its metallic luster, indicating severe oxidation and poor effect.
对比例2Comparative example 2
与实施例1的提供的方法基本相同，不同之处在于：有机抗氧化组合物的配置方法为：取丙三酮300mL，放置在一个容量瓶中混合均匀。取环氧树脂8mL，放入丙三酮组成的稀释剂中搅拌溶解均匀。取叔十二硫醇4mL，加入前面配置好的稀释剂和环氧树脂中搅拌溶解均匀，得到有机抗氧化组合物。The method is basically the same as that provided in Example 1, except that the preparation method of the organic antioxidant composition is: take 300 mL of glycerol, place it in a volumetric flask and mix it evenly. Take 8 mL of epoxy resin, put it into a diluent composed of glycerin, stir and dissolve evenly. Take 4 mL of tert-dodecyl mercaptan, add it to the previously prepared diluent and epoxy resin, stir and dissolve evenly to obtain an organic antioxidant composition.
图5中的左图为新制备得到的未氧化的镨钕合金锭，图5中的右图为经过对比例2的有机抗氧化组合物处理后的镨钕合金锭保存3个月的照片。The left picture in Figure 5 is a newly prepared unoxidized praseodymium and neodymium alloy ingot, and the right picture in Figure 5 is a photo of the praseodymium and neodymium alloy ingot treated with the organic antioxidant composition of Comparative Example 2 and stored for 3 months.
由图5可知：采用对比例2提供的有机抗氧化组合物处理的镨钕合金锭，虽然经过了对比例2的有机抗氧化组合物处理，但是与新制备得到的未氧化的镨钕合金锭相比，表面失去金属光泽，表明氧化比较严重。与实施例1相比较，对比例2中有机抗氧化组合物中省略乙醇，图5中右图处理后的样品也失去了金属光泽，说明氧化严重，效果变差。It can be seen from Figure 5 that although the praseodymium and neodymium alloy ingots treated with the organic antioxidant composition provided in Comparative Example 2 are different from the newly prepared unoxidized praseodymium and neodymium alloy ingots, In contrast, the surface loses its metallic luster, indicating serious oxidation. Compared with Example 1, ethanol was omitted from the organic antioxidant composition in Comparative Example 2, and the treated sample in the right picture in Figure 5 also lost its metallic luster, indicating severe oxidation and poor effect.
对比例3Comparative example 3
与实施例1的提供的方法基本相同，不同之处在于：有机抗氧化组合物的配置方法为：取丙三酮300mL，乙醇100mL，放置在一个容量瓶中混合均匀。取环氧树脂8mL，放入丙三酮和乙醇组成的稀释剂中搅拌溶解均匀。取二丁基羟基甲苯4mL，加入前面配置好的稀释剂和环氧树脂中搅拌溶解均匀，得到有机抗氧化组合物。The method is basically the same as that provided in Example 1, except that the preparation method of the organic antioxidant composition is: take 300 mL of glycerol and 100 mL of ethanol, place them in a volumetric flask and mix them evenly. Take 8 mL of epoxy resin, put it into a diluent composed of glycerin and ethanol, stir and dissolve evenly. Take 4 mL of dibutyl hydroxytoluene, add it to the previously prepared diluent and epoxy resin, stir and dissolve evenly to obtain an organic antioxidant composition.
图6中的左图为新制备得到的未氧化的镨钕合金锭，图6中的右图为经过对比例3的有机抗氧化组合物处理后的镨钕合金锭保存3个月的照片。The left picture in Figure 6 is a newly prepared unoxidized praseodymium and neodymium alloy ingot, and the right picture in Figure 6 is a photo of a praseodymium and neodymium alloy ingot that has been treated with the organic antioxidant composition of Comparative Example 3 and stored for 3 months.
由图6可知：采用对比例3提供的有机抗氧化组合物处理的镨钕合金锭，虽然经过了对比例3的有机抗氧化组合物处理，但是与新制备得到的未氧化的镨钕合金锭相比，表面失去金属光泽，表明氧化比较严重。与实施例1相比较，对比例3中有机抗氧化组合物中将叔十二硫醇替换为二丁基羟基甲苯，图6中的右图的样品也失去了金属光泽，说明氧化严重，效果变差。It can be seen from Figure 6 that although the praseodymium and neodymium alloy ingots treated with the organic antioxidant composition provided in Comparative Example 3 are different from the newly prepared unoxidized praseodymium and neodymium alloy ingots, In contrast, the surface loses its metallic luster, indicating serious oxidation. Compared with Example 1, in Comparative Example 3, tert-dodecanethiol was replaced by dibutylhydroxytoluene in the organic antioxidant composition. The sample on the right in Figure 6 also lost its metallic luster, indicating that oxidation was serious and the effect was get worse.
对比例4Comparative example 4
与实施例1的提供的方法基本相同，不同之处在于：有机抗氧化组合物的配置方法为：取丙三酮300mL，乙醇100mL，放置在一个容量瓶中混合均匀。取环氧树脂8mL，放入丙三酮和乙醇组成的稀释剂中搅拌溶解均匀。取叔十二硫醇4mL，加入前面配置好的稀释剂和环氧树脂中搅拌溶解均匀，得到有机抗氧化组合物。在实施过程中省略第一步的热水水洗过程，将打磨抛光后的镨钕合金锭直接放入有机抗氧化组合物中浸泡，确保每个面都沾有抗氧化剂。取出后放置于通风处风干。结果如图7。The method is basically the same as that provided in Example 1, except that the preparation method of the organic antioxidant composition is: take 300 mL of glycerol and 100 mL of ethanol, place them in a volumetric flask and mix them evenly. Take 8 mL of epoxy resin, put it into a diluent composed of glycerin and ethanol, stir and dissolve evenly. Take 4 mL of tert-dodecyl mercaptan, add it to the previously prepared diluent and epoxy resin, stir and dissolve evenly to obtain an organic antioxidant composition. In the implementation process, the hot water washing process in the first step is omitted, and the polished praseodymium and neodymium alloy ingots are directly soaked in the organic antioxidant composition to ensure that every surface is stained with antioxidants. Take it out and place it in a ventilated place to dry. The results are shown in Figure 7.
图7中的左图为新制备得到的未氧化的镨钕合金锭，图7中的右图为经过对比例4处理后的镨钕合金锭保存3个月的照片。The left picture in Figure 7 is a newly prepared non-oxidized praseodymium and neodymium alloy ingot, and the right picture in Figure 7 is a photo of the praseodymium and neodymium alloy ingot after being processed in Comparative Example 4 and stored for 3 months.
由图7可知：采用对比例4的处理方法，虽然经过了与实施例1相同的有机抗氧化组合物处理，但是由于未经过热水水洗，与新制备得到的未氧化的镨钕合金锭相比，表面失去金属光泽，表明氧化比较严重。与实施例1相比较，对比例4中的合金样品打磨抛光后未经过热水水洗，图7中的右图的样品也失去了金属光泽，说明氧化严重，效果变差。It can be seen from Figure 7 that the treatment method of Comparative Example 4 was used. Although it was treated with the same organic antioxidant composition as Example 1, it was not washed with hot water and was different from the newly prepared unoxidized praseodymium and neodymium alloy ingot. ratio, the surface loses metallic luster, indicating serious oxidation. Compared with Example 1, the alloy sample in Comparative Example 4 was not washed with hot water after polishing. The sample on the right in Figure 7 also lost its metallic luster, indicating severe oxidation and poor effect.
由以上实施例可知本发明提供的方法方法，用叔十二硫醇作为有机抗氧化剂，以环氧树脂为粘附剂，以丙三酮和/或乙醇为稀释剂；按照所述有机抗氧化组合物中：叔十二硫醇的质量百分含量为0.5~1%，所述树脂粘结剂的质量百分含量为1~3%，所述有机稀释剂的质量百分含量为96~98.5%的质量比例配置，采用热水水洗稀土金属或者稀土合金后，再经过有机抗氧化组合物浸泡稀土金属或者稀土合金，在稀土金属或者稀土合金表面形成一层有机膜，阻隔了稀土金属或者稀土合金和空气的直接接触，减少了稀土金属或者稀土合金的表面氧化。由实施例的结果表明，本发明提供的经过有机抗氧化组合物处理的稀土金属或者稀土合金可以放置3~4个月仍然具有金属光泽而不变颜色。It can be seen from the above examples that the method provided by the present invention uses tert-dodecanethiol as an organic antioxidant, epoxy resin as an adhesive, and glycerol and/or ethanol as a diluent; according to the organic antioxidant In the composition: the mass percentage of tert-dodecanethiol is 0.5~1%, the mass percentage of the resin binder is 1~3%, and the mass percentage of the organic diluent is 96~ Configured with a mass ratio of 98.5%, after washing the rare earth metal or rare earth alloy with hot water, the rare earth metal or rare earth alloy is soaked with an organic antioxidant composition to form an organic film on the surface of the rare earth metal or rare earth alloy, blocking the rare earth metal or rare earth alloy. The direct contact between the rare earth alloy and the air reduces the surface oxidation of the rare earth metal or rare earth alloy. The results of the examples show that the rare earth metal or rare earth alloy treated with the organic antioxidant composition provided by the present invention can still have a metallic luster without changing color after being left for 3 to 4 months.
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。Although the above embodiments describe the present invention in detail, they are only part of the embodiments of the present invention, not all embodiments. Other embodiments can also be obtained according to this embodiment without any inventive step, and these embodiments are all It belongs to the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311703553.9ACN117385365B (en) | 2023-12-13 | 2023-12-13 | Organic antioxidation composition and antioxidation method for rare earth metal or rare earth alloy surface |
| Application Number | Priority Date | Filing Date | Title |
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| CN202311703553.9ACN117385365B (en) | 2023-12-13 | 2023-12-13 | Organic antioxidation composition and antioxidation method for rare earth metal or rare earth alloy surface |
| Publication Number | Publication Date |
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| CN117385365Atrue CN117385365A (en) | 2024-01-12 |
| CN117385365B CN117385365B (en) | 2024-03-22 |
| Application Number | Title | Priority Date | Filing Date |
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| CN202311703553.9AActiveCN117385365B (en) | 2023-12-13 | 2023-12-13 | Organic antioxidation composition and antioxidation method for rare earth metal or rare earth alloy surface |
| Country | Link |
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| CN (1) | CN117385365B (en) |
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| US20040159548A1 (en)* | 2003-02-13 | 2004-08-19 | Peffer Robin M. | Electrodepositable coating compositions and processes related thereto |
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| CN109913012A (en)* | 2019-02-01 | 2019-06-21 | 刘建卡 | A kind of humidity application over rust solvent-free epoxy heavy-duty anticorrosive coating and preparation method thereof |
| CN113185857A (en)* | 2021-04-26 | 2021-07-30 | 包头市中鑫安泰磁业有限公司 | Graphite anode plate antioxidant coating composition and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01290209A (en)* | 1988-05-18 | 1989-11-22 | Tdk Corp | Rare-earth alloy magnet having protective coating |
| US20040159548A1 (en)* | 2003-02-13 | 2004-08-19 | Peffer Robin M. | Electrodepositable coating compositions and processes related thereto |
| US20070051634A1 (en)* | 2005-08-26 | 2007-03-08 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions and related methods |
| CN101407568A (en)* | 2008-11-21 | 2009-04-15 | 山东轻工业学院 | High solid low viscosity acrylic resin and preparation thereof |
| CN109913012A (en)* | 2019-02-01 | 2019-06-21 | 刘建卡 | A kind of humidity application over rust solvent-free epoxy heavy-duty anticorrosive coating and preparation method thereof |
| CN113185857A (en)* | 2021-04-26 | 2021-07-30 | 包头市中鑫安泰磁业有限公司 | Graphite anode plate antioxidant coating composition and application thereof |
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| 谢旭豪;许胜超;徐志勇;赵文波;: "硫醇类化合物合成工艺与方法", 材料导报, no. 07* |
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| CN117385365B (en) | 2024-03-22 |
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