CN103771520B - A kind of preparation method of twin spherical calcium wolframate crystallite - Google Patents
A kind of preparation method of twin spherical calcium wolframate crystallite Download PDFInfo
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 42
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011575 calcium Substances 0.000 title claims abstract description 40
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 36
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 22
- 229920000858 Cyclodextrin Polymers 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001116 FEMA 4028 Substances 0.000 claims description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 8
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 8
- 229960004853 betadex Drugs 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000013081 microcrystal Substances 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229920001353 Dextrin Polymers 0.000 abstract 1
- 239000004375 Dextrin Substances 0.000 abstract 1
- 235000019425 dextrin Nutrition 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 11
- FDMFQOCGNBYKPY-UHFFFAOYSA-N calcium;dioxido(dioxo)tungsten Chemical compound [Ca+2].[O-][W]([O-])(=O)=O FDMFQOCGNBYKPY-UHFFFAOYSA-N 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 241000219122 Cucurbita Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明提供了一种孪生球状钨酸钙微晶的制备方法，其特征在于原料包括0.05～0.2mol/L钨酸钠、0.05～0.2mol/L硝酸钙和3.8～7.6g/L β-环糊精。本发明具有环保节能、高效快捷等特点，制备的钨酸钙孪生球形貌规整、分散性好、产率高、稳定性好，形成的球体达到4μm，尺寸均一；所需原料环保易得，制备过程简单易于实施，适合大规模工业生产。
The invention provides a method for preparing twin spherical calcium tungstate microcrystals, which is characterized in that the raw materials include 0.05-0.2mol/L sodium tungstate, 0.05-0.2mol/L calcium nitrate and 3.8-7.6g/L β-ring dextrin. The invention has the characteristics of environmental protection, energy saving, high efficiency and quickness. The prepared calcium tungstate twin spheres have regular appearance, good dispersibility, high yield and good stability. The formed spheres reach 4 μm and have uniform size; the required raw materials are environmentally friendly and easy to obtain. The preparation process is simple and easy to implement, and is suitable for large-scale industrial production.
Description
技术领域 technical field
本发明属于微纳米材料制备技术领域，主要涉及一种钨酸钙微米孪生球的制备方法。 The invention belongs to the technical field of preparation of micro-nano materials, and mainly relates to a preparation method of calcium tungstate micron twin spheres.
技术背景 technical background
钨酸钙(CaWO4)是一种典型的自激活发光材料，具有稳定的物理化学性质。因具有优越的发光性能，使其可以用作示波器中的蓝色磷光体，以及医学中检测Χ射线、γ射线的闪烁器。同时，钨酸钙可以作为一种激光基质材料，若将稀土离子如 Eu3+，Pr3+等作为激发剂掺入钨酸钙材料中，可使其产生红色长余辉发光，从而获得重要应用。微纳米钨酸钙因其在尺寸上的特殊优越性，将使其在未来的发光设备中发挥至关重要的作用。 Calcium tungstate (CaWO 4 ) is a typical self-activated luminescent material with stable physical and chemical properties. Due to its superior luminous performance, it can be used as a blue phosphor in an oscilloscope, and a scintillator for detecting X-rays and gamma rays in medicine. At the same time, calcium tungstate can be used as a laser host material. If rare earth ions such as Eu 3+ , Pr 3+ , etc. are mixed into calcium tungstate materials as exciters, it can produce red long afterglow luminescence, thus gaining important applications . Due to its special advantages in size, micro-nano calcium tungstate will play a vital role in future light-emitting devices.
目前，钨酸钙微纳米材料的制备方法很多，如固态反应法、水热法、超声辐照法、微波辐射法、沉淀法、凝胶法等，但这些方法在一定程度上仍存在不足，譬如产物形貌单一或尺寸难于控制；产率不高；高温反应条件苛刻或制备过程比较复杂；成本相对较高；环境污染大等。因此，探索简单环保的方法制备形貌新颖、产率高、分散性好的钨酸钙微纳米材料仍然是一个挑战。 At present, there are many preparation methods for calcium tungstate micro-nano materials, such as solid-state reaction method, hydrothermal method, ultrasonic irradiation method, microwave radiation method, precipitation method, gel method, etc., but these methods still have shortcomings to a certain extent. For example, the shape of the product is single or the size is difficult to control; the yield is not high; the high-temperature reaction conditions are harsh or the preparation process is relatively complicated; the cost is relatively high; the environmental pollution is large, etc. Therefore, it is still a challenge to explore simple and environmentally friendly methods to prepare calcium tungstate micro-nano materials with novel morphology, high yield and good dispersion.
发明内容 Contents of the invention
本发明的目的在于提供一种孪生球状钨酸钙微晶的制备方法，所制备的钨酸钙形貌独特、分散性好、尺寸均一、产率高、稳定性好。 The purpose of the present invention is to provide a method for preparing twin spherical calcium tungstate microcrystals. The prepared calcium tungstate has unique appearance, good dispersibility, uniform size, high yield and good stability.
本发明的目的是通过以下措施实现的： The object of the present invention is achieved by the following measures:
一种孪生球状钨酸钙微晶的制备方法，其特征在于原料包括0.05～0.2mol/L钨酸钠、0.05～0.2mol/L硝酸钙和3.8～7.6g/L β-环糊精。优选地，0.1mol/L钨酸钠、0.1mol/L硝酸钙和7.6g/L环糊精。以β-环糊精在溶液中自组装作为模板，当钨酸根和钙离子接触时，产物钨酸钙将在环糊精提供的结构平台上成核、生长，使之形成光滑、均一的孪生球状。 A method for preparing twin spherical calcium tungstate microcrystals is characterized in that raw materials include 0.05-0.2mol/L sodium tungstate, 0.05-0.2mol/L calcium nitrate and 3.8-7.6g/L β-cyclodextrin. Preferably, 0.1 mol/L sodium tungstate, 0.1 mol/L calcium nitrate and 7.6 g/L cyclodextrin. Using β-cyclodextrin self-assembly in solution as a template, when tungstate and calcium ions come into contact, the product calcium tungstate will nucleate and grow on the structural platform provided by cyclodextrin, making it form smooth and uniform twins spherical.
为了有效控制钨酸钙的熟化程度，形成规整的孪生球状，钨酸钠、硝酸钙和环糊精反应时间为1～6小时，其中最优的反应时间为3小时。 In order to effectively control the aging degree of calcium tungstate and form regular twin spheres, the reaction time of sodium tungstate, calcium nitrate and cyclodextrin is 1 to 6 hours, and the optimal reaction time is 3 hours.
为了有利于钨酸根和钙离子有效定位，以β-环糊精为模板形成钨酸钙微晶，上述孪生球状钨酸钙微晶的制备方法，β-环糊精溶于水，加入钨酸钠配成溶液A；将硝酸钙溶于水配成溶液B；在常温搅拌下，将溶液B加入溶液A，继续常温搅拌1～6小时制得钨酸钙孪生球。 In order to facilitate the effective positioning of tungstate and calcium ions, β-cyclodextrin is used as a template to form calcium tungstate microcrystals. In the preparation method of twin spherical calcium tungstate microcrystals, β-cyclodextrin is dissolved in water and tungstic acid is added. Make solution A with sodium; dissolve calcium nitrate in water to make solution B; add solution B to solution A under room temperature stirring, and continue stirring at room temperature for 1 to 6 hours to prepare calcium tungstate twin balls.
具体地，本发明的孪生球状钨酸钙微晶的制备方法，包括以下步骤： Specifically, the preparation method of twin spherical calcium tungstate microcrystals of the present invention comprises the following steps:
1）将β-环糊精溶于去离子水中，搅匀后加入钨酸钠，配成溶液A，所述溶液A中钨酸钠的摩尔浓度为0.1mol/L，环糊精的质量浓度为7.6g/ L； 1) Dissolve β-cyclodextrin in deionized water, stir well and add sodium tungstate to make solution A. The molar concentration of sodium tungstate in solution A is 0.1mol/L, and the mass concentration of cyclodextrin 7.6g/L;
将硝酸钙溶于去离子水中配成溶液B，所述溶液B中硝酸钙的摩尔浓度为0.1mol/L； Calcium nitrate is dissolved in deionized water to form solution B, and the molar concentration of calcium nitrate in the solution B is 0.1mol/L;
2）在搅拌下将溶液B加入溶液A中，继续常温下搅拌反应3小时，溶液A与溶液B的体积比为1:1； 2) Add solution B to solution A under stirring, continue to stir and react at room temperature for 3 hours, the volume ratio of solution A to solution B is 1:1;
3）离心分离沉淀，然后用去离子水和无水乙醇洗涤沉淀； 3) Centrifuge the precipitate, then wash the precipitate with deionized water and absolute ethanol;
4）将沉淀放在真空干燥箱内50℃下干燥，最终得到白色的钨酸钙粉末。 4) Dry the precipitate in a vacuum drying oven at 50°C to finally obtain white calcium tungstate powder.
本发明所述孪生球结构是由两个相同的半球体组成的对称构型，类似葫芦结构。 The twin sphere structure of the present invention is a symmetrical configuration composed of two identical hemispheres, similar to a gourd structure.
有益效果Beneficial effect
1. 本发明以常见的硝酸钙、钨酸钠为反应原料，以环保易得的环糊精作为表面活性剂，采用常温搅拌法即可制得形貌规整的孪生球状钨酸钙微晶。 1. The present invention uses common calcium nitrate and sodium tungstate as reaction raw materials, and cyclodextrin, which is environmentally friendly and easy to obtain, as surfactant, and can prepare twin spherical calcium tungstate microcrystals with regular shape by stirring at room temperature.
2. 本发明具有环保节能、高效快捷等特点，制备的钨酸钙孪生球形貌规整、分散性好、产率高、稳定性好，形成的球体达到4μm，尺寸均一；所需原料环保易得，制备过程简单易于实施，适合大规模工业生产。本发明制备的钨酸钙微晶在示波器、闪烁器等领域具有广阔的应用前景。 2. The present invention has the characteristics of environmental protection, energy saving, high efficiency and quickness. The prepared calcium tungstate twin spheres have regular appearance, good dispersibility, high yield and good stability. The formed spheres reach 4 μm and have uniform size; Therefore, the preparation process is simple and easy to implement, and is suitable for large-scale industrial production. The calcium tungstate microcrystals prepared by the invention have broad application prospects in the fields of oscilloscopes, scintillators and the like.
附图说明 Description of drawings
图1为本发明实施例1制备的钨酸钙孪生球的扫描电子显微镜SEM图； Fig. 1 is the scanning electron microscope SEM picture of the calcium tungstate twin spheres that the embodiment of the present invention 1 prepares;
图2为本发明实施例2制备的钨酸钙孪生球的扫描电子显微镜SEM图； Fig. 2 is the scanning electron microscope SEM figure of the calcium tungstate twin spheres that the embodiment of the present invention 2 prepares;
图3为本发明实施例3制备的钨酸钙孪生球的扫描电子显微镜SEM图； Fig. 3 is the scanning electron microscope SEM figure of the calcium tungstate twin spheres that the embodiment of the present invention 3 prepares;
图4为本发明实施例4制备的钨酸钙孪生球的扫描电子显微镜SEM图。 Fig. 4 is a scanning electron microscope SEM image of calcium tungstate twin spheres prepared in Example 4 of the present invention.
具体实施方式 Detailed ways
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。 The specific implementation of the present invention will be further described below in conjunction with the examples, and the present invention is not limited to the scope of the examples.
实施例1Example 1
本实施例制备的钨酸钙孪生球SEM图如图1所示，制备方法包括以下步骤： The SEM image of the calcium tungstate twin spheres prepared in this embodiment is shown in Figure 1 , and the preparation method includes the following steps:
1）称取0.076g环糊精溶于10ml去离子水中，搅拌均匀后，加入钨酸钠0.3299g，配成溶液A；称取0.2361g硝酸钙溶于10ml去离子水中配成溶液B； 1) Weigh 0.076g cyclodextrin and dissolve it in 10ml deionized water, stir well, add 0.3299g sodium tungstate to make solution A; weigh 0.2361g calcium nitrate and dissolve it in 10ml deionized water to make solution B;
2）在搅拌下，将10ml溶液B加入10ml溶液A中，常温下搅拌反应1h，制得钨酸钙孪生球； 2) Under stirring, add 10ml of solution B into 10ml of solution A, and stir for 1 hour at room temperature to prepare calcium tungstate twin balls;
3）反应后，将反应液进行离心分离，然后用去离子水和无水乙醇洗涤沉淀数次； 3) After the reaction, the reaction solution was centrifuged, and then the precipitate was washed several times with deionized water and absolute ethanol;
4）将沉淀物放在真空干燥箱内50℃下干燥，最终得到白色的钨酸钙粉末。 4) Dry the precipitate in a vacuum drying oven at 50°C to finally obtain white calcium tungstate powder.
实施例2Example 2
本实施例制备的钨酸钙孪生球SEM图如图2所示，制备方法包括以下步骤： The SEM image of the calcium tungstate twin spheres prepared in this embodiment is shown in Figure 2 , and the preparation method includes the following steps:
1）称取0.076g环糊精溶于10ml去离子水中，搅拌均匀后，加入钨酸钠0.3299g，配成溶液A；称取0.2361g硝酸钙溶于10ml去离子水中配成溶液B； 1) Weigh 0.076g cyclodextrin and dissolve it in 10ml deionized water, stir well, add 0.3299g sodium tungstate to make solution A; weigh 0.2361g calcium nitrate and dissolve it in 10ml deionized water to make solution B;
2）在搅拌下，将10ml溶液B加入10ml溶液A中，常温下搅拌反应3h，制得钨酸钙孪生球； 2) Under stirring, add 10ml of solution B into 10ml of solution A, stir and react for 3 hours at room temperature to obtain calcium tungstate twin balls;
3）反应后，将反应液进行离心分离，然后用去离子水和无水乙醇洗涤沉淀数次； 3) After the reaction, the reaction solution was centrifuged, and then the precipitate was washed several times with deionized water and absolute ethanol;
4）将沉淀物放在真空干燥箱内50℃下干燥，最终得到白色的钨酸钙粉末。 4) Dry the precipitate in a vacuum drying oven at 50°C to finally obtain white calcium tungstate powder.
实施例3Example 3
本实施例制备的钨酸钙孪生球SEM图如图3所示，制备方法包括以下步骤： The SEM image of the calcium tungstate twin spheres prepared in this embodiment is shown in Figure 3 , and the preparation method includes the following steps:
1）称取0.076g环糊精溶于10ml去离子水中，搅拌均匀后，加入钨酸钠0.3299g，配成溶液A；称取0.2361g硝酸钙溶于10ml去离子水中配成溶液B； 1) Weigh 0.076g cyclodextrin and dissolve it in 10ml deionized water, stir well, add 0.3299g sodium tungstate to make solution A; weigh 0.2361g calcium nitrate and dissolve it in 10ml deionized water to make solution B;
2）在搅拌下，将10ml溶液B加入10ml溶液A中，常温下搅拌反应6h，制得钨酸钙孪生球； 2) Under stirring, add 10ml of solution B into 10ml of solution A, stir and react for 6 hours at room temperature, and obtain calcium tungstate twin balls;
3）反应后，将反应液进行离心分离，然后用去离子水和无水乙醇洗涤沉淀数次； 3) After the reaction, the reaction solution was centrifuged, and then the precipitate was washed several times with deionized water and absolute ethanol;
4）将沉淀物放在真空干燥箱内50℃下干燥，最终得到白色的钨酸钙粉末。 4) Dry the precipitate in a vacuum drying oven at 50°C to finally obtain white calcium tungstate powder.
实施例4Example 4
本实施例制备的钨酸钙孪生球SEM图如图4所示，制备方法包括以下步骤： The SEM image of the calcium tungstate twin spheres prepared in this embodiment is shown in Figure 4 , and the preparation method includes the following steps:
1）称取0.038g环糊精溶于10ml去离子水中，搅拌均匀后，加入钨酸钠0.3299g，配成溶液A；称取0.2361g硝酸钙溶于10ml去离子水中配成溶液B； 1) Weigh 0.038g cyclodextrin and dissolve it in 10ml deionized water, stir well, add 0.3299g sodium tungstate to make solution A; weigh 0.2361g calcium nitrate and dissolve it in 10ml deionized water to make solution B;
2）在搅拌下，将10ml溶液B加入10ml溶液A中，常温下搅拌反应3h，制得钨酸钙孪生球； 2) Under stirring, add 10ml of solution B into 10ml of solution A, stir and react for 3 hours at room temperature to obtain calcium tungstate twin balls;
3）反应后，将反应液进行离心分离，然后用去离子水和无水乙醇洗涤沉淀数次； 3) After the reaction, the reaction solution was centrifuged, and then the precipitate was washed several times with deionized water and absolute ethanol;
4）将沉淀物放在真空干燥箱内50℃下干燥，最终得到白色的钨酸钙粉末。 4) Dry the precipitate in a vacuum drying oven at 50°C to finally obtain white calcium tungstate powder.
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| CN101613120A (en) * | 2009-07-29 | 2009-12-30 | 中国科学院青海盐湖研究所 | Sphere, radial magnesium carbonate and preparation method thereof |
| CN102992374A (en) * | 2012-12-10 | 2013-03-27 | 江苏大学 | Preparation method of calcium carbonate micro-spheres |
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| CN101613120A (en) * | 2009-07-29 | 2009-12-30 | 中国科学院青海盐湖研究所 | Sphere, radial magnesium carbonate and preparation method thereof |
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