CN105967748A - A kind of preparation method of BaTiO3 porous ceramics - Google Patents
A kind of preparation method of BaTiO3 porous ceramics Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 108
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000011975 tartaric acid Substances 0.000 claims abstract description 7
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001422 barium ion Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 13
- 239000000908 ammonium hydroxide Substances 0.000 abstract 2
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract 2
- 238000000465 moulding Methods 0.000 abstract 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 229960001484 edetic acid Drugs 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 9
- WNKMTAQXMLAYHX-UHFFFAOYSA-N barium(2+);dioxido(oxo)titanium Chemical compound [Ba+2].[O-][Ti]([O-])=O WNKMTAQXMLAYHX-UHFFFAOYSA-N 0.000 description 5
- 238000001879 gelation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 titanium ions Chemical class 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
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Abstract
Description
技术领域technical field
本发明属于材料技术领域，特别涉及一种BaTiO3多孔陶瓷的制备方法。The invention belongs to the technical field of materials, in particular to a preparation method of BaTiO3 porous ceramics.
背景技术Background technique
钛酸钡(BaTiO3)属于典型的钙钛矿(ABO3)结构，具有优异的压电铁电性、高的介电常数以及高的正温度系数等，是一种重要的陶瓷材料。钛酸钡多孔陶瓷由于其多孔的结构，当孔隙小而分布均匀时，可使钛酸钡多孔陶瓷的比表面积大大增大，活性增强。相比于多孔纳米钛酸钡粉体材料，由于纳米粉体材料的表面断键数较多，比表面积增大，使钛酸钡纳米颗粒间易相互团聚，纳米颗粒越小，则表面活性越大，团聚越严重。如果钛酸钡多孔陶瓷中的细孔分布均匀，则可解决这个问题，且保持了较高的比表面积和表面活性。Barium titanate (BaTiO 3 ) is a typical perovskite (ABO 3 ) structure, which has excellent piezoelectric ferroelectricity, high dielectric constant and high positive temperature coefficient, etc., and is an important ceramic material. Due to its porous structure, when the pores are small and evenly distributed, the specific surface area of the barium titanate porous ceramic can be greatly increased and the activity can be enhanced. Compared with the porous nano-barium titanate powder material, due to the large number of broken bonds on the surface of the nano-powder material, the specific surface area increases, so that the barium titanate nanoparticles are easy to agglomerate with each other, and the smaller the nano-particles, the higher the surface activity. The bigger, the more serious the reunion. If the pores in the barium titanate porous ceramics are evenly distributed, this problem can be solved, and a high specific surface area and surface activity can be maintained.
发明内容Contents of the invention
为了克服上述现有技术的缺点，本发明的目的在于提供一种BaTiO3多孔陶瓷的制备方法，具有生产工艺简单、设备要求简单、周期短的特点。In order to overcome the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a method for preparing BaTiO 3 porous ceramics, which has the characteristics of simple production process, simple equipment requirements and short cycle time.
为了实现上述目的，本发明采用的技术方案是：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种BaTiO3多孔陶瓷的制备方法，包括如下步骤： A preparation method of BaTiO porous ceramics, comprising the steps of:
(1)将柠檬酸溶于氨水中得到柠檬酸溶液，量取1/2的柠檬酸溶液，将醋酸钡溶于其中，形成溶液A备用；将钛酸丁酯溶于剩余柠檬酸溶液中形成溶液B；(1) Dissolve citric acid in ammonia water to obtain a citric acid solution, measure 1/2 of the citric acid solution, and dissolve barium acetate in it to form solution A for later use; dissolve butyl titanate in the remaining citric acid solution to form Solution B;
(2)将溶液A和溶液B混合，搅拌均匀后加入分散剂，再加入无水乙醇搅拌溶解，之后调节pH值至5～7获得溶胶C；(2) Mix solution A and solution B, stir evenly, add dispersant, then add absolute ethanol and stir to dissolve, then adjust the pH value to 5-7 to obtain sol C;
(3)将溶胶C于80～85℃下水浴2～4h至凝胶化，再在140～160℃下干燥形成干凝胶，在200℃～250℃烘1h后，自然冷却，进行研磨过筛得到干凝胶粉体；(3) Put sol C in a water bath at 80-85°C for 2-4 hours to gel, then dry at 140-160°C to form xerogel, bake at 200-250°C for 1 hour, cool naturally, and grind Sieve to obtain dry gel powder;
(4)将干凝胶粉体直接干压成型，形成块状坯体材料，最后将块状坯体材料进行热处理得到BaTiO3多孔陶瓷。(4) directly dry-press the xerogel powder to form a block-shaped green body material, and finally heat-treat the block-shaped green body material to obtain BaTiO 3 porous ceramics.
所述步骤(1)中，氨水的量以能溶解柠檬酸为准。In described step (1), the amount of ammoniacal liquor is as the criterion that can dissolve citric acid.
所述硝酸钡和钛酸丁酯的用量满足Ba与Ti的摩尔比为1:1，且Ba离子与Ti离子之和与柠檬酸的摩尔比为1：(1～2)。The dosages of the barium nitrate and butyl titanate satisfy that the molar ratio of Ba to Ti is 1:1, and the molar ratio of the sum of Ba ions and Ti ions to citric acid is 1:(1-2).
所述分散剂由乙二胺四乙酸、柠檬酸、二乙烯三胺五羧酸、酒石酸、乙二醇和聚乙二醇组成。The dispersant is composed of ethylenediaminetetraacetic acid, citric acid, diethylenetriaminepentacarboxylic acid, tartaric acid, ethylene glycol and polyethylene glycol.
所述溶液A和溶液B中加入分散剂后，分散剂各组份的浓度范围均为0～0.8mol/L。After the dispersant is added to the solution A and solution B, the concentration range of each component of the dispersant is 0-0.8 mol/L.
所述无水乙醇的体积是氨水体积的1～2倍。The volume of the absolute ethanol is 1 to 2 times the volume of ammonia water.
所述步骤(4)中，所述热处理是在ZnO粉体中700℃埋烧1h，再在1000～1400℃下烧结1～3h。In the step (4), the heat treatment is burying the ZnO powder at 700°C for 1 hour, and then sintering at 1000-1400°C for 1-3 hours.
与现有技术相比，本发明的有益效果是：本发明提供的BaTiO3多孔陶瓷的制备方法中，以乙二胺四乙酸、柠檬酸、二乙烯三胺五羧酸、酒石酸、乙二醇、聚乙二醇(如聚乙二醇400、聚乙二醇4000、聚乙二醇6000)等作为分散剂直接进行络合发泡的凝胶化过程，通过控制各物质的浓度，特别是各分散剂的用量，干燥后所形成的中间粉体物质可直接成型成块状材料，在这个制备方法中，不仅利用分散剂使钛离子和钡离子均匀地存在于体系中，使BaTiO3多孔陶瓷的结晶过程更加均匀，而且减少造粒、陈腐的过程，使结晶过程与烧结一步完成，这都使制备周期缩短，成本降低。结合埋烧的热处理过程，利用有机物的发泡和分解燃烧过程形成BaTiO3多孔陶瓷，可获得开孔结构。Compared with the prior art, the beneficial effects of the present invention are: in the preparation method of BaTiO3 porous ceramics provided by the present invention, ethylenediaminetetraacetic acid, citric acid, diethylenetriaminepentacarboxylic acid, tartaric acid, ethylene glycol , polyethylene glycol (such as polyethylene glycol 400, polyethylene glycol 4000, polyethylene glycol 6000) etc. directly carry out the gelation process of complexing and foaming as a dispersant, by controlling the concentration of each substance, especially The amount of each dispersant, the intermediate powder material formed after drying can be directly formed into a block material. In this preparation method, not only the dispersant is used to make titanium ions and barium ions evenly exist in the system, but also to make BaTiO 3 porous The crystallization process of ceramics is more uniform, and the process of granulation and decay is reduced, and the crystallization process and sintering are completed in one step, which shortens the preparation cycle and reduces the cost. Combined with the heat treatment process of buried firing, the foaming and decomposition combustion process of organic matter is used to form BaTiO 3 porous ceramics, and an open-pore structure can be obtained.
具体实施方式detailed description
下面结合实施例详细说明本发明的实施方式。The implementation of the present invention will be described in detail below in conjunction with the examples.
实施例1Example 1
一种BaTiO3多孔陶瓷的制备方法，包括如下步骤： A preparation method of BaTiO porous ceramics, comprising the steps of:
(1)将柠檬酸溶于氨水(体积浓度25％～28％)中，氨水的量以能溶解柠檬酸为准，量取1/2的柠檬酸溶液，将醋酸钡溶于其中形成溶液A备用；将钛酸丁酯溶于剩余柠檬酸溶液中形成溶液B，其中，Ba：Ti(摩尔比)符合化学计量比1:1，且Ba离子与Ti离子之和与柠檬酸的摩尔比为＝1：1。(1) Dissolve citric acid in ammonia water (volume concentration 25% to 28%), the amount of ammonia water is based on the amount of citric acid that can be dissolved, measure 1/2 of the citric acid solution, and dissolve barium acetate in it to form solution A Standby; butyl titanate is dissolved in the remaining citric acid solution to form solution B, wherein Ba:Ti (molar ratio) meets the stoichiometric ratio of 1:1, and the molar ratio of the sum of Ba ions and Ti ions to citric acid is =1:1.
(2)混合溶液A和溶液B，搅拌均匀后称量一定量的分散剂(由乙二胺四乙酸、柠檬酸、二乙烯三胺五羧酸、酒石酸、乙二醇、聚乙二醇组成，其中聚乙二醇又包括聚乙二醇400、聚乙二醇4000和聚乙二醇6000)加入其中，分散剂各组份的浓度控制在0.8mol/L，再加入无水乙醇搅拌溶解(无水乙醇的体积是氨水体积的2倍)，调节pH值至5～7即获得溶胶C。(2) Mix solution A and solution B, weigh a certain amount of dispersant (composed of ethylenediaminetetraacetic acid, citric acid, diethylenetriaminepentacarboxylic acid, tartaric acid, ethylene glycol, polyethylene glycol) after stirring evenly , wherein polyethylene glycol (including polyethylene glycol 400, polyethylene glycol 4000 and polyethylene glycol 6000) is added therein, the concentration of each component of the dispersing agent is controlled at 0.8mol/L, then add absolute ethanol and stir to dissolve (The volume of absolute ethanol is twice the volume of ammonia water), adjust the pH value to 5-7 to obtain Sol C.
(3)将溶胶C于80℃下水浴2～4h至凝胶化。再在140℃下干燥形成干凝胶，在200℃烘1h后，自然冷却，将粉体进行研磨过筛。(3) Put Sol C in a water bath at 80°C for 2-4 hours until gelation. Then dry at 140°C to form a xerogel, bake at 200°C for 1 hour, cool naturally, and grind and sieve the powder.
(4)将过筛后的干粉直接干压成形，形成块状坯体材料，最后将块状坯体材料在ZnO粉体中700℃进行埋烧1h，之后再在1000℃下烧结1h即获得BaTiO3多孔材料。所得BaTiO3多孔材料中为开孔结构，晶粒尺寸约为150nm～300nm，间隙尺寸为100nm～200nm。(4) The sieved dry powder is directly dry-pressed to form a block-shaped green body material, and finally the block-shaped green body material is buried and fired in ZnO powder at 700°C for 1h, and then sintered at 1000°C for 1h to obtain BaTiO 3 porous material. The obtained BaTiO 3 porous material has an open-pore structure, the grain size is about 150nm-300nm, and the gap size is 100nm-200nm.
实施例2Example 2
一种BaTiO3多孔陶瓷的制备方法，包括如下步骤： A preparation method of BaTiO porous ceramics, comprising the steps of:
(1)将柠檬酸溶于氨水(体积浓度25％～28％)中，氨水的量以能溶解柠檬酸为准，量取1/2的柠檬酸溶液，将醋酸钡溶于其中形成溶液A备用；将钛酸丁酯溶于剩余柠檬酸溶液中形成溶液B，其中，Ba：Ti(摩尔比)符合化学计量比1:1，且Ba离子与Ti离子之和与柠檬酸的摩尔比为＝1：2。(1) Dissolve citric acid in ammonia water (volume concentration 25% to 28%), the amount of ammonia water is based on the amount of citric acid that can be dissolved, measure 1/2 of the citric acid solution, and dissolve barium acetate in it to form solution A Standby; butyl titanate is dissolved in the remaining citric acid solution to form solution B, wherein Ba:Ti (molar ratio) meets the stoichiometric ratio of 1:1, and the molar ratio of the sum of Ba ions and Ti ions to citric acid is =1:2.
(2)混合溶液A和溶液B，搅拌均匀后称量一定量的分散剂(由乙二胺四乙酸、柠檬酸、二乙烯三胺五羧酸、酒石酸、乙二醇、聚乙二醇组成)加入其中，分散剂各组份的浓度控制在0.8mol/L，再加入无水乙醇搅拌溶解(无水乙醇的体积与氨水体积的相等)，调节pH值至5～7即获得溶胶C。(2) Mix solution A and solution B, weigh a certain amount of dispersant (composed of ethylenediaminetetraacetic acid, citric acid, diethylenetriaminepentacarboxylic acid, tartaric acid, ethylene glycol, polyethylene glycol) after stirring evenly ) was added therein, the concentration of each component of the dispersant was controlled at 0.8mol/L, then absolute ethanol was added and stirred to dissolve (the volume of absolute ethanol was equal to the volume of ammonia water), and the pH value was adjusted to 5-7 to obtain Sol C.
(3)将溶胶C于85℃下水浴2～4h至凝胶化。再在160℃下干燥形成干凝胶，在250℃烘1h后，自然冷却，将粉体进行研磨过筛。(3) Put Sol C in a water bath at 85°C for 2-4 hours until gelation. Then dry at 160°C to form xerogel, bake at 250°C for 1 hour, cool naturally, grind the powder and sieve it.
(4)将过筛后的干粉直接干压成形，形成块状坯体材料，最后将块状坯体材料在ZnO粉体中700℃进行埋烧1h，之后再在1400℃下烧结1h即获得BaTiO3多孔材料。所得BaTiO3多孔材料中为开孔结构，晶粒尺寸约为150nm～300nm，间隙尺寸为100nm～200nm。(4) The sieved dry powder is directly dry-pressed to form a block-shaped green body material, and finally the block-shaped green body material is buried and fired in ZnO powder at 700°C for 1h, and then sintered at 1400°C for 1h to obtain BaTiO 3 porous material. The obtained BaTiO 3 porous material has an open-pore structure, the grain size is about 150nm-300nm, and the gap size is 100nm-200nm.
实施例3Example 3
一种BaTiO3多孔陶瓷的制备方法，包括如下步骤： A preparation method of BaTiO porous ceramics, comprising the steps of:
(1)将柠檬酸溶于氨水(体积浓度25％～28％)中，氨水的量以能溶解柠檬酸为准，量取1/2的柠檬酸溶液，将醋酸钡溶于其中形成溶液A备用；将钛酸丁酯溶于剩余柠檬酸溶液中形成溶液B，其中，Ba：Ti(摩尔比)符合化学计量比1:1，且Ba离子与Ti离子之和与柠檬酸的摩尔比为＝1：1.5。(1) Dissolve citric acid in ammonia water (volume concentration 25% to 28%), the amount of ammonia water is based on the amount of citric acid that can be dissolved, measure 1/2 of the citric acid solution, and dissolve barium acetate in it to form solution A Standby; butyl titanate is dissolved in the remaining citric acid solution to form solution B, wherein Ba:Ti (molar ratio) meets the stoichiometric ratio of 1:1, and the molar ratio of the sum of Ba ions and Ti ions to citric acid is =1:1.5.
(2)混合溶液A和溶液B，搅拌均匀后称量一定量的分散剂(由乙二胺四乙酸、柠檬酸、二乙烯三胺五羧酸、酒石酸、乙二醇、聚乙二醇组成)加入其中，分散剂各组份的浓度控制在0.01、0.1、0.1、0.5、0.7、0.8mol/L，再加入无水乙醇搅拌溶解(无水乙醇的体积是氨水体积的2倍)，调节pH值至5～7即获得溶胶C。(2) Mix solution A and solution B, weigh a certain amount of dispersant (composed of ethylenediaminetetraacetic acid, citric acid, diethylenetriaminepentacarboxylic acid, tartaric acid, ethylene glycol, polyethylene glycol) after stirring evenly ) into it, the concentration of each component of the dispersant is controlled at 0.01, 0.1, 0.1, 0.5, 0.7, 0.8mol/L, then add dehydrated alcohol and stir to dissolve (the volume of dehydrated alcohol is 2 times the volume of ammonia water), adjust Sol C is obtained when the pH value reaches 5-7.
(3)将溶胶C于80℃下水浴2～4h至凝胶化。再在150℃下干燥形成干凝胶，在220℃烘1h后，自然冷却，将粉体进行研磨过筛。(3) Put Sol C in a water bath at 80°C for 2-4 hours until gelation. Then dry at 150°C to form a xerogel, bake at 220°C for 1 hour, cool naturally, and grind and sieve the powder.
(4)将过筛后的干粉直接干压成形，形成块状坯体材料，最后将块状坯体材料在ZnO粉体中700℃进行埋烧1h，之后再在1200℃下烧结2h即获得BaTiO3多孔材料。所得BaTiO3多孔材料中为开孔结构，晶粒尺寸约为150nm～300nm，间隙尺寸为100nm～200nm。(4) The sieved dry powder is directly dry-pressed to form a block-shaped green body material, and finally the block-shaped green body material is buried and fired in ZnO powder at 700°C for 1 hour, and then sintered at 1200°C for 2 hours to obtain BaTiO 3 porous material. The obtained BaTiO 3 porous material has an open-pore structure, the grain size is about 150nm-300nm, and the gap size is 100nm-200nm.
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