技术领域technical field
本发明涉及稀土氧化物制备领域，具体提供一种纳米稀土氧化物的制备方 法，进一步涉及一种纳米稀土氧化物。The invention relates to the field of preparation of rare earth oxides, specifically provides a preparation method of nanometer rare earth oxides, and further relates to a nanometer rare earth oxide.
背景技术Background technique
全球稀土资源匮乏，而我国在稀土资源的储量和产量方面，在世界上均占 有优势。稀土元素由于其独特的4f电子结构，为其带来了电、光、磁、热等物 理和化学方面的优良性能，被广泛的应用于石油、化工、冶金、陶瓷、纺织、 玻璃、永磁材料等传统工业和高科技领域中，如金属基复合材料、抛光材料、 发光材料、激光材料、纤维、陶瓷材料等制备。The global rare earth resources are scarce, and my country has an advantage in the world in terms of reserves and production of rare earth resources. Due to its unique 4f electronic structure, rare earth elements bring it excellent physical and chemical properties such as electricity, light, magnetism, heat, etc., and are widely used in petroleum, chemical industry, metallurgy, ceramics, textiles, glass, permanent magnets. Materials and other traditional industries and high-tech fields, such as metal matrix composite materials, polishing materials, luminescent materials, laser materials, fibers, ceramic materials, etc.
稀土氧化物可以作为材料的掺杂成分、烧结助剂、催化及磁光储存等等， 是当今高新材料领域中的关键基础材料。随着科学技术的进步，稀土氧化物的 价值将越来越大。Rare earth oxides can be used as doping components, sintering aids, catalysis and magneto-optical storage of materials, etc., and are key basic materials in the field of high-tech materials today. With the advancement of science and technology, the value of rare earth oxides will increase.
而纳米化的稀土氧化物在具备有原有稀土氧化物的优良性质外，同时还兼 备有纳米材料的独特性质，具有更大的比表面积、表面能以及更好的流动性和 分散性，呈现出独特的物理化学综合特性，使其各项性能有质的提升，应用前 景更加广泛。In addition to the excellent properties of the original rare earth oxides, the nano-sized rare earth oxides also have the unique properties of nanomaterials, with larger specific surface area, surface energy, and better fluidity and dispersion. It has unique comprehensive physical and chemical characteristics, which makes its various properties qualitatively improved and has a wider application prospect.
随着稀土应用领域和层次范围的不端延申拓展，高新材料对纳米稀土氧化 物晶型、粒度、形貌、比表面等物性控制兼顾的品质要求也会越来越高。With the unreasonable expansion of rare earth application fields and levels, high-tech materials will have higher and higher quality requirements for the control of nanometer rare earth oxide crystal form, particle size, morphology, specific surface and other physical properties.
目前，用于制备纳米稀土氧化物的方法有沉淀法，沉淀法通过将稀土金属 盐和沉淀剂反应、洗涤干燥、煅烧制备而成。At present, the methods used to prepare nano-rare earth oxides include precipitation method, which is prepared by reacting rare earth metal salts with precipitants, washing, drying, and calcining.
采用沉淀法的制备过程中主要存在两种情况：一种是为了放置团聚而加入 分散剂、表面活性剂、模板剂等表面修饰剂，促进分散粉体的形成，例如，申 请号为CN201910230266.8中国专利将聚乙二醇等分散剂与稀土硝酸盐溶液混 合，并在零下20-50℃的环境下预冻并冷冻干燥，再经研磨、煅烧制得10-50nm 的超细纳米稀土氧化物；申请号为CN201010623570.8中国专利以稀土氧化物粗 粉为原料，加入尿素作为沉淀剂和表面活性剂，通过水热法制备了单分散 60-320nm的稀土氧化物纳米球。这种方法得到的稀土氧化物纳米球径大小分布 不均匀，这种方法不仅提高了成本，而且会对产品的纯度造成了一定的影响。There are two main situations in the preparation process of the precipitation method: one is to add surface modifiers such as dispersants, surfactants, and template agents for the purpose of placing agglomeration to promote the formation of dispersed powders. For example, the application number is CN201910230266.8 The Chinese patent mixes a dispersant such as polyethylene glycol with a rare earth nitrate solution, pre-freezes and freeze-drys it in an environment of minus 20-50 ℃, and then grinds and calcines to obtain ultra-fine nano-rare earth oxides of 10-50 nm. ; Application No. CN201010623570.8 Chinese patent uses rare earth oxide coarse powder as raw material, adds urea as precipitant and surfactant, and prepares monodisperse 60-320nm rare earth oxide nanospheres by hydrothermal method. The size distribution of rare earth oxide nanospheres obtained by this method is not uniform. This method not only increases the cost, but also has a certain impact on the purity of the product.
另一种，不添加表面修饰剂，而是通过增加尿素的摩尔量。例如，申请号 为CN201010623570.8中国专利以稀土氧化物粗粉为原料，加入尿素作为沉淀剂 和表面活性剂，通过水热法制备了单分散60-320nm的稀土氧化物纳米球；该专 利是降低了稀土离子的浓度来实现纳米稀土氧化物的制备，但制备时间长、产 量低，而且获得的纳米稀土氧化物粒径分布范围广。Another, without adding surface modifiers, but by increasing the molar amount of urea. For example, the Chinese patent application number CN201010623570.8 uses rare earth oxide coarse powder as raw material, adds urea as precipitant and surfactant, and prepares monodisperse 60-320nm rare earth oxide nanospheres by hydrothermal method; the patent is The concentration of rare earth ions is reduced to realize the preparation of nano rare earth oxide, but the preparation time is long, the yield is low, and the obtained nano rare earth oxide has a wide particle size distribution range.
另外，水热法制备的纳米稀土氧化物团聚现象比较严重，需要大量溶剂， 分离困难，对纯度造成影响，工序多，产量低，成本高。溶胶-凝胶法通常以金 属有机物或有机物助剂为原料，成本高，易板结，工耗时间长。不适用于工业 化大规模生产。In addition, the agglomeration phenomenon of nano rare earth oxides prepared by hydrothermal method is relatively serious, requires a large amount of solvent, is difficult to separate, affects the purity, has many processes, low yield and high cost. The sol-gel method usually uses metal organics or organic additives as raw materials, which is expensive, easy to harden, and takes a long time. Not suitable for industrial mass production.
发明内容SUMMARY OF THE INVENTION
为了解决现有技术中产品的纯度以及成本高、制备时间长等问题，本发明 提出了一种纳米稀土氧化物的制备方法，提出了以不溶性稀土盐为原料，通过 加入熔融盐，采取特殊的高温煅烧的工艺手段，得到的纳米稀土氧化物具有粒 度尺寸小、粒度分布均匀、纯度高等特点。In order to solve the problems of high product purity, high cost and long preparation time in the prior art, the present invention proposes a preparation method of nano rare earth oxides, and proposes using insoluble rare earth salts as raw materials, by adding molten salts, and taking special The high-temperature calcination process method, the obtained nano-rare earth oxide has the characteristics of small particle size, uniform particle size distribution and high purity.
本发明要解决的另一个技术问题在于根据上述纳米稀土氧化物的制备方法 提供一种对应的纳米稀土氧化物。Another technical problem to be solved by the present invention is to provide a corresponding nano rare earth oxide according to the above-mentioned preparation method of nano rare earth oxide.
一种纳米稀土氧化物的制备方法，其具体制备方法如下：A preparation method of nanometer rare earth oxide, the specific preparation method is as follows:
S1：将一定量的熔融盐加入到一定量的水中搅拌溶解，加入一定量的聚乙 二醇、表面活性剂，将混合溶液逐步加入到一定量的不溶于水的稀土盐中，通 过搅拌分散均匀，得到浆料；S1: Add a certain amount of molten salt to a certain amount of water and stir to dissolve, add a certain amount of polyethylene glycol and surfactant, gradually add the mixed solution to a certain amount of water-insoluble rare earth salt, and disperse by stirring uniform to obtain slurry;
S2：将S1中所得到的浆料加入一定量的水球磨，经过过滤筛得到均匀的乳 浊液/悬浮液；S2: add a certain amount of water ball mill to the slurry obtained in S1, obtain a uniform emulsion/suspension through a sieve;
S3：将S2得到的乳浊液/悬浮液一边搅拌一边经喷雾干燥得到粉体；S3: the emulsion/suspension obtained in S2 is stirred to obtain powder through spray drying;
S4：将S3中得到的粉体在炉体中煅烧，煅烧的温度为从室温～900℃，一 段时间后，随炉体降温即得纳米稀土氧化物。S4: calcining the powder obtained in S3 in the furnace body, the calcining temperature is from room temperature to 900°C, and after a period of time, the nano-rare earth oxide is obtained by cooling the furnace body.
进一步的，在S1中，所述表面活性剂为十六烷基三甲基溴化铵、聚乙二醇、 硬酯酸、季铵化物中的至少一种。Further, in S1, the surfactant is at least one of cetyltrimethylammonium bromide, polyethylene glycol, stearic acid, and quaternary ammonium compound.
进一步的，在S1中，其中所述稀土盐和所述熔融盐的质量比为1:0.01～5； 所述稀土盐和水的质量比为1:0.1～5。Further, in S1, the mass ratio of the rare earth salt and the molten salt is 1:0.01-5; the mass ratio of the rare earth salt and water is 1:0.1-5.
进一步的，在S1中，所述稀土盐为碳酸盐、醋酸盐和草酸盐中的至少一种。Further, in S1, the rare earth salt is at least one of carbonate, acetate and oxalate.
进一步的，在S1中，所述稀土盐设为草酸镨、草酸铥、草酸铒、草酸钬、 草酸铽、草酸钐、碳酸钆、碳酸镧、碳酸钕。Further, in S1, the rare earth salt is set to praseodymium oxalate, thulium oxalate, erbium oxalate, holmium oxalate, terbium oxalate, samarium oxalate, gadolinium carbonate, lanthanum carbonate, and neodymium carbonate.
进一步的，在S1中，所述熔融盐为氯化铵、氯化钠、氯化钾、氟化钠、碳 酸铵、氨水、碳酸钠、碳酸钾、柠檬铵、柠檬酸钠、柠檬酸钾中的至少一种。Further, in S1, the molten salt is in ammonium chloride, sodium chloride, potassium chloride, sodium fluoride, ammonium carbonate, ammonia water, sodium carbonate, potassium carbonate, ammonium citrate, sodium citrate, potassium citrate at least one of.
进一步的，在S2中，所述球磨时间为5～10min，优选为8min；其中，所 述浆料和水的质量比为1：0.5～4。Further, in S2, the ball milling time is 5-10min, preferably 8min; wherein, the mass ratio of the slurry and water is 1:0.5-4.
进一步的，在S3中，所述喷雾干燥温度为100～200℃，优选为115℃；其 中，喷雾干燥后粉体的含水量不高于20wt％。Further, in S3, the spray drying temperature is 100-200°C, preferably 115°C; wherein, the water content of the powder after spray drying is not higher than 20wt%.
进一步的，在S1中，所述搅拌的方式为机械搅拌。Further, in S1, the stirring method is mechanical stirring.
进一步的，本发明还要求保护一种纳米稀土氧化物，其采用所述纳米稀土 氧化物的制备方法制得。Further, the present invention also claims to protect a nanometer rare earth oxide, which is prepared by the preparation method of the nanometer rare earth oxide.
进一步的，所述纳米稀土氧化物设为纳米氧化镨、纳米氧化钆、纳米氧化 铥、纳米氧化镧、纳米氧化铒、纳米氧化钬、纳米氧化铽、纳米氧化钐、纳米 氧化钕。Further, the nanometer rare earth oxide is set to nanometer praseodymium oxide, nanometer gadolinium oxide, nanometer thulium oxide, nanometer lanthanum oxide, nanometer erbium oxide, nanometer holmium oxide, nanometer terbium oxide, nanometer samarium oxide, nanometer neodymium oxide.
本发明技术方案，具备如下有益效果：The technical scheme of the present invention has the following beneficial effects:
1、本发明提供了一种以不溶性稀土盐为原料，通过加入熔融盐，采取特殊 的高温煅烧的工艺手段，得到的纳米稀土氧化物具有粒度尺寸小、粒度分布均 匀、纯度高等特点。1. The present invention provides a kind of insoluble rare earth salt as raw material, by adding molten salt and adopting special high temperature calcining process means, the obtained nano rare earth oxide has the characteristics of small particle size, uniform particle size distribution and high purity.
2、本发明纳米稀土氧化物的制备方法简单且稳定，工序少，对设备要求不 高，所用的原材料种类少，产生易于吸收处理的尾气，无毒无污染，生产成本 低，易于工业化生产。2. The preparation method of the nanometer rare earth oxide of the present invention is simple and stable, has few procedures, does not require high equipment, uses few types of raw materials, produces tail gas that is easy to absorb and handle, is non-toxic and pollution-free, has low production cost, and is easy to industrialized production.
3、本发明所用的搅拌分散方式为室温下的机械搅拌，机械搅拌分散的作用 在于将熔融盐充分的与不溶于水的稀土盐混合分散均匀，使得熔融盐吸附在不 溶于水的稀土盐表面。3. The stirring and dispersing method used in the present invention is mechanical stirring at room temperature. The function of mechanical stirring and dispersing is to fully mix and disperse the molten salt with the water-insoluble rare earth salt, so that the molten salt is adsorbed on the surface of the water-insoluble rare earth salt. .
4、本发明球磨的作用在于：第一，使得熔融盐更加均匀全面的吸附在不溶 于水的稀土盐表面；第二，由于不溶于水的稀土盐在机械力的作用下发生解离， 新生断面上会生成游离的电价键，使得颗粒分子相互聚集，这样的结果便是使 得煅烧后所得的稀土氧化物团聚更加严重，而盐溶液在水溶液中发生解离生成 的正负离子可以吸附在球磨产物表面，进而阻止颗粒的团聚现象发生。4. The functions of the ball milling of the present invention are as follows: first, the molten salt is more uniformly and comprehensively adsorbed on the surface of the water-insoluble rare earth salt; Free valence bonds will be formed on the cross section, causing the particles and molecules to aggregate with each other. The result is that the agglomeration of rare earth oxides obtained after calcination is more serious, and the positive and negative ions generated by the dissociation of the salt solution in the aqueous solution can be adsorbed on the ball-milled product. surface, thereby preventing the occurrence of particle agglomeration.
5、本发明采取喷雾干燥目的在于将前料更加细化、均匀，便于熔融盐更加 均匀有效的吸附在不溶于水的稀土盐的表面。5. The purpose of spray drying in the present invention is to make the precursor more refined and uniform, so that the molten salt can be more uniformly and effectively adsorbed on the surface of the water-insoluble rare earth salt.
6、本发明通过控制煅烧温度的高低和升至最大温度的时间长短及最大温度 保温时间的长短来促进纳米稀土氧化物的结晶、控制纳米稀土氧化物的晶粒大 小。6. The present invention promotes the crystallization of nanometer rare earth oxides and controls the grain size of nanometer rare earth oxides by controlling the height of calcination temperature, the length of time to rise to the maximum temperature and the length of the maximum temperature holding time.
7、本发明所生产的纳米稀土氧化物纯度高，粒径小，粒径分布范围窄；比 表面积大，高表面活性。7. The nanometer rare earth oxide produced by the present invention has high purity, small particle size, narrow particle size distribution range, large specific surface area and high surface activity.
具体实施方式Detailed ways
实施例1Example 1
本发明提供一种纳米稀土氧化物的制备方法，其具体制备方法如下：The invention provides a preparation method of nanometer rare earth oxide, and its specific preparation method is as follows:
S1：将一定量的熔融盐加入到一定量的水中搅拌溶解，加入一定量的聚乙 二醇、表面活性剂，将混合溶液逐步加入到一定量的不溶于水的稀土盐中，通 过搅拌分散均匀，得到浆料；S1: Add a certain amount of molten salt to a certain amount of water and stir to dissolve, add a certain amount of polyethylene glycol and surfactant, gradually add the mixed solution to a certain amount of water-insoluble rare earth salt, and disperse by stirring uniform to obtain slurry;
S2：将S1中所得到的浆料加入一定量的水球磨，经过过滤筛得到均匀的乳 浊液/悬浮液；S2: add a certain amount of water ball mill to the slurry obtained in S1, obtain a uniform emulsion/suspension through a sieve;
S3：将S2得到的乳浊液/悬浮液一边搅拌一边经喷雾干燥得到粉体；S3: the emulsion/suspension obtained in S2 is stirred to obtain powder through spray drying;
S4：将S3中得到的粉体在炉体中煅烧，煅烧的温度为从室温～900℃，一 段时间后，随炉体降温即得纳米稀土氧化物。S4: calcining the powder obtained in S3 in the furnace body, the calcining temperature is from room temperature to 900°C, and after a period of time, the nano-rare earth oxide is obtained by cooling the furnace body.
本发明提供了一种以不溶性稀土盐为原料，通过加入熔融盐，采取特殊的 高温煅烧的工艺手段，得到的纳米稀土氧化物具有粒度尺寸小、粒度分布均匀、 纯度高等特点。The present invention provides a kind of nano rare earth oxide with small particle size, uniform particle size distribution and high purity by adding molten salt as raw material and adopting special high-temperature calcination process.
本发明纳米稀土氧化物的制备方法简单且稳定，工序少，对设备要求不高， 所用的原材料种类少，产生易于吸收处理的尾气，无毒无污染，生产成本低， 易于工业化生产。The preparation method of the nanometer rare earth oxide of the present invention is simple and stable, has few steps, does not require high equipment, uses few types of raw materials, produces exhaust gas that is easy to absorb and treat, is non-toxic and pollution-free, has low production cost and is easy to industrialize production.
在本实施例中，步骤S1中熔融盐为氯化铵、氯化钠、氯化钾、氟化钠、碳 酸铵、氨水、碳酸钠、碳酸钾、柠檬铵、柠檬酸钠、柠檬酸钾中的一种或者多 种；其中，做为优选的实施方式，熔融盐设为氯化铵或氯化钠。In this embodiment, the molten salt in step S1 is ammonium chloride, sodium chloride, potassium chloride, sodium fluoride, ammonium carbonate, ammonia water, sodium carbonate, potassium carbonate, ammonium citrate, sodium citrate, potassium citrate One or more of; wherein, as a preferred embodiment, the molten salt is set as ammonium chloride or sodium chloride.
在本实施例中，步骤S1中表面活性剂或分散剂可以是十六烷基三甲基溴化 铵、聚乙二醇、硬酯酸、季铵化物中的一种或多种；其中，做为优选的实施方 式，表面活性剂或分散剂设为十六烷基三甲基溴化铵和聚乙二醇。In this embodiment, the surfactant or dispersant in step S1 may be one or more of cetyltrimethylammonium bromide, polyethylene glycol, stearic acid, and quaternary ammonium compound; wherein, As a preferred embodiment, the surfactant or dispersant is set to cetyltrimethylammonium bromide and polyethylene glycol.
在本实施例中，分散剂、表面活性剂的质量分别占原料固体质量的千分之 一到千分之十，作为优选的实施方式，分散剂和表面活性剂分别占原料固定质 量的千分之三。In this embodiment, the mass of the dispersant and the surfactant respectively account for one thousandth to ten thousandths of the solid mass of the raw material. As a preferred embodiment, the dispersant and the surfactant respectively account for one thousandth of the fixed mass of the raw material. ter.
在本实施例中，步骤S1中不溶于水的稀土盐为碳酸盐、醋酸盐和草酸盐中 的一种或多种；In the present embodiment, the water-insoluble rare earth salt in step S1 is one or more of carbonate, acetate and oxalate;
在本实施例中，稀土盐设为草酸镨、草酸铥、草酸铒、草酸钬、草酸铽、 草酸钐、碳酸钆、碳酸镧、碳酸钕。In this embodiment, the rare earth salts are praseodymium oxalate, thulium oxalate, erbium oxalate, holmium oxalate, terbium oxalate, samarium oxalate, gadolinium carbonate, lanthanum carbonate, and neodymium carbonate.
在本实施例中，步骤S1中所用的搅拌分散方式为室温下的机械搅拌。In this embodiment, the stirring and dispersing method used in step S1 is mechanical stirring at room temperature.
本发明机械搅拌分散的作用在于将熔融盐充分的与不溶于水的稀土盐混合 分散均匀，使得熔融盐吸附在不溶于水的稀土盐表面。The function of the mechanical stirring and dispersing of the present invention is to fully mix and disperse the molten salt with the water-insoluble rare earth salt, so that the molten salt is adsorbed on the surface of the water-insoluble rare earth salt.
在本实施例中，所述稀土盐和所述熔融盐的质量比为1:0.01～5；所述稀土 盐和水的质量比为1:0.1～5。In this embodiment, the mass ratio of the rare earth salt and the molten salt is 1:0.01-5; the mass ratio of the rare earth salt and water is 1:0.1-5.
在本实施例中，做为优选的实施方式，水设为去离子水。In this embodiment, as a preferred embodiment, water is set as deionized water.
本发明去离子水可保证物料的纯度，避免物料受到污染，从而提高纳米稀 土氧化物的纯度。The deionized water of the present invention can ensure the purity of the material, avoid the material being polluted, thereby improving the purity of the nanometer rare earth oxide.
在本实施例中，步骤S2中浆料和水的质量比为1：0.5～4。In this embodiment, the mass ratio of slurry and water in step S2 is 1:0.5-4.
在本实施例中，做为优选的实施方式，步骤S2中过滤筛设为80目的过滤 筛。In the present embodiment, as a preferred embodiment, the filter screen in step S2 is set as an 80-mesh filter screen.
在本实施例中，步骤S2中球磨时间为5～10min，其中，做为优选的实施方 式，球磨时间设为8min；本发明可在球磨机中进行球磨处理。In this embodiment, the ball milling time in step S2 is 5～10min, wherein, as a preferred embodiment, the ball milling time is set to 8min; the present invention can carry out ball milling treatment in a ball mill.
本发明球磨的作用在于：1、使得熔融盐更加均匀全面的吸附在不溶于水的 稀土盐表面；2、由于不溶于水的稀土盐在机械力的作用下发生解离，新生断面 上会生成游离的电价键，使得颗粒分子相互聚集，这样的结果便是使得煅烧后 所得的稀土氧化物团聚更加严重，而盐溶液在水溶液中发生解离生成的正负离 子可以吸附在球磨产物表面，进而阻止颗粒的团聚现象发生。The functions of the ball milling of the present invention are as follows: 1. The molten salt is more uniformly and comprehensively adsorbed on the surface of the water-insoluble rare earth salt; The free valence bonds make the particles and molecules agglomerate with each other. The result is that the agglomeration of the rare earth oxides obtained after calcination is more serious, and the positive and negative ions generated by the dissociation of the salt solution in the aqueous solution can be adsorbed on the surface of the ball-milled product, thereby preventing the Agglomeration of particles occurs.
在本实施例中，步骤S3中喷雾干燥温度为100～200℃，其中，做为优选的 实施方式，喷雾干燥温度设为115℃，喷雾干燥后得到的干粉的含水量不高于 20wt％。In this embodiment, the spray-drying temperature in step S3 is 100-200°C, wherein, as a preferred embodiment, the spray-drying temperature is set to 115°C, and the water content of the dry powder obtained after spray-drying is not higher than 20wt%.
本发明采取喷雾干燥目的在于将前料更加细化、均匀，便于熔融盐更加均 匀有效的吸附在不溶于水的稀土盐的表面。The purpose of spray drying in the present invention is to make the pre-material more refined and uniform, so that the molten salt can be more uniformly and effectively adsorbed on the surface of the water-insoluble rare earth salt.
在本实施例中，步骤S4中煅烧所用的炉体可以是马弗炉、管式炉、回旋炉、 坩埚电阻炉、箱式炉、升降炉、井式炉、台车炉、网带炉、辊道窑、推板窑、 隧道炉、回转窑、悬浮煅烧炉或带气氛的该类煅烧设备；其中，做为优选的实 施方式，煅烧所用的炉体设为马弗炉。In this embodiment, the furnace body used for calcination in step S4 may be a muffle furnace, a tube furnace, a rotary furnace, a crucible resistance furnace, a box furnace, a lift furnace, a pit furnace, a trolley furnace, a mesh belt furnace, Roller kiln, push-plate kiln, tunnel furnace, rotary kiln, suspension calcining furnace or such calcination equipment with atmosphere; wherein, as a preferred embodiment, the furnace body used for calcination is set as a muffle furnace.
在本实施例中，步骤S4中煅烧的温度为从室温～900℃，这个煅烧的过程 具体如下：In this embodiment, the temperature of calcination in step S4 is from room temperature to 900 ° C, and the process of this calcination is as follows:
第一阶段处于预热过程，预热温度从室温～400℃，其中升温速率为0.1℃～ 50℃/min，这个阶段可将前料特别是熔融盐活化，部分熔融盐开始溶解或分解；The first stage is in the preheating process, the preheating temperature is from room temperature to 400 °C, and the heating rate is 0.1 °C to 50 °C/min. In this stage, the pre-material, especially the molten salt, can be activated, and part of the molten salt begins to dissolve or decompose;
第二阶段处于加热过程，加热温度从400～600℃，其中升温速率为0.1℃～50℃/min，这个阶段熔融盐加速不溶于水的稀土盐的分解动力学速率和促进氧 化铈的结晶；高温下熔融盐的分解，产生的上升热气流在一定程度上可以打破 部分团聚或具有团聚趋势的稀土盐或稀土氧化物；有效阻止稀土氧化物晶核的 长大和团聚，熔融盐也以助磨剂的机制保留了稀土氧化物的颗粒的分散功能；The second stage is in the heating process, the heating temperature is from 400 to 600 °C, and the heating rate is 0.1 °C to 50 °C/min. In this stage, the molten salt accelerates the decomposition kinetic rate of the water-insoluble rare earth salt and promotes the crystallization of cerium oxide; Decomposition of molten salt at high temperature, the resulting rising hot air flow can break partial agglomeration or rare earth salt or rare earth oxide with agglomeration tendency to a certain extent; effectively prevent the growth and agglomeration of the crystal nucleus of rare earth oxide, and molten salt can also help grinding The mechanism of the agent retains the dispersion function of the particles of rare earth oxides;
第三阶段处于高温加热过程，高温加热温度从600～900℃，其中升温速率 为0.1℃～50℃/min，这个阶段目的在于产物稀土氧化物晶核的快速成型以及晶 粒的长大，高温使得产物稀土氧化物的晶核快速成型，熔融盐的存在有效组织 稀土氧化物晶核的长大和团聚，一定程度上控制颗粒的粒径；The third stage is in the high-temperature heating process. The high-temperature heating temperature is from 600 to 900 °C, and the heating rate is 0.1 °C to 50 °C/min. The purpose of this stage is the rapid prototyping of the product rare earth oxide crystal nucleus and grain growth. The crystal nucleus of the product rare earth oxide is rapidly formed, and the presence of molten salt effectively organizes the growth and agglomeration of the rare earth oxide crystal nucleus, and controls the particle size to a certain extent;
第四阶段处于保温过程，当达到最高温度时进行保温处理，通过恒定的温 度及其时间的长短来促进稀土氧化物的结晶、控制产物稀土氧化物晶粒的大小； 其中，保温时间为0～300min；The fourth stage is in the heat preservation process. When the highest temperature is reached, heat preservation treatment is performed to promote the crystallization of rare earth oxides and control the size of the product rare earth oxide crystal grains through a constant temperature and the length of time; wherein, the heat preservation time is 0～ 300min;
第五阶段处于降温过程，这个阶段目的在于随炉体冷却至室温，可制得纳 米稀土氧化物。The fifth stage is in the cooling process, the purpose of this stage is to cool down to room temperature with the furnace body, and nano rare earth oxides can be obtained.
在本实施例中，步骤S4中可通过煅烧温度的高低和升至最大温度的时间长 短及最大温度保温时间的长短来促进纳米稀土氧化物的结晶，同时可控制纳米 稀土氧化物的晶粒大小。In this embodiment, in step S4, the crystallization of the nano rare earth oxide can be promoted by the calcination temperature, the length of time to rise to the maximum temperature and the length of the maximum temperature holding time, and the grain size of the nano rare earth oxide can be controlled at the same time .
实施例2Example 2
本发明还提供一种纳米稀土氧化物，其采用纳米稀土氧化物的制备方法制 得。The present invention also provides a nanometer rare earth oxide, which is prepared by the preparation method of the nanometer rare earth oxide.
在本实施例中，纳米稀土氧化物设为纳米氧化镨、纳米氧化钆、纳米氧化 铥、纳米氧化镧、纳米氧化铒、纳米氧化钬、纳米氧化铽、纳米氧化钐、纳米 氧化钕。In this embodiment, the nanometer rare earth oxides are set as nanopraseodymium oxide, nanometer gadolinium oxide, nanometer thulium oxide, nanometer lanthanum oxide, nanometer erbium oxide, nanometer holmium oxide, nanometer terbium oxide, nanometer samarium oxide, and nanometer neodymium oxide.
本发明得到的纳米稀土氧化物具有粒度尺寸小、粒度分布均匀、纯度高等 特点。The nanometer rare earth oxide obtained by the invention has the characteristics of small particle size, uniform particle size distribution and high purity.
实施例3Example 3
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸镨中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25 g of praseodymium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀，将其放入球磨机中以 400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并用适量去 离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly, put it into a ball mill for 8 minutes at a speed of about 400r/min, pass the ball-milled slurry through an 80-mesh sieve and use an appropriate amount of deionized water Rinse and sieve the slurry, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为50nm左右并且 分布均匀的纳米氧化镨。In the fifth step, when it reaches 800 ° C, heat preservation treatment is performed, and the heat preservation time is 90 minutes; after the heat preservation, cooling treatment is performed, and as the furnace body is cooled to room temperature, the time is 40 minutes, and the nano-oxidation with a particle size of about 50 nm and a uniform distribution can be obtained. praseodymium.
实施例4Example 4
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g碳酸钆中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25 g of gadolinium carbonate, and the slurry was uniformly dispersed by stirring to obtain a slurry;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为50nm左右并且 分布均匀的纳米氧化钆。In the fifth step, when it reaches 800 ° C, heat preservation treatment is performed, and the heat preservation time is 90 minutes; after the heat preservation, cooling treatment is performed, and as the furnace body is cooled to room temperature, the time is 40 minutes, and the nano-oxidation with a particle size of about 50 nm and a uniform distribution can be obtained. gadolinium.
实施例5Example 5
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸铥中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25 g of thulium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为100～200nm并 且分布均匀的纳米氧化铥。In the fifth step, when it reaches 800 ° C, heat preservation treatment is carried out, and the heat preservation time is 90 minutes; after heat preservation, cooling treatment is carried out, and as the furnace body is cooled to room temperature, the time is 40 minutes, and the particle size is 100 ~ 200nm and uniformly distributed nanometers can be obtained. Thulium oxide.
实施例6Example 6
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g碳酸镧中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25g of lanthanum carbonate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为50nm并且分布 均匀的纳米氧化镧。In the fifth step, when it reaches 800 ° C, heat preservation treatment is carried out, and the heat preservation time is 90 minutes; after the heat preservation, cooling treatment is carried out, and as the furnace body is cooled to room temperature, the time is 40 minutes, and the nanometer lanthanum oxide with a particle size of 50 nm and a uniform distribution can be obtained. .
实施例7Example 7
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸铒中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25 g of erbium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为50nm并且分布 均匀的纳米氧化铒。The fifth step, when it reaches 800 ℃, heat preservation treatment is carried out, and the heat preservation time is 90min; after heat preservation, cooling treatment is carried out, and the time is 40min as the furnace body is cooled to room temperature, and the nanometer erbium oxide with a particle size of 50nm and a uniform distribution can be obtained .
实施例8Example 8
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸钬中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25g of holmium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为50nm并且分布 均匀的纳米氧化钬。The fifth step, when it reaches 800 ℃, heat preservation treatment is carried out, and the heat preservation time is 90min; after heat preservation, cooling treatment is carried out, and the time is 40min as the furnace body is cooled to room temperature, and the nanometer holmium oxide with a particle size of 50nm and a uniform distribution can be obtained .
实施例9Example 9
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸铽中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25g of terbium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为50nm并且分布 均匀的纳米氧化铽。In the fifth step, when it reaches 800 ° C, heat preservation treatment is carried out, and the heat preservation time is 90 minutes; after the heat preservation, cooling treatment is carried out, and as the furnace body is cooled to room temperature, the time is 40 minutes, and the nanometer terbium oxide with a particle size of 50 nm and a uniform distribution can be obtained. .
实施例10Example 10
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸钐中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25g of samarium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为50nm并且分布 均匀的纳米氧化钐。In the fifth step, when it reaches 800 ° C, heat preservation treatment is carried out, and the heat preservation time is 90 minutes; after heat preservation, cooling treatment is carried out, and as the furnace body is cooled to room temperature, the time is 40 minutes, and the nanometer samarium oxide with a particle size of 50 nm and a uniform distribution can be obtained. .
实施例11Example 11
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g碳酸钕中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25g of neodymium carbonate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为60min；In the fourth step, the dry powder of the mixture is placed in a ceramic crucible, and the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 60min;
第五步，当达到800℃时进行保温处理，保温时间为90min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为50nm并且分布 均匀的纳米氧化钕。In the fifth step, when it reaches 800 ° C, heat preservation treatment is carried out, and the heat preservation time is 90 minutes; after the heat preservation, cooling treatment is carried out, and the furnace body is cooled to room temperature for 40 minutes to obtain nanometer neodymium oxide with a particle size of 50 nm and a uniform distribution. .
实施例12Example 12
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸镨中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25 g of praseodymium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从300～850℃，时间为30min；The 4th step, the mixture dry powder is placed in a ceramic crucible, the ceramic crucible is placed in a muffle furnace for calcination, and the calcining temperature is set from 300 to 850°C, and the time is 30min;
第五步，当达到850℃时进行保温处理，保温时间为60min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为100-200nm并 且分布均匀的纳米氧化镨。The fifth step, when it reaches 850°C, heat preservation treatment is carried out, and the heat preservation time is 60min; after the heat preservation, cooling treatment is carried out, and as the furnace body is cooled to room temperature, the time is 40min, and the particle size is 100-200nm and uniformly distributed nanometers can be obtained. Praseodymium oxide.
实施例13Example 13
第一步，将1.75g氯化钠加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸镨中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of sodium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, and 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution. The mixed solution was gradually added to 25 g of praseodymium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～900℃，时间为90min；The 4th step, the mixture dried powder is placed in a ceramic crucible, the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 900°C, and the time is 90min;
第五步，当达到900℃时进行保温处理，保温时间为60min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为300-400nm并 且分布均匀的纳米氧化镨。In the fifth step, when it reaches 900 ° C, heat preservation treatment is performed, and the heat preservation time is 60 minutes; after the heat preservation, cooling treatment is performed, and as the furnace body is cooled to room temperature, the time is 40 minutes, and nanometers with a particle size of 300-400 nm and uniform distribution can be obtained. Praseodymium oxide.
实施例14Example 14
第一步，将1.75g氯化铵加入到7.5g、90℃的去离子水中搅拌溶解，加入 0.025g聚乙二醇以及0.025g十六烷基三甲基溴化铵得到混合溶液，再将混合溶 液逐步加入到25g草酸镨中，通过搅拌分散均匀，得到浆料；In the first step, 1.75g of ammonium chloride was added to 7.5g of deionized water at 90°C and stirred to dissolve, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide were added to obtain a mixed solution, and then The mixed solution was gradually added to 25 g of praseodymium oxalate, and the slurry was obtained by stirring and dispersing evenly;
第二步，将得到的浆料加入7.5g去离子水搅拌均匀后得浆料，将其放入球 磨机中以400r/min左右的转速球磨8min，将球磨后的浆料过80目的过滤筛并 用适量去离子水将浆料冲洗过筛，控制得到的乳浊液/悬浮液质量分数为40％；In the second step, add 7.5g of deionized water to the obtained slurry and stir evenly to obtain a slurry, put it into a ball mill for ball milling at a speed of about 400 r/min for 8 minutes, and pass the ball-milled slurry through an 80-mesh sieve and use Rinse and sieve the slurry with an appropriate amount of deionized water, and control the mass fraction of the obtained emulsion/suspension to be 40%;
第三步，将乳浊液/悬浮液一边搅拌一边喷雾干燥，控制喷雾干燥的温度为 115℃，进料量为550ml/h，得到混合物干燥粉体；其中，喷雾干燥后粉体的含 水量不高于20wt％；In the third step, the emulsion/suspension is spray-dried while stirring, and the temperature of the spray-drying is controlled to be 115° C., and the feed rate is 550 ml/h to obtain a dry mixture powder; wherein, the water content of the powder after spray-drying not higher than 20wt%;
第四步，将混合物干燥粉体置于陶瓷坩埚中，将陶瓷坩埚置于马弗炉里进 行煅烧处理，设置煅烧的温度从室温～800℃，时间为90min；The 4th step, the mixture dry powder is placed in a ceramic crucible, the ceramic crucible is placed in a muffle furnace for calcination treatment, and the calcining temperature is set from room temperature to 800°C, and the time is 90min;
第五步，当达到800℃时进行保温处理，保温时间为60min；保温过后进行 冷却处理，随着炉体冷却至室温，时间为40min，即可得到粒径为30nm并且分 布均匀的纳米氧化镨。The fifth step, when reaching 800 ° C, carry out heat preservation treatment, and the heat preservation time is 60min; after heat preservation, carry out cooling treatment, as the furnace body is cooled to room temperature, the time is 40min, the particle size is 30nm and uniformly distributed nano praseodymium oxide can be obtained .
通过将实施例3～11分别和实施例14对比，可以得出在煅烧最大温度以及 煅烧时间相同的情况下，随着煅烧时间越长，其纳米氧化物的粒径越小。By comparing Examples 3 to 11 with Example 14, it can be concluded that with the same maximum calcination temperature and calcination time, as the calcination time is longer, the particle size of the nano-oxides is smaller.
通过实施例13与实施例14对比，可以得出在煅烧时间以及最大温度的保 温时间相同的情况下，随着最大温度的升高，其纳米氧化物的粒径越大，且变 化较大。Through the comparison between Example 13 and Example 14, it can be concluded that under the same conditions of calcination time and maximum temperature holding time, with the increase of maximum temperature, the particle size of its nano-oxides is larger, and the change is larger.
通过分析实施例3～14，可以得出最大煅烧温度在800℃时，得到的纳米氧 化物粒径最小为30nm，可以看出本发明得到的纳米稀土氧化物的粒度尺寸小、 而且粒度分布比较均匀。By analyzing Examples 3 to 14, it can be concluded that when the maximum calcination temperature is 800° C., the particle size of the obtained nano-oxide is at least 30 nm. It can be seen that the particle size of the nano-rare earth oxide obtained by the present invention is small, and the particle size distribution is relatively small. evenly.
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的 限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何 熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示 的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发 明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、 等同变化与修饰，均仍属于本发明技术方案的范围内。The above are only preferred embodiments of the present invention, and do not limit the present invention in any form. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Technical personnel, within the scope of the technical solution of the present invention, can make some changes or modifications to equivalent examples of equivalent changes by using the technical content disclosed above, provided that the content of the technical solution of the present invention is not deviated from, according to the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solutions of the present invention.
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