CN1328402C - 用于电解电容器的精炼铝薄板或带 - Google Patents
用于电解电容器的精炼铝薄板或带 Download PDFInfo
- Publication number
- CN1328402C CN1328402C CNB038226251A CN03822625A CN1328402C CN 1328402 C CN1328402 C CN 1328402C CN B038226251 A CNB038226251 A CN B038226251A CN 03822625 A CN03822625 A CN 03822625A CN 1328402 C CN1328402 C CN 1328402C
- Authority
- CN
- China
- Prior art keywords
- carbide
- aluminium
- atom
- thin plate
- band
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000004411 aluminium Substances 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 title abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- TWHBEKGYWPPYQL-UHFFFAOYSA-N aluminium carbide Chemical compound [C-4].[C-4].[C-4].[Al+3].[Al+3].[Al+3].[Al+3] TWHBEKGYWPPYQL-UHFFFAOYSA-N 0.000 claims abstract 5
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005098 hot rolling Methods 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000005097 cold rolling Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 12
- ZBZHVBPVQIHFJN-UHFFFAOYSA-N trimethylalumane Chemical compound C[Al](C)C.C[Al](C)C ZBZHVBPVQIHFJN-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000005530 etching Methods 0.000 description 7
- 238000005204 segregation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003887 surface segregation Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910020068 MgAl Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Metal Rolling (AREA)
- Electrolytic Production Of Metals (AREA)
- ing And Chemical Polishing (AREA)
- Chemical Treatment Of Metals (AREA)
- Heat Treatment Of Sheet Steel (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Conductive Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
本发明涉及纯度高于99.9%的精炼铝薄板或带，用于制造电解电容器的阳极，其在厚度为10nm的表面区域中包含原子含量为5—25%，优选10—20%的碳化铝。
Description
技术领域
本发明涉及纯度高于99.9％的精炼铝薄板或带，在经过旨在提高其比表面积的点蚀表面处理后，其用于制造电解电容器(尤其是高压电容器)的阳极。
背景技术
许多研究者已经研究了精炼铝的表面对其蚀刻性的影响，并阐明了以下两个主要参数的影响：
-表面氧化物层
-在表面上偏析的杂质和掺杂剂。
Osawa和Fukuoka最近对有关表面氧化物层的知识进行了综述(Hyomen Gijutsu(2000)51(11)1117-1120)。研究表明，点蚀可在氧化物层中存在的微晶周围被引发，并且已确认两种类型：γ-Al2O3和MgAl2O4(尖晶石)。点蚀在与氧化物膜的结晶密切相关的裂纹中被引发。
多个专利申请还提到氧化物层结晶的尺寸(importance)，具体的是JP 08222487和JP08-222488(Mitsubishi Aluminium)，JP2000-216063和JP 2000-216064(Nippon Foil Mfg)，其中要求保护γ-Al2O3的量的作用。
专利申请JP 10-189397(Sumitomo Light Metal Industries)提到MgAl2O4(尖晶石)的尺寸，其作为引发点蚀的有利因素而存在。
多个专利提到氧化物层的大量水合作用的有利效果，在各种添加剂的存在下在沸水中进行浸渍处理可以提高薄板的蚀刻性，例如JP08-306592(Kobe Steel)，JP 2000-232038(Kobe Steel)，JP05-006840(Nippon Seihaku)，JP 07-150279(Nippon Seihaku)，JP 07-297089(Nippon Seihaku)，US 5417839(Showa Aluminum)和JP 06-104147(Sumitomo Light Metal Indutries)。
对于在表面上偏析的杂质和掺杂剂来说，已知在浇铸期间金属中存在的许多杂质对薄板的蚀刻性是有影响的，其中这些杂质是有意添加或者来源于所用的矿物，并且在不同的转化步骤期间，尤其是在热轧和最终热处理期间在表面上偏析。
Osawa和Fukuoka提到了已知影响蚀刻的主要杂质。铋在氧化物-铝的界面偏析，并且象硼一样具有有害的影响。镁在氧化物层表面偏析。已知铅和铟偏析的深度最多可达50nm，并且对蚀刻具有有利的影响。Fukuoka描述了硼、镁、铁和铋的表面偏析分布(Journal of JapanInstitute of Light Metals，51(7)2001，第370-377页)。
多个专利要求保护如铅、铋和铟这样的杂质的深度分布，具体地是JP 57-194516(Toyo Aluminium)，US 5128836(Sumitomo LightMetal)和本申请人的专利申请EP 1031638。
Showa Aluminium的专利EP 0490574描述了或者在氧化物层表面，或者在氧化物层与金属的界面，或者在氧化物层表面和所述界面上16种元素的表面富集的有益效果。离子探头测定的浓度比是1.2-30。
专利申请JP 04-062820(Showa Aluminium)描述了包含1-50ppm的碳的薄板，并且在0.1μm厚的表面层中富集的碳是内部浓度的5-300倍。表面的碳源于内部碳的表面偏析。
本发明的目的是提供精炼铝薄板和带，与现有技术相比，其具有更好的蚀刻性，并且还可以改善由这些薄板或带制造的电解电容器的性能。
发明目的
本发明的目的在于一种纯度大于99.9％的精炼铝薄板或带，其用于制造电解电容器的阳极，其在厚度为10nm的表面区域中包含原子含量为5-25％，优选10-20％的碳化铝。
本发明的描述
本发明是基于申请人在实验过程中发现的精炼铝薄板，所述精炼铝薄板具有不同寻常的蚀刻性，并使得由这些薄板制造的电容器的电容明显增加。这些薄板的许多特性被认为是这种不同寻常的性能的原因，并且已经表明，其在金属与氧化物之间的界面包含有非常规量的碳化铝。
可用两种分析方法显示所形成的碳化铝，即ESCA(化学分析用电子能谱法)，又名XPS(X射线光电子能谱法)，和TEM(透射电子显微镜)。
使用XPS表明在退火之后形成碳化物(Al4C3≈282eV，使用72.8eV位置作为金属铝峰的基准)。如在下面的文献中所指出的，在能量为283-281eV之间的碳C 1s峰上观察到金属碳化物，这些文献是NIST(National Institute of Standards and Technology)的XPS数据库或C.D.WAGNER，W.M.RIGGS，L.E.DAVIS，J.F.MOULDER的手册《Handbook of X-ray Photoelectron Spectroscopy》，Perkin-ElmerCorporation，Physical Electronics Division。
更具体地，对于碳化铝来说，C.Hinnen，D.Imbert，J.M.Siffre和P.Marcus的文章“Aninsitu XPS Study of Sputter-depositedAluminium Thin Films on Graphite”(Applied Surface Science，78，(1994)，219-231)提到了对于Al4C3来说的282.4eV的峰。B.Maruyama，F.S.Ohuchi和L.Rabenberg的文章“Catalytic Carbide Formationat Aluminium-Carbon Interface”(Journal of Materials ScienceLetters，9，(1990)，第864-866页)指出了对于Al4C3来说的281.5eV的峰和对于碳氧化物来说的282.5eV的峰。
P.J.Cumpson的文章“Angle-resolved XPS and AESDeDth-resolution and a General Comparison of Properties ofDepth-profile Reconstruction Methods”(Journal of ElectronSpetroscopy and Related Phenomena，73(1995)，第25-52页)中的角度XPS分析法显示，与由于样品受到气氛的污染而存在的表面碳不同，碳化物位于氧化物层下。碳化物具有类似于金属铝的角度分布，所述金属铝理所当然地位于氧化物层下。
XPS法可进行材料表面的定量分析。这种方法目前得到了广泛地认可，其结果以原子％来表示。由于碳化物的原子％受到表面层的尺寸(污染碳、氧化物层厚度)的影响，因而定义了一种方法来对这些参数进行独立定量。
由于碳化物和金属二者均位于氧化物层下并因此以完全相同的方式受到表面层的影响，因此所提出的方法要确定碳化铝与金属形式的铝的原子％之比。因而使用按照如下方式计算的碳化铝在金属铝中的％：
金属Al中的碳化物％＝碳化物的原子％/(碳化物的原子％+金属Al的原子％)*100％。金属铝和碳化物的百分数通过XPS测量法来确定；分析角是分析仪与表面之间的45°，射线源是AlKα单色化射线(1486.8eV)。
在铝的选择性溶解之后进行的TEM检验通过其晶体结构(Al4C3)确认在氧化物层下存在碳化物。
尽管难以定量，但TEM检验无可争辨地表明了本发明的薄板和带存在碳化铝。对于其在铝中5-25％的原子浓度来说，已经看到了碳化铝的有利效果，并且对其来源进行了研究。
由于碳在固体铝中非常难溶(小于0.1ppm)并且由于所形成的碳化物非常稳定，因而这意味着铝材中所含的碳以碳化物形式被封闭，并且不能向表面迁移，下面的出版物对此均有涉及：
L.Svendsen和A.Jarfors：《Al-Ti-C Phase Diagram》，MaterialsScience and Technology，1993 Vol.9，
R.C.Dorward：Discussion of《Comments on the Solubility ofCarbon in Molten Aluminium》，Metallurgical Transactions A，1990，Vol.21A，
C.Qiu，R.Met selaar：《Solubility of Carbon in liquid Al andStability of Al4C3》，Journal of Alloys and Compounds，1994，216，55-60。
因此，表面上存在的碳化物不可能是由内部碳的偏析而产生的。相反，这种碳来源于外部，并且与表面的铝在高温下反应。
本发明的薄板和带是采用一种已知方式生产的，直到最终的退火步骤为止。所述生产包括产生纯度至少等于99.9％的精炼铝。所使用的精炼方法可以是如专利FR759588和FR832528所描述的所谓“3-层”电解精炼，或者是如专利FR1594154所描述的偏析方法。金属以板的形式浇铸，均化，随后是热轧，然后冷轧至最终厚度，该厚度约为0.1mm。该生产过程在热轧和冷轧之间通常包括中间退火，以及在两次冷轧之间的另一次退火。随后在中性气氛下，如在氩气中，在500-580℃的温度下，对薄板或带进行最终的退火。
为了获得本发明的薄板或带，在中性气体中引入含有碳原子的气体，这样可在最终退火温度下形成碳化铝。例如可使用甲烷CH4或者碳的其它气态衍生物，如丙烷、丁烷、异丁烷、乙烯、乙炔、丙烯、丙炔、丁二烯等。
众所周知，氧化物微晶的存在有利于蚀刻，而且本发明人提出，在氧化物层下引入碳化物具有类似的效果，并且可以提高表面微晶密度并进而提高通道(tunnel)密度，由此提高电容器的电容。
实施例
通过使用下面的转化操作步骤制备纯度为99.99％精炼铝薄板的12个样品：
-浇铸板材并将所述板材在600℃下均化30小时，
-热轧和冷轧至厚度为0.125mm，
-在200℃下进行中间退火30小时，
-冷轧至厚度为0.1mm，
-在表1所述条件的氩气中(把5％或10％的甲烷加到氩气中)，
对本发明样品进行最终的退火。
随后根据下面的方法测量由点蚀的样品制得的电容器的电容：在含有5％HCl和15％H2SO4的溶液中，在200mA/cm2的直流电流强度下，在85℃下将铝薄板电解60s。随后，在5％HCl的溶液中，在50mA/cm2的直流电流强度下，在80℃下将铝薄板电解8分钟。氧化物在硼酸铵溶液中在450V的电压下形成。以μF/cm2测量电容，并在随后将其转换为相对于参比精炼薄板的百分数。其结果在表1中示出：
表1
| 样品 | Ar中的CH4％ | 退火温度 | 退火时间(h) | 表面上的碳化物％ | 电容(％) |
| 1 | 5 | 545℃ | 15 | 7 | 97 |
| 2 | 5 | 545℃ | 10 | 3 | 101 |
| 3 | 5 | 570℃ | 15 | 12 | 112 |
| 4 | 5 | 570℃ | 10 | 8 | 105 |
| 5 | 10 | 545℃ | 15 | 15 | 108 |
| 6 | 10 | 545℃ | 10 | 12 | 111 |
| 7 | 10 | 570℃ | 15 | 23 | 107 |
| 8 | 10 | 570℃ | 10 | 18 | 106 |
| 9 | 0 | 520℃ | 20 | 0 | 95 |
| 10 | 0 | 545℃ | 15 | 0 | 98 |
| 11 | 0 | 570℃ | 10 | 0 | 97 |
| 12 | 0 | 595℃ | 5 | 0 | 99 |
可以看到，样品1-8中有7个的电容增加了，在这8个样品中，最终的退火是在向氩气中添加甲烷的情况下进行的，尤其是对于添加更多甲烷的5-8这四个样品来说，平均为108％，而样品1-4为104％，现有技术的样品9-12为97％。
Claims (4)
1.纯度高于99.9％的精炼铝薄板或带，用于制造电解电容器的阳极，其在厚度为10nm的表面区域中包含原子含量为5-25％的在金属铝中的碳化铝，碳化铝在金属铝中的％按照如下方程式计算：
金属Al中的碳化物％＝碳化物的原子％/(碳化物的原子％+金属Al的原子％)*100％
其中在厚度为10nm的表面区域中的碳化物的原子％和金属Al的原子％通过XPS测量法来确定。
2.权利要求1的薄板或带，其特征在于该表面区域中的碳化铝的原子含量为10-20％。
3.权利要求1或2的薄板或带的生产方法，包括浇铸精炼铝板，对其均化、热轧、冷轧和在中性气体中进行最终退火，其特征在于将中性气体与能够在所述最终退火过程中形成碳化铝的含有碳原子的气体混合。
4.权利要求3的方法，其特征在于包含碳原子的气体是甲烷、丙烷、丁烷、异丁烷、乙烯、乙炔、丙烯、丙炔或丁二烯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0211774A FR2844810B1 (fr) | 2002-09-24 | 2002-09-24 | Feuille ou bande en aluminium raffine pour condensateurs electrolytiques |
| FR02/11774 | 2002-09-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1685068A CN1685068A (zh) | 2005-10-19 |
| CN1328402C true CN1328402C (zh) | 2007-07-25 |
Family
ID=31970922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038226251A Expired - Fee Related CN1328402C (zh) | 2002-09-24 | 2003-09-22 | 用于电解电容器的精炼铝薄板或带 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US20050205645A1 (zh) |
| EP (1) | EP1543173B1 (zh) |
| JP (1) | JP2006503179A (zh) |
| KR (1) | KR20050061482A (zh) |
| CN (1) | CN1328402C (zh) |
| AT (1) | ATE314500T1 (zh) |
| AU (1) | AU2003282180A1 (zh) |
| DE (1) | DE60303048T2 (zh) |
| FR (1) | FR2844810B1 (zh) |
| HK (1) | HK1082004A1 (zh) |
| RU (1) | RU2318912C2 (zh) |
| TW (1) | TWI277991B (zh) |
| WO (1) | WO2004029311A1 (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007055121A1 (ja) * | 2005-11-10 | 2007-05-18 | Toyo Aluminium Kabushiki Kaisha | 電極構造体、コンデンサおよび電極構造体の製造方法 |
| JPWO2009118774A1 (ja) * | 2008-03-24 | 2011-07-21 | 日本軽金属株式会社 | 電解コンデンサ用アルミニウムエッチド板、電解コンデンサ用アルミニウム電極板、およびそれらの製造方法 |
| JP5649285B2 (ja) * | 2009-03-17 | 2015-01-07 | 東洋アルミニウム株式会社 | 導電物被覆アルミニウム材とその製造方法 |
| RU2748842C1 (ru) * | 2020-06-01 | 2021-05-31 | Виктор Валентинович Стрелков | Алюминиевая конденсаторная исходная фольга, легированная эрбием |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0462820A (ja) * | 1990-06-25 | 1992-02-27 | Showa Alum Corp | 電解コンデンサ電極用アルミニウム箔 |
| EP0490574A1 (en) * | 1990-12-11 | 1992-06-17 | Showa Aluminum Kabushiki Kaisha | Aluminum foil as electrolytic condenser electrodes |
| CN1264906A (zh) * | 1999-02-23 | 2000-08-30 | 皮西尼何纳吕公司 | 用于电解电容器的精铝箔 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5518823A (en) * | 1990-12-11 | 1996-05-21 | Showa Aluminum Kabushiki | Aluminum foil as electrolytic condenser electrodes |
| US6077774A (en) * | 1996-03-29 | 2000-06-20 | Texas Instruments Incorporated | Method of forming ultra-thin and conformal diffusion barriers encapsulating copper |
| US20040240152A1 (en) * | 2003-05-30 | 2004-12-02 | Schott Joachim Hossick | Capacitor and method for producing a capacitor |
| WO2004088690A1 (ja) * | 2003-03-31 | 2004-10-14 | Toyo Aluminium Kabushiki Kaisha | コンデンサ陰極用箔およびその製造方法 |
| US6812110B1 (en) * | 2003-05-09 | 2004-11-02 | Micron Technology, Inc. | Methods of forming capacitor constructions, and methods of forming constructions comprising dielectric materials |
-
2002
- 2002-09-24 FR FR0211774A patent/FR2844810B1/fr not_active Expired - Fee Related
-
2003
- 2003-08-06 TW TW092121496A patent/TWI277991B/zh not_active IP Right Cessation
- 2003-09-22 AU AU2003282180A patent/AU2003282180A1/en not_active Abandoned
- 2003-09-22 RU RU2005112257/02A patent/RU2318912C2/ru not_active IP Right Cessation
- 2003-09-22 AT AT03773800T patent/ATE314500T1/de not_active IP Right Cessation
- 2003-09-22 DE DE60303048T patent/DE60303048T2/de not_active Expired - Fee Related
- 2003-09-22 EP EP03773800A patent/EP1543173B1/fr not_active Expired - Lifetime
- 2003-09-22 KR KR1020057005086A patent/KR20050061482A/ko not_active Application Discontinuation
- 2003-09-22 CN CNB038226251A patent/CN1328402C/zh not_active Expired - Fee Related
- 2003-09-22 JP JP2004539120A patent/JP2006503179A/ja active Pending
- 2003-09-22 US US10/524,118 patent/US20050205645A1/en not_active Abandoned
- 2003-09-22 WO PCT/FR2003/002778 patent/WO2004029311A1/fr active IP Right Grant
-
2006
- 2006-02-17 HK HK06102128A patent/HK1082004A1/xx not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0462820A (ja) * | 1990-06-25 | 1992-02-27 | Showa Alum Corp | 電解コンデンサ電極用アルミニウム箔 |
| EP0490574A1 (en) * | 1990-12-11 | 1992-06-17 | Showa Aluminum Kabushiki Kaisha | Aluminum foil as electrolytic condenser electrodes |
| CN1264906A (zh) * | 1999-02-23 | 2000-08-30 | 皮西尼何纳吕公司 | 用于电解电容器的精铝箔 |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1082004A1 (en) | 2006-05-26 |
| RU2005112257A (ru) | 2005-09-20 |
| AU2003282180A1 (en) | 2004-04-19 |
| DE60303048T2 (de) | 2006-08-31 |
| TW200407920A (en) | 2004-05-16 |
| FR2844810A1 (fr) | 2004-03-26 |
| DE60303048D1 (de) | 2006-02-02 |
| ATE314500T1 (de) | 2006-01-15 |
| WO2004029311A1 (fr) | 2004-04-08 |
| JP2006503179A (ja) | 2006-01-26 |
| RU2318912C2 (ru) | 2008-03-10 |
| KR20050061482A (ko) | 2005-06-22 |
| TWI277991B (en) | 2007-04-01 |
| US20050205645A1 (en) | 2005-09-22 |
| EP1543173A1 (fr) | 2005-06-22 |
| EP1543173B1 (fr) | 2005-12-28 |
| FR2844810B1 (fr) | 2004-11-05 |
| CN1685068A (zh) | 2005-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Composition and microstructure dependent corrosion behaviour of Mg-Li alloys | |
| Duan et al. | Cooperative effect of Cr and Al elements on passivation enhancement of eutectic high-entropy alloy AlCoCrFeNi2. 1 with precipitates | |
| Hamid et al. | Influence of deposition temperature and heat treatment on the performance of electroless Ni–B films | |
| Petković et al. | Characterization of oxide coatings formed on tantalum by plasma electrolytic oxidation in 12-tungstosilicic acid | |
| Jiang et al. | Electrolyte–electrode interface and surface characterization of plasma electrolytic nitrocarburizing | |
| Verdalet-Guardiola et al. | Nucleation and growth mechanisms of trivalent chromium conversion coatings on 2024-T3 aluminium alloy | |
| Qi et al. | Formation of a trivalent chromium conversion coating on AZ91D magnesium alloy | |
| Lv et al. | Effects of graphite additives in electrolytes on the microstructure and corrosion resistance of Alumina PEO coatings | |
| Li et al. | Porous nanocrystalline Ti (CxN1− x) thick films by plasma electrolytic carbonitriding | |
| US20110315278A1 (en) | Titanium alloy excellent in intergranular corrosion resistance | |
| Lin et al. | Active screen plasma surface co-alloying treatments of 316 stainless steel with nitrogen and silver for fuel cell bipolar plates | |
| EP3467155A1 (en) | Sn alloy-plated steel sheet | |
| Sanjid et al. | Durable degradation resistance of graphene coated nickel and Monel-400 as bi-polar plates for proton exchange membrane fuel cell | |
| Smirnov et al. | Effect of electrolyte depletion on the characteristics of the anodic plasma electrolytic nitriding of a VT22 titanium alloy | |
| CN1328402C (zh) | 用于电解电容器的精炼铝薄板或带 | |
| EP4079705A1 (en) | Cubic boron nitride sintered compact | |
| Chen et al. | Effects of alloying concentration on the aqueous corrosion and passivation of aluminum-manganese-molybdenum concentrated alloys | |
| Student et al. | Influence of the composition of electrolyte for hard anodizing of aluminum on the characteristics of oxide layer | |
| JP2011504548A (ja) | 高速電気分解プロセスを用いた被覆のホウ素化のための方法 | |
| Beura et al. | Role of gradient nanograined surface layer on corrosion behavior of aluminum 7075 alloy | |
| Gong et al. | Effect of boron doping levels on the microstructure and characteristics of high-quality boron-doped diamond electrodes prepared by MPCVD | |
| Rosalbino et al. | Effect of silicon and germanium alloying additions on the passivation characteristics of Fe3Al intermetallic in sulphuric acid solution | |
| Amstutz et al. | Applications of surface‐analytical techniques to aluminium surfaces in commercial semifabricated and finished products | |
| WO2018021466A1 (ja) | 窒化バナジウム膜、窒化バナジウム膜の被覆部材およびその製造方法 | |
| Niu et al. | Microscopic origin of high corrosion resistance in 316L stainless steel by acidic passivation treatments |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1082004 Country of ref document: HK |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070725 Termination date: 20091022 |