KR20200004642A - Scaling cleaning agent for removing scaling of aluminum alloy which is generated during heat treatment and heat treatment method of aluminum alloy using the same - Google Patents
Scaling cleaning agent for removing scaling of aluminum alloy which is generated during heat treatment and heat treatment method of aluminum alloy using the same Download PDFInfo
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- KR20200004642A KR20200004642A KR1020180077776A KR20180077776A KR20200004642A KR 20200004642 A KR20200004642 A KR 20200004642A KR 1020180077776 A KR1020180077776 A KR 1020180077776A KR 20180077776 A KR20180077776 A KR 20180077776A KR 20200004642 A KR20200004642 A KR 20200004642A
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- scaling
- aluminum alloy
- heat treatment
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 52
- 238000010438 heat treatment Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000012459 cleaning agent Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 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 3
- 235000021314 Palmitic acid Nutrition 0.000 claims abstract description 3
- 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 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 3
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 3
- 239000011975 tartaric acid Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000002253 acid Substances 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002738 chelating agent Substances 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 6
- 150000004673 fluoride salts Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- UWBHMRBRLOJJAA-UHFFFAOYSA-N oxaluric acid Chemical compound NC(=O)NC(=O)C(O)=O UWBHMRBRLOJJAA-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 13
- 150000005324 oxide salts Chemical class 0.000 abstract description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- 238000005554 pickling Methods 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000956 alloy Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 238000000053 physical method Methods 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 alkylbenzene sulfonates Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
Images
Classifications
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/0005—Special cleaning or washing methods
- C11D11/0011—Special cleaning or washing methods characterised by the objects to be cleaned
- C11D11/0023—"Hard" surfaces
- C11D11/0029—Metals
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
-
- C11D2111/16—
Abstract
Description
본 발명은, 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제 및 이를 이용한 알루미늄 합금의 열처리 방법에 관한 것이다.The present invention relates to a scaling detergent for removing the scaling of the aluminum alloy generated during the heat treatment and a method of heat treatment of the aluminum alloy using the same.
금속의 가공 상에 있어서 열처리 가공은 금속의 표면 경도 및 강도, 연신율, 등의 물리적 성질을 개선하거나 두께, 형태, 등을 변형시키기 위하여 실행하는 가공 공정이다.In the processing of metals, heat treatment is a processing process performed to improve physical properties such as surface hardness and strength, elongation, and the like of metals, or to modify thicknesses, shapes, and the like.
일반적으로 금속의 열처리 가공에는 표면에 스케일이 형성되고, 이 스케일은 후속 공정으로의 진행 전 표면에 형성된 스케일을 제거해야만 후속 공정에 문제(불량)가 발생하지 않는데 이때 사용되는 방법으로는 물리적인 처리와 화학적인 처리 방법이 사용된다.Generally, a scale is formed on the surface during heat treatment of a metal, and the scale does not cause a problem (defect) in the subsequent process only by removing the scale formed on the surface before proceeding to the subsequent process. And chemical treatment methods are used.
금속 표면의 스케일 및 산화물(녹)을 제거하는 방법 중 물리적인 처리 방법에는 쇼트 및 샌드 블라스트 방식이 대표적이고 시설비 및 유지관리비용이 많이 들지만 처리 시간이 빠르고, 공정이 간단한 장점으로 현장에서 쉽게 적용하고 많이 사용하는 방법이며, 화학적 방법으로는 산 세정(피클링)이 대표적이며, 물리적 방법에 비해 시설비는 저렴하나 산성 약품을 사용하여 환경 및 작업장의 규제가 심하고, 공정관리에 전문성이 필요한 단점이 있으나 자동화 라인 및 대량의 물량을 처리할 수 있는 장점이 있다.Physical and physical methods of removing metal scales and oxides (rusts) are short and sand blasts, which are expensive in terms of facility and maintenance costs, but are fast to process and simple to process. Acid cleaning (pickling) is the most common method, and the cost of facilities is lower than that of physical methods. However, although the cost of facilities is lower than that of physical methods, the environment and workplace are severely regulated by using acidic chemicals. It has the advantage of handling automated lines and large volumes.
산세정(피클링)의 목적은 금속 표면의 손상 및 부식을 최소화하는 동시에 표면에 불필요하게 형성된 스케일을 최대한 빠른 속도로 제거하는 것이나 스케일의 제거 기전은 화학적 반응에 의한 기전으로 상기의 두 가지 목적을 동시에 만족하기는 힘들다.The purpose of pickling is to remove undesired scales on the surface as quickly as possible while minimizing damage and corrosion of the metal surface, but the mechanism of removing scales is a chemical reaction mechanism. At the same time it is hard to be satisfied.
알루미늄 및 그 합금은 다른 금속에 비해 산에 강하고, 알칼리에 취약하여 강력한 화학연마에는 강알칼리 베이스의 처리제를 사용하고 있으나, 열처리 가공에서 형성된 스케일의 경우 그 두께가 0.05 ~ 0.5 ㎛로 얇아 강알칼리 화학연마 시 제거되는 30 ~ 500 ㎛로는 약품 및 공정의 제어가 힘들어 산성의 화학연마를 통한 산 세정(피클링)을 실시한다.Aluminum and its alloys are more resistant to acids than other metals and are vulnerable to alkalis, so that strong alkali-based treatment agents are used for strong chemical polishing. It is difficult to control chemicals and processes with 30 to 500 μm removed, and acid cleaning (pickling) is performed through acidic chemical polishing.
일반적으로 알루미늄 및 그 합금의 산 세정(피클링)에 사용되는 물질은 무기 산 종류인 불화수소산 또는 질산과 불화수소산의 혼산(1:1)을 사용하였으나, 불화수소산의 위험도 및 규제가 강화되면서 고농도의 질산 또는 질산과 황산의 혼산(1:1~2:1 ro 1:2)을 사용하고 있는 추세이며, 처리시간을 늘리고 조금 더 안전한 질산과 인산의 혼산(1:1~1:5)을 사용하기도 한다.In general, the material used for acid cleaning (pickling) of aluminum and its alloys is an inorganic acid hydrofluoric acid or a mixture of nitric acid and hydrofluoric acid (1: 1), but the concentration of hydrofluoric acid is increased due to the increased risk and regulation of hydrofluoric acid. Nitric acid or a mixture of nitric acid and sulfuric acid (1: 1 to 2: 1 ro 1: 2) is increasing, and the treatment time is increased and a safer mixture of nitric acid and phosphoric acid (1: 1 to 1: 5) Also used.
하지만, 이러한 질산이나 황산은 성질 자체가 강산이므로 작업 중 사고의 위험이 매우 높을 뿐 아니라, 최종 처리 한 후 강산 물질에 대한 처리 비용이 올라가는 문제점이 있다.However, since the nitric acid or sulfuric acid itself is a strong acid, the risk of accident during operation is very high, and there is a problem in that the treatment cost for the strong acid material increases after the final treatment.
이에 본 발명은, 강산인 질산이나 불화수소산을 포함하지 않고 약산 물질을 포함하여 사용성과 안정성을 높이면서도, 충분한 열처리 스케일링에 대한 처리 효과를 보이는, 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제 및 이를 이용한 알루미늄 합금의 열처리 방법을 제공하기 위한 것이다. Accordingly, the present invention provides a scaling cleaner that does not include strong acid nitric acid or hydrofluoric acid, and includes a weak acid material to improve the usability and stability while removing scaling of the aluminum alloy generated during heat treatment, which exhibits a treatment effect on sufficient heat treatment scaling. And to provide a heat treatment method of the aluminum alloy using the same.
상술한 과제를 해결하기 위하여 안출된 본 발명의 일실시예인 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제는, 증류수 80~88중량%, 카르복시산, 술폰산, 세트산,뷰티르산,팔미트산,옥살 및 타타르산 중 적어도 하나를 포함하는 유기산 5.0~10.0 중량%, 산화물염으로 이루어지는 촉진제 0.1~10.0중량%를 포함할 수 있따.In order to solve the above problems, the scaling detergent for removing the scaling of the aluminum alloy produced during the heat treatment, which is an embodiment of the present invention, 80 to 88% by weight of distilled water, carboxylic acid, sulfonic acid, set acid, butyric acid, palmitic acid , 5.0-10.0 wt% of an organic acid comprising at least one of oxal and tartaric acid, and 0.1-10.0 wt% of an accelerator consisting of an oxide salt.
여기서, 상기 촉진제는, 0.1~5.0중량%의 불화물염일 수 있다.Here, the accelerator may be 0.1 to 5.0% by weight of the fluoride salt.
여기서, 상기 촉진제는, 5~10 중량%의 질산염일 수 있다.Here, the accelerator may be 5 to 10% by weight of nitrate.
여기서, 상기 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제는, 제거된 스케일링이 상기 알루미늄 합금에 재부착되는 것을 방지하기 위하여 1.0~2.0 중량%의 킬레이트제를 더 포함할 수 있다.Here, the scaling cleaner for removing the scaling of the aluminum alloy generated during the heat treatment may further include 1.0 to 2.0% by weight of a chelating agent to prevent the removed scaling is reattached to the aluminum alloy.
여기서, 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제는, 상기 알루미늄 합금에 대하여 균일한 반응이 발생하도록 1.0~3.0 중량%의 계면 활성제가 더 포함할 수 있다.Here, the scaling cleaner for removing the scaling of the aluminum alloy generated during the heat treatment may further include 1.0 to 3.0% by weight of a surfactant so that a uniform reaction with respect to the aluminum alloy.
본 발명의 다른 실시예인 알루미늄 합금의 열처리 방법은, 알루미늄 합금에 대하여 열처리를 행하는 단계; 열처리된 상기 알루미늄 합금을 냉각시키는 단계; 냉각된 상기 알루미늄 합금에 대하여 산세정을 행하여 스케일링을 제거하는 스케일링 제거 단계; 및 스케일링이 제거된 상기 알루미늄 합금을 수세한 후 건조하는 단계를 포함하고, 상기 스케일링 제거 단계는, 상술한 스케일링 세정제에 상기 알루미늄 합금을 3~10분간 처리하는 단계를 포함할 수 있다. Another embodiment of the present invention, the heat treatment method of the aluminum alloy, the step of performing a heat treatment for the aluminum alloy; Cooling the heat treated aluminum alloy; A scaling removal step of removing scaling by performing acid washing on the cooled aluminum alloy; And washing and drying the aluminum alloy in which the scaling is removed, and the scaling removing step may include treating the aluminum alloy with the above-described scaling cleaner for 3 to 10 minutes.
상술한 구성을 가진 본 발명의 일실시예에 따르면, 질산과 불화수소산과 같은 강산을 사용하지 않고, 조성물 자체가 약산이므로, 초기 반응속도는 느려서 사용상 안정성이 우수하게 되지만, 낮은 초기 반응속도에도 알루미늄 및 그 합금 구조물의 표면을 손상시키지 않고 10분 이내의 처리시간으로도 충분한 열처리시 발생하는 스케일링을 제거하여서 현장에서 원하는 상태의 소재를 확보할 수 있다.According to one embodiment of the present invention having the above-described configuration, since the composition itself is a weak acid without using a strong acid such as nitric acid and hydrofluoric acid, the initial reaction rate is slow and excellent in use stability, but even at a low initial reaction rate, aluminum And it is possible to secure the material in the desired state in the field by removing the scaling generated during sufficient heat treatment with a treatment time within 10 minutes without damaging the surface of the alloy structure.
또한, 본 발명의 일실싱예에 따른 세정제는 약산이므로 인체 피부에 미치는 영향이 적은 제품으로 일상생활에서도 활용이 가능한 조성으로 보일러, 가로등 및 난간대 등의 금속 구조물의 스케일 및 산화물을 제거하는 것도 유용하게된다.In addition, since the cleaning agent according to an embodiment of the present invention is a weak acid, it is a product having a low impact on the human skin, and thus it is also useful to remove scales and oxides of metal structures such as boilers, street lamps, and handrails in a composition that can be utilized in daily life. .
또한, 음이온 계면 활성제가 첨가되어 처리 중에는 본 소재를 직접 보호하여 알루미늄 및 그 합금 소재의 구조물 표면이 손상되지 않도록 작용하고, 처리 후에는 표면에 코팅 보호막을 형성하여 대기 중에 산소와 소재가 반응하는 것을 차단하여 구조물의 산화를 방지한다.In addition, an anionic surfactant is added to protect the material directly during the treatment so as not to damage the surface of the structure of aluminum and its alloy material, and after treatment, a coating protective film is formed on the surface to react with oxygen in the atmosphere. To prevent oxidation of the structure.
도 1은 본 발명의 일실시예와 비교예에 의해 산세정 전 및 산세정 후 알루미늄 합금의 표면 상태를 나타내는 이미지들.
도 2는 본 발명의 다른 실시예인 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제를 이용한 알루미늄 합금의 열처리 방법을 설명하기 위한 순서도.1 is an image showing the surface state of the aluminum alloy before and after pickling and pickling by one embodiment and a comparative example of the present invention.
Figure 2 is a flow chart for explaining a heat treatment method of the aluminum alloy using a scaling cleaner to remove the scaling of the aluminum alloy generated during the heat treatment of another embodiment of the present invention.
이하에서는 첨부된 도면들을 참조하여 본원 발명을 한정하지 않는 실시 예를 통해 본원 발명을 보다 상세히 설명하며, 일부 도면에서 동일한 요소에 대해서는 동일한 부호를 부여한다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings, which do not limit the present invention, and like reference numerals designate like elements in some drawings.
본원 발명에 따른 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제는 증류수, 유기산, 산화물염으로 이루어지는 촉진제, 및 킬레이트제, 그리고 계면 활성제를 포함하여 구성될 수 있다.The scaling detergent for removing the scaling of the aluminum alloy produced during the heat treatment according to the present invention may comprise an accelerator consisting of distilled water, an organic acid, an oxide salt, and a chelating agent, and a surfactant.
상술한 바와 같이, 본원 발명은 황산이나 질산과 같은 강산을 대신하여 산세정제로서 유기산을 사용한다. 유기산은 무기산을 대응하는 것으로서, 일반적으로 무기산보다 약한 산성을 띤다. 본 발명세서 유기산은 산세정제의 주원료로서 열처리 중 알루미늄 합금 프레이트의 표면에 형성되는 스케일링을 산세정을 통해 제거하는 주요성분이다. 본 발명에서 유기산은 5~10중량% 함유되게 되며, 5중량% 이하인 경우 산세정의 효과가 충분하지 않고, 10 중량% 이상인 경우 과반응을 일으키게 된다. As described above, the present invention uses organic acids as pickling agents in place of strong acids such as sulfuric acid and nitric acid. An organic acid corresponds to an inorganic acid, and generally has a weaker acid than the inorganic acid. In the present invention, the organic acid is a main ingredient of the pickling agent, and is a main component that removes the scaling formed on the surface of the aluminum alloy plate during pickling through pickling. In the present invention, the organic acid is contained 5 to 10% by weight, when the amount of less than 5% by weight of the effect of pickling is not sufficient, if more than 10% by weight will cause overreaction.
산화물염으로 이루어지는 촉진제는 0.1~10중량% 포함되게 된다. 산화물염은 옥시염이라고도 하는데, 염기성염 가운데 금속과 결합하고 있는 독립된 산소 원자(O2－라고 간주할 수 있는 것)를 갖고 있는 염을 말한다. 이와 같은 촉진제는 유기산과 알루미늄 합금의 스케일링과의 반응을 촉진하는 역할을 하며, 촉진제로서는, 불화물염 또는 질산염이 이용될 수 있다. 불화물염이 이용되는 경우 0.1~5.0중량%가 포함되게 되며, 질산염인 경우 5~10중량%가 포함되게 된다. 이러한 산화물 염으로서 질산 제 2 철(Iron(Ⅱ) nitrate)이 이용될 수 있다.The accelerator consisting of an oxide salt is to be contained 0.1 to 10% by weight. Oxide salt, also called oxy salt, refers to a salt having an independent oxygen atom (which can be regarded as O 2-) which is bonded to a metal among basic salts. Such a promoter serves to accelerate the reaction between the organic acid and the scaling of the aluminum alloy, and as the accelerator, fluoride salt or nitrate may be used. If fluoride salt is used, 0.1 to 5.0% by weight will be included, and nitrate will contain 5 to 10% by weight. As such an oxide salt, ferric nitrate (Iron (II) nitrate) can be used.
한편, 본 발명에 따른 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제는 킬레이트제를 부가적으로 더 가질 수 있다.On the other hand, the scaling cleaner for removing the scaling of the aluminum alloy generated during the heat treatment according to the present invention may further have a chelating agent.
킬레이트제는, 상기 유기산과 촉진제에 의해 대상물인 알루미늄 합금에서 분리된 스케일링이 알루미늄 합금에 재부착되는 것을 방지하는 기능을 한다. 이러한 킬레이트제는 위하여 1.0~2.0 중량% 포함될 수 있으며, 1.0 중량 % 이하로 포함되는 경우, 재부착 방지기능이 현저하게 저하되고, 2.0 중량% 이상인 경우, 타 성분의 성분비를 낮추어서 경제성이 떨어지는 문제점이 발생된다.The chelating agent functions to prevent re-attachment of the scaling separated from the aluminum alloy as the object by the organic acid and the accelerator to the aluminum alloy. Such a chelating agent may be included in the 1.0 to 2.0% by weight, when included in less than 1.0% by weight, the re-attachment prevention function is significantly lowered, when more than 2.0% by weight, lowering the component ratio of the other components have a problem of low economic efficiency Is generated.
한편, 상기 유기산과 촉진제의 스케일링과의 균일한 반응을 유도하기 위하여, 본 발명에 따른 스케일링 세정제는 계면 활성제가 포함되게 된다. 계면활성제는 묽은 용액 속에서 계면에 흡착하여 그 표면장력을 감소시키는 물질이다. 보통 1분자 속에 친유기와 친수기가 함께 들어 있는 양쪽 친매성(親媒性)인 물질이다. 이러한 계면 활성제로서, 알킬벤젠설폰산염, 고급아민할로젠화물·제사암모늄염·알킬피리디늄염 등이 이용될 수 있다. 이러한 계면 활성제는, 1.0~3.0 중량% 포함되게 구성될 수 있다. On the other hand, in order to induce a uniform reaction between the scaling of the organic acid and the accelerator, the scaling detergent according to the present invention will contain a surfactant. Surfactants are substances that adsorb to the interface in dilute solutions to reduce their surface tension. Usually, both molecules are lipophilic (親 媒 性) containing both lipophilic and hydrophilic groups in one molecule. As such surfactants, alkylbenzene sulfonates, higher amine halides, quaternary ammonium salts, alkylpyridinium salts, and the like can be used. Such surfactant, may be configured to contain 1.0 to 3.0% by weight.
이러한 계면 활성제는, 방청기능을 향상시킬 수 있다. 계면 활성제 중 비이온 계면 활성제 또는 음이온 계면 활성제가 활용된다. 알루미늄 합금의 경우 상온 보관 또는 열처리 시 합금 표면에 산화알루미늄(Al2O3)이 형성된다. 그러나 피클링 작업 시 알루미늄 합금의 표면은 순수 알루미늄(Al2 +) 형성되어 계면활성제의 선택 시 양이온이 아닌 음이온 또는 비이온 계면활성제를 사용하는 것이 평활성과 방청성이 우수하게 된다.Such a surfactant can improve the rust prevention function. Among the surfactants, nonionic surfactants or anionic surfactants are utilized. In the case of an aluminum alloy, aluminum oxide (Al 2 O 3 ) is formed on the surface of the alloy during normal temperature storage or heat treatment. However, the surface of the pickled aluminum alloy during operation is made of pure aluminum (Al + 2) is the selection of surfactants to use an anionic or nonionic surface active agent other than the cationic excellent in smoothness and corrosion protection.
이와 같은 구성을 가진 본 발명의 실시예와 강산을 사용하는 비교예를 도 1을 통해 보다 상세하게 설명하도록 한다. An embodiment of the present invention having such a configuration and a comparative example using a strong acid will be described in more detail with reference to FIG. 1.
비교예는 물 70 중량%, 질산 15 중량% 그리고 황산 15중량% 포함하는 종래의 산세정제로서, 강산이면서 유독물질인 질산과 황산을 다량 함유하고 있음을 확인할 수 있다.Comparative Example is a conventional pickling agent containing 70% by weight of water, 15% by weight of nitric acid and 15% by weight of sulfuric acid, it can be seen that it contains a large amount of nitric acid and sulfuric acid, which are strong and toxic.
본원 발명의 제 1 실시예는, 물 85 중량%, 유기산 10.0 중량%, 킬레이트제 2.0 중량%, 계면 활성제 2.0중량%, 촉진제로서 불화물염 1.0 중량%를 포함하고 있으며, 본원 발명의 제 2 실시예는 물 88 중량%, 유기산 5.0 중량%, 킬레이트제 1.0 중량%, 계면 활성제 1.0중량%, 촉진제로서 질산염 5.0 중량%를 포함한다.The first embodiment of the present invention includes 85% by weight of water, 10.0% by weight of organic acid, 2.0% by weight of chelating agent, 2.0% by weight of surfactant, 1.0% by weight of fluoride salt as accelerator, and the second embodiment of the present invention. Comprises 88% by weight of water, 5.0% by weight of organic acid, 1.0% by weight of chelating agent, 1.0% by weight of surfactant, and 5.0% by weight of nitrate as accelerator.
한편 대상물인 알루미늄 합금은 밀도가 2.78g/㎤이고,길이가 150.0mm이고, 폭이 20.0mm, 두께가 1.6mm인 열처리된 알루미늄 합금이 열처리되는 상태를 나타내는 것이 도 1의 도면이다. On the other hand, the aluminum alloy as an object shows a state in which the heat-treated aluminum alloy having a density of 2.78 g / cm 3, a length of 150.0 mm, a width of 20.0 mm, and a thickness of 1.6 mm is heat treated.
도 1에 도시된 바와 같이, 처리전에 검정색 스케일링이 있던 알루미늄 합금은 비교예 뿐 아니라 제 1 및 제 2 실시예에서 스케일링이 모두 제거된 것을 알 수 있다.As shown in FIG. 1, it can be seen that the aluminum alloy that had black scaling before treatment had all the scaling removed in the first and second embodiments as well as the comparative example.
제 2 실시예는 비교예와 거의 동등하게 스케일링이 제거되었으며, 제 1 실시예는 비교예 보다 더 많은 반응이 일어나게 된 것을 나타내고 있다. 제거된 피막의 두께를 측정한바, 비교예는 0.25㎛의 두께의 피막이 제거되었고, 제 2 실시예는 이와 유사한 0.23㎛의 두께가 제거되었다. 그리고, 제 1 실시예에서는 0.95㎛의 피막이 제거됨을 확인할 수 있었다.The second example shows that the scaling is removed almost identically to the comparative example, and the first example shows that more reaction occurs than the comparative example. As a result of measuring the thickness of the removed film, the comparative example removed the film having a thickness of 0.25 탆, and the second example removed the similar thickness of 0.23 탆. In the first embodiment, it was confirmed that the coating of 0.95 μm was removed.
이와 같은 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제를 이용한 알루미늄 합금의 열처리 방법은 도 2에 도시된 바와 같은 공정을 통해 스케일링 제거가 완료된다.In the heat treatment method of the aluminum alloy using the scaling cleaner which removes the scaling of the aluminum alloy generated during the heat treatment, the scaling removal is completed through the process as shown in FIG. 2.
도 2에 도시된 바와 같이, 우선 대상물이 알루미늄 합금에 대하여 열처리를 한 후(S1), 냉각을 진행한다(S2). 이 때 스케일링이 표면에 형성된다. 그 다음, 상술한 구성을 가진 세정제를 통하여 산세정(피클링)을 진행하게 된다(S3). 이 때 산세정 단계는 3~10분간 진행되면 족하다. 그 다음, 스케일링이 제거된 상기 알루미늄 합금을 수세한 후 건조하는 단계를 통해 스케일링 제거 공정이 완료된다.As shown in FIG. 2, first, an object is heat-treated with respect to an aluminum alloy (S1), and then cooling is performed (S2). At this time scaling is formed on the surface. Then, pickling is performed through the cleaning agent having the above-described configuration (S3). At this time, the pickling step is enough for 3 to 10 minutes. Then, the descaling process is completed by washing and then drying the descaled aluminum alloy.
상술한 구성을 가진 본 발명의 일실시예에 따르면, 질산과 불화수소산과 같은 강산을 사용하지 않고, 조성물 자체가 약산이므로, 초기 반응속도는 느려서 사용상 안정성이 우수하게 되지만, 낮은 초기 반응속도에도 알루미늄 및 그 합금 구조물의 표면을 손상시키지 않고 10분 이내의 처리시간으로도 충분한 열처리시 발생하는 스케일링을 제거하여서 현장에서 원하는 상태의 소재를 확보할 수 있다.According to one embodiment of the present invention having the above-described configuration, since the composition itself is a weak acid without using strong acids such as nitric acid and hydrofluoric acid, the initial reaction rate is slow and excellent in use stability, but even at a low initial reaction rate, aluminum And it is possible to secure the material in the desired state in the field by removing the scaling generated during sufficient heat treatment with a treatment time within 10 minutes without damaging the surface of the alloy structure.
또한, 본 발명의 일실싱예에 따른 세정제는 약산이므로 인체 피부에 미치는 영향이 적은 제품으로 일상생활에서도 활용이 가능한 조성으로 보일러, 가로등 및 난간대 등의 금속 구조물의 스케일 및 산화물을 제거하는 것도 유용하게된다.In addition, since the cleaning agent according to an embodiment of the present invention is a weak acid, it is a product having a low impact on the human skin, and thus it is also useful to remove scales and oxides of metal structures such as boilers, street lamps, and handrails in a composition that can be utilized in daily life. .
또한, 음이온 계면 활성제에 의해 열처리 중에는 본 소재를 직접 보호하여 알루미늄 및 그 합금 소재의 구조물 표면이 손상되지 않도록 작용하고, 처리 후에는 표면에 코팅 보호막을 형성하여 대기 중에 산소와 소재가 반응하는 것을 차단하여 구조물의 산화를 방지한다.In addition, during heat treatment by anionic surfactants, this material is directly protected to prevent damage to the surface of the structure of aluminum and its alloy material, and after treatment, a coating protective film is formed on the surface to prevent oxygen and the material from reacting in the air. To prevent oxidation of the structure.
상기와 같이 설명된 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제 및 이를 이용한 알루미늄 합금의 열처리 방법은 상기 설명된 실시 예들의 구성과 방법이 한정되게 적용될 수 있는 것이 아니라, 상기 실시 예들의 다양한 변형이 이루어질 수 있도록 각 실시 예들의 전부 또는 일부가 선택적으로 조합되어 구성될 수도 있다.The scaling cleaner for removing the scaling of the aluminum alloy generated during the heat treatment described above and the heat treatment method of the aluminum alloy using the same are not limited to the configuration and method of the above-described embodiments, but various All or some of the embodiments may be selectively combined to enable modification.
Claims (6)
80 to 88% by weight of distilled water, carboxylic acid, sulfonic acid, acetic acid, butyric acid, palmitic acid, 5.0 to 10.0% by weight of oxal and tartaric acid, 0.1 to 10.0% by weight of accelerator A scaling detergent for removing the scaling of the aluminum alloy produced during the heat treatment.
상기 촉진제는, 0.1~5.0중량%의 불화물염인, 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제.
The method of claim 1,
The accelerator is a scaling cleaner for removing the scaling of the aluminum alloy produced during the heat treatment, which is 0.1 to 5.0% by weight of the fluoride salt.
상기 촉진제는, 5.0~10.0 중량%의 질산염인, 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제.
The method of claim 1,
The accelerator is a scaling cleaner for removing the scaling of the aluminum alloy produced during the heat treatment, which is 5.0 to 10.0% by weight of nitrate.
제거된 스케일링이 상기 알루미늄 합금에 재부착되는 것을 방지하기 위하여 1.0~2.0 중량%의 킬레이트제를 더 포함하는, 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제.
The method of claim 1,
A scaling detergent for removing scaling of the aluminum alloy produced during heat treatment, further comprising 1.0 to 2.0 wt% chelating agent to prevent the removed scaling from reattaching to the aluminum alloy.
상기 알루미늄 합금에 대하여 균일한 반응이 발생하도록 1.0~3.0 중량%의 계면 활성제가 더 포함하는, 열처리중 생성되는 알루미늄 합금의 스케일링을 제거하는 스케일링 세정제.
The method of claim 1,
Scaling cleaner to remove the scaling of the aluminum alloy produced during the heat treatment, further comprising 1.0 to 3.0% by weight of a surfactant to cause a uniform reaction to the aluminum alloy.
열처리된 상기 알루미늄 합금을 냉각시키는 단계;
냉각된 상기 알루미늄 합금에 대하여 산세정을 행하여 스케일링을 제거하는 스케일링 제거 단계; 및
스케일링이 제거된 상기 알루미늄 합금을 수세한 후 건조하는 단계를 포함하고,
상기 스케일링 제거 단계는,
제 1 항 내지 제 5 항 중 어느 한항에 기재된 스케일링 세정제에 상기 알루미늄 합금을 3~10분간 처리하는 단계를 포함하는, 알루미늄 합금의 열처리 방법.
Heat-treating the aluminum alloy;
Cooling the heat treated aluminum alloy;
A scaling removal step of removing scaling by performing acid washing on the cooled aluminum alloy; And
Washing and drying the aluminum alloy from which the scaling has been removed;
The descaling step,
A method for heat treatment of an aluminum alloy, comprising the step of treating the aluminum alloy with the scaling cleaner according to any one of claims 1 to 5 for 3 to 10 minutes.
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| US3003896A (en) * | 1958-01-17 | 1961-10-10 | Rohr Aircraft Corp | Process and composition for treating aluminum alloys |
| KR970070244A (en) * | 1996-04-29 | 1997-11-07 | 이기원 | Descaling method of stainless steel and chromium and / or nickel alloy steel, pickling composition and pickling waste recycling method |
| KR20040000230A (en) * | 2002-06-24 | 2004-01-03 | 삼성전자주식회사 | Cleaning Solution and Method of Cleaning Ceramic Part |
| JP2008291336A (en) * | 2007-05-28 | 2008-12-04 | Nippon Steel Corp | Method for continuously treating aluminum alloy sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3003896A (en) * | 1958-01-17 | 1961-10-10 | Rohr Aircraft Corp | Process and composition for treating aluminum alloys |
| KR970070244A (en) * | 1996-04-29 | 1997-11-07 | 이기원 | Descaling method of stainless steel and chromium and / or nickel alloy steel, pickling composition and pickling waste recycling method |
| KR20040000230A (en) * | 2002-06-24 | 2004-01-03 | 삼성전자주식회사 | Cleaning Solution and Method of Cleaning Ceramic Part |
| JP2008291336A (en) * | 2007-05-28 | 2008-12-04 | Nippon Steel Corp | Method for continuously treating aluminum alloy sheet |
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