WO2012065575A1 - Process for preparing red fluorescent powder of low europium content - Google Patents

Process for preparing red fluorescent powder of low europium content Download PDF

Info

Publication number
WO2012065575A1
WO2012065575A1 PCT/CN2011/082440 CN2011082440W WO2012065575A1 WO 2012065575 A1 WO2012065575 A1 WO 2012065575A1 CN 2011082440 W CN2011082440 W CN 2011082440W WO 2012065575 A1 WO2012065575 A1 WO 2012065575A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder
red phosphor
solution
europium
cerium
Prior art date
Application number
PCT/CN2011/082440
Other languages
French (fr)
Chinese (zh)
Inventor
吴建华
梁敏婷
万国江
徐燕
Original Assignee
江门市科恒实业股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 江门市科恒实业股份有限公司 filed Critical 江门市科恒实业股份有限公司
Publication of WO2012065575A1 publication Critical patent/WO2012065575A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7784—Chalcogenides
    • C09K11/7787—Oxides

Definitions

  • the invention relates to a method for preparing a phosphor, in particular to a method for preparing a low-yield red phosphor.
  • the world's first compact three-primary energy-saving fluorescent lamp was introduced in the early 1980s, marking the birth of the third generation of lighting products.
  • the development of rare earth separation technology and rare earth trichromatic phosphor production technology plays an important role in the promotion of energy-saving fluorescent lamps.
  • the phosphor component used in the rare earth trichromatic fluorescent lamp is: the red powder is generally prepared by a solid phase reaction method using cerium activated cerium oxide.
  • the existing red phosphor that is, the europium-activated cerium oxide powder, generally has a mass content of Eu 2 O 3 of 5% or more. In order to obtain a better luminescent effect, it is generally required to use more. Oh, this is also an important reason for the cost of red phosphors.
  • a preparation method of low bismuth content red phosphor comprises the following steps:
  • the calcined powder is sintered at 1300 to 1500 ° C for 2 to 4 hours, and the solid obtained by sintering is ground, washed and dried to obtain a red phosphor.
  • the calcined powder is added to the dispersant and uniformly mixed and then sintered.
  • the dispersing agent is at least one of BaCl 2 , BaF 2 , CaF 2 and SrF 2 , and the dispersing agent is added in an amount of 0.05 to 0.5% by mass of the calcined powder.
  • the weakly alkaline solution is at least one of a urea solution, an aqueous ammonia solution, an ammonium carbonate solution, and an ammonium hydrogencarbonate solution.
  • the method of the invention effectively improves the utilization rate of the crucible and reduces the amount of antimony.
  • the red phosphor prepared by the method of the invention can greatly reduce the amount of ruthenium used without reducing or slightly reducing the luminescent properties of the phosphor, so that the overall cost is reduced by about 10%.
  • Fig. 1 is a chart showing the emission spectrum of the red phosphor obtained in Example 1.
  • a preparation method of low bismuth content red phosphor comprises the following steps:
  • the calcined powder is sintered at 1300 to 1500 ° C for 2 to 4 hours, and the solid obtained by sintering is ground, washed and dried to obtain a red phosphor.
  • the calcined powder is added to the dispersant and uniformly mixed and then sintered.
  • the dispersing agent is at least one of BaCl 2 , BaF 2 , CaF 2 and SrF 2 , and the dispersing agent is added in an amount of 0.05 to 0.5% by mass of the calcined powder.
  • various dispersing agents can be used in combination, and other dispersing agents commonly used in the art can also be used.
  • the weakly alkaline solution is at least one of a urea solution, an aqueous ammonia solution, an ammonium carbonate solution, and an ammonium hydrogencarbonate solution.
  • a urea solution aqueous ammonia solution
  • an ammonium carbonate solution aqueous ammonium carbonate solution
  • an ammonium hydrogencarbonate solution aqueous ammonia solution
  • those skilled in the art can mix and use various solutions as needed. From the viewpoint of ease of operation, in the following examples, only a single weakly alkaline solution is used.
  • the red phosphor had a cerium oxide content of 5.6% and a relative brightness of 107.8%.
  • the red phosphor had a cerium oxide content of 4.1% and a relative brightness of 104.5%.
  • the red phosphor showed a cerium oxide content of 5.8% and a relative brightness of 108.0%.
  • the red phosphor had a cerium oxide content of 4.6% and a relative brightness of 106.0%.
  • the phosphor prepared by the method of the invention has better luminescent properties than the existing commercial red powder.
  • the strontium element used is nearly 20% lower than the existing commercial red powder, and the dosage is greatly increased. cut back.
  • the present invention employs a solid phase sintering diffusion technique to prepare cerium oxide activated by a lower concentration of rare earth red phosphor.
  • a solid phase sintering diffusion technique to prepare cerium oxide activated by a lower concentration of rare earth red phosphor.
  • a small amount of activator is precipitated on the surface of the lower doping concentration powder, and then the sintering temperature and time are controlled to prevent the doping element from diffusing into the luminescence particle phase.
  • the ytterbium-activated yttrium oxide red phosphor with a high surface doping concentration and a low inner layer doping concentration reduces the amount of yttrium oxide while ensuring the performance of the product.
  • the method of the invention effectively improves the utilization rate of the crucible and reduces the amount of antimony.
  • the red phosphor prepared by the method of the invention can greatly reduce the amount of ruthenium used without reducing or slightly reducing the luminescent properties of the phosphor, so that the overall cost is reduced by about 10%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

Disclosed is a process for preparing a red fluorescent powder of a low europium content, which comprises having an yttrium-europium oxide powder dispersed and co-precipitated in a weak alkaline solution; adding, under stirring, a water-soluble solution of europium salt into the weak alkaline solution to have the europium element therein precipitated; washing and drying by baking the precipitate and then firing the same for one hour at 800-1000°C to obtain a pre-fired powder; having the pre-fired powder sintered for 2 to 4 hours at 1300-1500°C, and having the sintered solid ground, washed and dried by baking, so as to obtain the red fluorescent powder. The process of the present invention has effectively improved the utilization of europium and reduced the amount of europium used. By using the red fluorescent powder prepared in the process of the present invention, the amount of the europium used can be reduced significantly and the overall costs thereof can be reduced by 10% under the premise of not reducing or only slightly reducing the light-emitting performance of the fluorescent powder.

Description

一种低铕含量红色荧光粉的制备方法  Preparation method of low bismuth content red phosphor
技术领域Technical field
本发明涉及一种荧光粉的制备方法，特别涉及一种低铕含量红色荧光粉的制备方法。The invention relates to a method for preparing a phosphor, in particular to a method for preparing a low-yield red phosphor.
背景技术Background technique
20世纪80年代初世界上第一支紧凑型三基色节能荧光灯问世，标志着第三代照明产品的诞生。稀土分离技术和稀土三基色荧光粉生产技术的发展为节能荧光灯的推广起非常重要的作用。The world's first compact three-primary energy-saving fluorescent lamp was introduced in the early 1980s, marking the birth of the third generation of lighting products. The development of rare earth separation technology and rare earth trichromatic phosphor production technology plays an important role in the promotion of energy-saving fluorescent lamps.
制造高品质的节能灯要求荧光粉的化学稳定性好、制灯后光效高、使用寿命长和光衰低。目前我国的荧光粉制备工业已经有了长足的进步，然而，和国外相比，我国的荧光粉工业还是以简单的重复建设和规模扩张为主，在技术进步和原材料特性上没有差异化，荧光粉的质量也大同小异。The manufacture of high-quality energy-saving lamps requires good chemical stability of the phosphor, high luminous efficiency after lamp making, long service life and low light decay. At present, China's phosphor preparation industry has made great progress. However, compared with foreign countries, China's phosphor industry is mainly based on simple repeated construction and scale expansion, and there is no difference in technological progress and raw material characteristics. The quality of the powder is similar.
进入21世纪，随着能源和环境问题的加剧，高效节能荧光灯的发展遇到了前所未有的机遇，作为节能荧光灯的关键材料―稀土三基色荧光粉的发展也面临着重大的机遇和挑战：一方面不断增长的需求带来了巨大的商机，一方面却不得不面临着日益趋紧的稀土资源的制约。由于稀土元素不可再生，战略意义重大，我国已对稀土进行保护性开发。In the 21st century, with the intensification of energy and environmental issues, the development of high-efficiency energy-saving fluorescent lamps has encountered unprecedented opportunities. As a key material for energy-saving fluorescent lamps, the development of rare earth trichromatic phosphors also faces major opportunities and challenges: The demand for growth has brought huge business opportunities, but on the other hand it has to face the constraints of increasingly tight rare earth resources. Since rare earth elements are not regenerable, the strategic significance is significant, and China has developed protective development for rare earths.
为此，如何在减少稀土元素使用量的同时，保持，甚至提高荧光粉的发光效率具有十分重要的意义。For this reason, how to reduce or even increase the luminous efficiency of the phosphor is of great significance while reducing the amount of rare earth elements used.
目前稀土三基色荧光灯中使用的荧光粉组分为：红粉普遍采用铕激活的氧化钇，通过固相反应法制得。为保证荧光粉的发光效率，现有的红色荧光粉，即铕激活的氧化钇粉中，Eu2O3质量含量一般在5%以上，为获得更好的发光效果，一般需要使用更多的铕，这也是影响红色荧光粉成本的一个重要原因。At present, the phosphor component used in the rare earth trichromatic fluorescent lamp is: the red powder is generally prepared by a solid phase reaction method using cerium activated cerium oxide. In order to ensure the luminous efficiency of the phosphor, the existing red phosphor, that is, the europium-activated cerium oxide powder, generally has a mass content of Eu 2 O 3 of 5% or more. In order to obtain a better luminescent effect, it is generally required to use more. Oh, this is also an important reason for the cost of red phosphors.
发明内容Summary of the invention
本发明的目的在于提供一种低铕含量红色荧光粉的制备方法。It is an object of the present invention to provide a method for preparing a low bismuth content red phosphor.
本发明所采取的技术方案是：The technical solution adopted by the present invention is:
一种低铕含量红色荧光粉的制备方法，包括以下步骤：A preparation method of low bismuth content red phosphor comprises the following steps:
1) 将氧化钇铕粉体共沉淀分散于弱碱性溶液中； 1) dispersing the cerium oxide powder coprecipitate in a weakly alkaline solution;
2) 在搅拌条件下，将水溶性铕盐溶液加入上述弱碱性溶液中，使铕元素沉淀；2) adding a water-soluble cerium salt solution to the above weak alkaline solution under stirring to precipitate cerium element;
3) 将沉淀物洗涤烘干， 800～1000℃灼烧1～小时，得到预烧粉体；3) Washing and drying the precipitate, burning at 800 to 1000 ° C for 1 to hour to obtain a pre-calcined powder;
4) 将预烧粉体在1300～1500℃烧结2～4h，将烧结得到的固体研磨，洗涤烘干，得到红色荧光粉。4) The calcined powder is sintered at 1300 to 1500 ° C for 2 to 4 hours, and the solid obtained by sintering is ground, washed and dried to obtain a red phosphor.
优选的，预烧粉体加入分散剂混合均匀后再烧结。分散剂为BaCl2、BaF2、CaF2、SrF2中的至少一种，分散剂的添加量为预烧粉体质量的0.05～0.5%。Preferably, the calcined powder is added to the dispersant and uniformly mixed and then sintered. The dispersing agent is at least one of BaCl 2 , BaF 2 , CaF 2 and SrF 2 , and the dispersing agent is added in an amount of 0.05 to 0.5% by mass of the calcined powder.
优选的，弱碱性溶液为尿素溶液、氨水溶液、碳酸铵溶液、碳酸氢铵溶液中的至少一种。Preferably, the weakly alkaline solution is at least one of a urea solution, an aqueous ammonia solution, an ammonium carbonate solution, and an ammonium hydrogencarbonate solution.
本发明方法有效地提高了铕的利用率，减少了铕的用量。通过本发明方法制备的红色荧光粉，在不降低，或很少降低荧光粉发光性能的前提下，可大大减少铕的使用量，使得其整体成本降低约10%。The method of the invention effectively improves the utilization rate of the crucible and reduces the amount of antimony. The red phosphor prepared by the method of the invention can greatly reduce the amount of ruthenium used without reducing or slightly reducing the luminescent properties of the phosphor, so that the overall cost is reduced by about 10%.
附图说明DRAWINGS
图1是实施例1所得红色荧光粉的发射光谱图。Fig. 1 is a chart showing the emission spectrum of the red phosphor obtained in Example 1.
具体实施方式detailed description
一种低铕含量红色荧光粉的制备方法，包括以下步骤：A preparation method of low bismuth content red phosphor comprises the following steps:
1) 将氧化钇铕粉体共沉淀分散于弱碱性溶液中； 1) dispersing the cerium oxide powder coprecipitate in a weakly alkaline solution;
2) 在搅拌条件下，将水溶性铕盐溶液加入上述弱碱性溶液中，使铕元素沉淀；2) adding a water-soluble cerium salt solution to the above weak alkaline solution under stirring to precipitate cerium element;
3) 将沉淀物洗涤烘干， 800～1000℃灼烧1～小时，得到预烧粉体；3) Washing and drying the precipitate, burning at 800 to 1000 ° C for 1 to hour to obtain a pre-calcined powder;
4) 将预烧粉体在1300～1500℃烧结2～4h，将烧结得到的固体研磨，洗涤烘干，得到红色荧光粉。4) The calcined powder is sintered at 1300 to 1500 ° C for 2 to 4 hours, and the solid obtained by sintering is ground, washed and dried to obtain a red phosphor.
优选的，预烧粉体加入分散剂混合均匀后再烧结。分散剂为BaCl2、BaF2、CaF2、SrF2 中的至少一种，分散剂的添加量为预烧粉体质量的0.05～0.5%。作为本领域技术人员的基本常识，可知各种分散剂可混合使用，亦可使用其他本领域中常用的分散剂。Preferably, the calcined powder is added to the dispersant and uniformly mixed and then sintered. The dispersing agent is at least one of BaCl 2 , BaF 2 , CaF 2 and SrF 2 , and the dispersing agent is added in an amount of 0.05 to 0.5% by mass of the calcined powder. As a basic common knowledge of those skilled in the art, various dispersing agents can be used in combination, and other dispersing agents commonly used in the art can also be used.
优选的，弱碱性溶液为尿素溶液、氨水溶液、碳酸铵溶液、碳酸氢铵溶液中的至少一种。当然，本领域的技术人员，可以根据需要将各种溶液混合使用，从操作方便方面考虑，以下实施例中，仅使用了单一的弱碱性溶液。Preferably, the weakly alkaline solution is at least one of a urea solution, an aqueous ammonia solution, an ammonium carbonate solution, and an ammonium hydrogencarbonate solution. Of course, those skilled in the art can mix and use various solutions as needed. From the viewpoint of ease of operation, in the following examples, only a single weakly alkaline solution is used.
下面结合实施例，进一步说明本发明。The invention will now be further described in conjunction with the examples.
以下实施例中的百分比，如无特别说明，均为质量百分比。The percentages in the following examples are percentages by mass unless otherwise stated.
实施例1Example 1
1) 将10g氧化铕含量为5.0%的氧化钇铕共沉淀分散于100ml 0.2mol/l的尿素溶液中；1) Dispersing 10 g of cerium oxide coprecipitate having a cerium oxide content of 5.0% in 100 ml of a 0.2 mol/l urea solution;
2) 搅拌条件下，向上述混合液中滴加含有0.06g氧化铕的硝酸铕溶液，继续搅拌使铕元素沉淀完全在氧化钇铕粉体上；2) Under stirring, a cerium nitrate solution containing 0.06 g of cerium oxide was added dropwise to the above mixture, and stirring was continued to precipitate the cerium element completely on the cerium oxide powder;
3) 将沉淀物洗涤、烘干，800℃灼烧3h，得到预烧粉体；3) Washing and drying the precipitate, burning at 800 ° C for 3 h to obtain a pre-calcined powder;
4) 在预烧粉体中混入0.05%的分散剂BaF2，1380℃烧结2h，得到烧结固体；4) mixing 0.05% dispersant BaF 2 in the calcined powder and sintering at 1380 ° C for 2 h to obtain a sintered solid;
5) 将烧结固体研磨，洗涤烘干得到红色荧光粉。5) The sintered solid is ground, washed and dried to obtain a red phosphor.
经检测，红色荧光粉中，氧化铕含量为5.6%，相对亮度为107.8%。After detection, the red phosphor had a cerium oxide content of 5.6% and a relative brightness of 107.8%.
实施例2Example 2
1) 将10g氧化铕含量为3.5%的氧化钇铕共沉淀分散于100ml 0.15mol/l的氨水溶液中；1) Dispersing 10 g of cerium oxide coprecipitate having a cerium oxide content of 3.5% in 100 ml of a 0.15 mol/l aqueous ammonia solution;
2) 搅拌条件下，向上述混合液中滴加含有0.06g氧化铕的硝酸铕溶液，继续搅拌使铕元素沉淀完全在氧化钇铕粉体上；2) Under stirring, a cerium nitrate solution containing 0.06 g of cerium oxide was added dropwise to the above mixture, and stirring was continued to precipitate the cerium element completely on the cerium oxide powder;
3) 将沉淀物洗涤、烘干，1000℃灼烧1h，得到预烧粉体；3) washing and drying the precipitate, and burning at 1000 ° C for 1 h to obtain a pre-calcined powder;
4) 在预烧粉体中混入0.3%的分散剂CaF2，1300℃烧结4h，得到烧结固体；4) 0.3% dispersant CaF 2 was mixed into the calcined powder, and sintered at 1300 ° C for 4 h to obtain a sintered solid;
5) 将烧结固体研磨，洗涤烘干得到红色荧光粉。5) The sintered solid is ground, washed and dried to obtain a red phosphor.
经检测，红色荧光粉中，氧化铕含量为4.1%，相对亮度为104.5%。The red phosphor had a cerium oxide content of 4.1% and a relative brightness of 104.5%.
实施例3Example 3
1) 将10g氧化铕含量为5.0%的氧化钇铕共沉淀分散于100ml 0.18mol/l的碳酸铵溶液中；1) Disperse 10 g of cerium oxide coprecipitate with a cerium oxide content of 5.0% in 100 ml 0.18 mol/l of ammonium carbonate solution;
2) 搅拌条件下，向上述混合液中滴加含有0.08g氧化铕的硝酸铕溶液，继续搅拌使铕元素沉淀完全在氧化钇铕粉体上；2) Under stirring, a cerium nitrate solution containing 0.08 g of cerium oxide was added dropwise to the above mixture, and stirring was continued to precipitate the cerium element completely on the cerium oxide powder;
3) 将沉淀物洗涤、烘干，850℃灼烧2h，得到预烧粉体；3) Washing and drying the precipitate, and burning at 850 ° C for 2 h to obtain a calcined powder;
4) 在预烧粉体中混入0.5%的分散剂SrF2，1450℃烧结3h，得到烧结固体；4) mixing 0.5% dispersant SrF 2 in the calcined powder and sintering at 1450 ° C for 3 h to obtain a sintered solid;
5) 将烧结固体研磨，洗涤烘干得到红色荧光粉。5) The sintered solid is ground, washed and dried to obtain a red phosphor.
经检测，红色荧光粉中，氧化铕含量为5.8%，相对亮度为108.0%。The red phosphor showed a cerium oxide content of 5.8% and a relative brightness of 108.0%.
实施例4Example 4
1) 将10g氧化铕含量为4.0%的氧化钇铕共沉淀分散于100ml 0.23mol/l的碳酸氢铵溶液中；1) Disperse 10 g of cerium oxide coprecipitate with a cerium oxide content of 4.0% in 100 ml 0.23 mol/l of ammonium hydrogencarbonate solution;
2) 搅拌条件下，向上述混合液中滴加含有0.06g氧化铕的硝酸铕溶液，继续搅拌使铕元素沉淀完全在氧化钇铕粉体上；2) Under stirring, a cerium nitrate solution containing 0.06 g of cerium oxide was added dropwise to the above mixture, and stirring was continued to precipitate the cerium element completely on the cerium oxide powder;
3) 将沉淀物洗涤、烘干，900℃灼烧2h，得到预烧粉体；3) Washing and drying the precipitate, and burning at 900 ° C for 2 h to obtain a pre-calcined powder;
4) 在预烧粉体中混入0.15%的分散剂BaF2，1500℃烧结2h，得到烧结固体；4) mixing 0.15% of dispersant BaF 2 into the calcined powder and sintering at 1500 ° C for 2 h to obtain a sintered solid;
5) 将烧结固体研磨，洗涤烘干得到红色荧光粉。5) The sintered solid is ground, washed and dried to obtain a red phosphor.
经检测，红色荧光粉中，氧化铕含量为4.6%，相对亮度为106.0%。After detection, the red phosphor had a cerium oxide content of 4.6% and a relative brightness of 106.0%.
选取与上述实施例产品相对亮度接近的商品红粉（常规固相反应法制备），比较其中的铕含量，其结果如下表所示：The commercial red powder (prepared by conventional solid phase reaction method) which is close to the relative brightness of the products of the above examples was selected, and the cerium content was compared, and the results are shown in the following table:
样品编号 Sample serial number 样品的 Eu203%Sample of Eu 2 0 3 % 相对亮度 /% Relative brightness /% 商品红粉的 Eu203%Compressed red powder of Eu 2 0 3 % 相对亮度 /% Relative brightness /%
实施例 1 Example 1 5.6 5.6 107.8 107.8 6.6 6.6 107.7 107.7
实施例 2 Example 2 4.1 4.1 104.5 104.5 5.0 5.0 104 104
实施例 3 Example 3 5.8 5.8 108.0 108.0 6.6 6.6 107.8 107.8
实施例 4 Example 4 4.6 4.6 105.6 105.6 5.0 5.0 104.2 104.2
由比中数据可清楚的看出，本发明方法制备得到的荧光粉，发光性能明显好于现有的商品红粉，同等亮度下，使用的铕元素较现有的商品红粉低近20%，用量大大减少。It can be clearly seen from the above data that the phosphor prepared by the method of the invention has better luminescent properties than the existing commercial red powder. Under the same brightness, the strontium element used is nearly 20% lower than the existing commercial red powder, and the dosage is greatly increased. cut back.
本发明采用固相烧结扩散技术来制备具有较低浓度稀土红色荧光粉铕激活的氧化钇。通过均相沉淀法在较低掺杂浓度粉体表面沉淀少量的激活剂，然后再分散剂存在的条件下，通过控制烧结温度和时间，使得掺杂元素扩散致发光颗粒体相中，形成了表层掺杂浓度高内层掺杂浓度低的铕激活的氧化钇红色荧光粉，在保证产品的性能的同时降低氧化铕用量。The present invention employs a solid phase sintering diffusion technique to prepare cerium oxide activated by a lower concentration of rare earth red phosphor. By means of homogeneous precipitation method, a small amount of activator is precipitated on the surface of the lower doping concentration powder, and then the sintering temperature and time are controlled to prevent the doping element from diffusing into the luminescence particle phase. The ytterbium-activated yttrium oxide red phosphor with a high surface doping concentration and a low inner layer doping concentration reduces the amount of yttrium oxide while ensuring the performance of the product.
本发明方法有效地提高了铕的利用率，减少了铕的用量。通过本发明方法制备的红色荧光粉，在不降低，或很少降低荧光粉发光性能的前提下，可大大减少铕的使用量，使得其整体成本降低约10%。The method of the invention effectively improves the utilization rate of the crucible and reduces the amount of antimony. The red phosphor prepared by the method of the invention can greatly reduce the amount of ruthenium used without reducing or slightly reducing the luminescent properties of the phosphor, so that the overall cost is reduced by about 10%.

Claims (5)

  1. 一种低铕含量红色荧光粉的制备方法，包括以下步骤： A preparation method of low bismuth content red phosphor comprises the following steps:
    1) 将氧化钇铕粉体共沉淀分散于弱碱性溶液中； 1) dispersing the cerium oxide powder coprecipitate in a weakly alkaline solution;
    2) 在搅拌条件下，将水溶性铕盐溶液加入上述弱碱性溶液中，使铕元素沉淀；2) adding a water-soluble cerium salt solution to the above weak alkaline solution under stirring to precipitate cerium element;
    3) 将沉淀物洗涤烘干， 800～1000℃灼烧1～3小时，得到预烧粉体； 3) Washing and drying the precipitate, burning at 800 to 1000 ° C for 1 to 3 hours to obtain a calcined powder;
    4) 将预烧粉体在1300～1500℃烧结2～4h，将烧结得到的固体研磨，洗涤烘干，得到红色荧光粉。 4) The calcined powder is sintered at 1300 to 1500 ° C for 2 to 4 hours, and the solid obtained by sintering is ground, washed and dried to obtain a red phosphor.
  2. 根据权利要求1所述的低铕含量红色荧光粉的制备方法，其特征在于：预烧粉体加入分散剂混合均匀后再烧结。The method for preparing a low bismuth content red phosphor according to claim 1, wherein the pre-sintered powder is added to the dispersant and uniformly mixed, followed by sintering.
  3. 根据权利要求2所述的低铕含量红色荧光粉的制备方法，其特征在于：分散剂为BaCl2、BaF2、CaF2、SrF2中的至少一种。The method for producing a low cerium content red phosphor according to claim 2, wherein the dispersing agent is at least one of BaCl 2 , BaF 2 , CaF 2 and SrF 2 .
  4. 根据权利要求2所述的低铕含量红色荧光粉的制备方法，其特征在于：分散剂的添加量为预烧粉体质量的0.05～0.5%。The method for preparing a low cerium content red phosphor according to claim 2, wherein the dispersing agent is added in an amount of 0.05 to 0.5% by mass of the calcined powder.
  5. 根据权利要求1所述的低铕含量红色荧光粉的制备方法，其特征在于：弱碱性溶液为尿素溶液、氨水溶液、碳酸铵溶液、碳酸氢铵溶液中的至少一种。The method for preparing a low bismuth content red phosphor according to claim 1, wherein the weakly alkaline solution is at least one of a urea solution, an ammonia solution, an ammonium carbonate solution, and an ammonium hydrogencarbonate solution.
PCT/CN2011/082440 2010-11-19 2011-11-18 Process for preparing red fluorescent powder of low europium content WO2012065575A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 201010550335 CN102051171B (en) 2010-11-19 2010-11-19 Method for preparing low-europium red fluorescent powder
CN201010550335.2 2010-11-19

Publications (1)

Publication Number Publication Date
WO2012065575A1 true WO2012065575A1 (en) 2012-05-24

Family

ID=43955979

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2011/082440 WO2012065575A1 (en) 2010-11-19 2011-11-18 Process for preparing red fluorescent powder of low europium content

Country Status (2)

Country Link
CN (1) CN102051171B (en)
WO (1) WO2012065575A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115448718A (en) * 2022-09-20 2022-12-09 中国核动力研究设计院 Europium hafnate material, preparation method and application
CN115477946A (en) * 2022-09-30 2022-12-16 云南大学 Green fluorescent material for non-contact temperature sensor and preparation method thereof
CN117004387A (en) * 2023-08-08 2023-11-07 烟台布莱特光电材料有限公司 Preparation method of nitride red fluorescent powder with high thermal stability

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102373060B (en) * 2011-10-19 2013-06-12 江门市科恒实业股份有限公司 Aluminate green fluorescent powder with core-shell structure and preparation method thereof
CN115466614B (en) * 2022-09-26 2024-04-05 山东大学 White luminescent soft material based on lanthanide eutectic solvent and carbon dots and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1105153C (en) * 1999-11-30 2003-04-09 上海跃龙有色金属有限公司 Preparation of red phosphor
CN100427400C (en) * 2006-10-09 2008-10-22 江阴加华新材料资源有限公司 Prepn process of high purity yttrium europium oxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YAO J. ET AL.: "Synthesis and Optical Properties of Nanosized Rare Earth Composite Oxides Re203:Eu (RE = Y, Gd)", ZHONGGUO XITU XUEBAO, vol. 19, no. 5, October 2001 (2001-10-01), pages 426 - 429 *
ZHAI, Y. Q. ET AL.: "Preparation of Nanocrystal Y203:Eu by the EDTA Complexing Sol-Gel Method", WUJI CAILIAO XUEBAO, vol. 18, no. 2, March 2003 (2003-03-01), pages 439 - 444 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115448718A (en) * 2022-09-20 2022-12-09 中国核动力研究设计院 Europium hafnate material, preparation method and application
CN115477946A (en) * 2022-09-30 2022-12-16 云南大学 Green fluorescent material for non-contact temperature sensor and preparation method thereof
CN115477946B (en) * 2022-09-30 2023-05-23 云南大学 Green fluorescent material for non-contact temperature sensor and preparation method thereof
CN117004387A (en) * 2023-08-08 2023-11-07 烟台布莱特光电材料有限公司 Preparation method of nitride red fluorescent powder with high thermal stability

Also Published As

Publication number Publication date
CN102051171A (en) 2011-05-11
CN102051171B (en) 2013-04-10

Similar Documents

Publication Publication Date Title
Zhang et al. Photoluminescence and cathode-luminescence of Eu 3+-doped NaLnTiO 4 (Ln= Gd and Y) phosphors
WO2012065575A1 (en) Process for preparing red fluorescent powder of low europium content
WO2012088788A1 (en) Oxynitride luminescent material, preparation method thereof and illumination light source made from such material
CN100572497C (en) The preparation method of high brilliancy environmental protection type alkaline earth ion solid solution titanate fluorescent powder
KR101420337B1 (en) White-light led red luminescent materials and preparation methods thereof
CN106520119B (en) A kind of fluorescent powder and preparation method thereof of capable of emitting cyan light
CN114686225A (en) Near-infrared fluorescent powder and preparation method and application thereof
CN103525409A (en) A high-luminous-efficiency high-stability nitride luminescent material and a manufacture method thereof
CN101787280B (en) Manufacturing method of yttrium aluminum garnet (YAG) fluorescent powder for white light LED
CN110591711B (en) Gallate red fluorescent powder for white light LED and preparation method thereof
JP5111181B2 (en) Phosphor and light emitting device
CN103666472A (en) Method for improving luminescent intensity and stability of synthesized YAG (yttrium aluminum garnet):Ce fluorescent powder
WO2010105424A1 (en) Germanate luminescence material and its preparation
CN108822842B (en) Red strontium magnesium phosphate fluorescent material and preparation method and application thereof
CN108276998B (en) Trivalent samarium ion doped barium gadolinium titanate red fluorescent powder and preparation method thereof
WO2010130075A1 (en) Full-color light-emitting material and preparation method thereof
CN111635756B (en) Non-rare earth fluorescent material with high quantum yield and synthetic method thereof
WO2013143102A1 (en) Silicate luminescent materials doped with metal nano particles and preparation methods therefor
WO2012079218A1 (en) Halo-borate fluorescent materials and preparation methods thereof
CN109294583B (en) Cerium ion doped barium gadolinium titanate blue fluorescent powder for white light LED and preparation method thereof
Iwaki et al. One-pot synthesis of single phase Eu2+-activated MSi2O2N2 (M= Sr, Ba) by Controlling precursors and oxygen/nitrogen ratio
CN111057546A (en) Eu with high quantum yield3+Activated red fluorescent powder and preparation method thereof
CN115353375B (en) Divalent europium ion activated single-matrix full-spectrum white light ceramic material and preparation method thereof
CN114163999B (en) Nitride fluorescent powder and preparation method and application thereof
CN108441213A (en) A kind of red fluorescence powder and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11842318

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11842318

Country of ref document: EP

Kind code of ref document: A1