KR100578215B1 - Method of manufacturing sulfuric acid bath galvanized steel sheet - Google Patents
Method of manufacturing sulfuric acid bath galvanized steel sheet Download PDFInfo
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- KR100578215B1 KR100578215B1 KR1020030089350A KR20030089350A KR100578215B1 KR 100578215 B1 KR100578215 B1 KR 100578215B1 KR 1020030089350 A KR1020030089350 A KR 1020030089350A KR 20030089350 A KR20030089350 A KR 20030089350A KR 100578215 B1 KR100578215 B1 KR 100578215B1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 7
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 8
- 239000010959 steel Substances 0.000 claims abstract description 8
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims abstract 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- -1 iron ion Chemical class 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 2
- 229960001763 zinc sulfate Drugs 0.000 claims 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000004070 electrodeposition Methods 0.000 description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910001439 antimony ion Inorganic materials 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
전기아연 도금욕에 무기원소를 가진 무기첨가제를 첨가하여 표면물성을 개선한 전기아연 도금 제조방법에 관한 것으로, 황산욕에서 생산되는 전기아연도금강판에 적정량의 Fe 및 Sb를 첨가하여 가공성 및 마찰특성을 향상시키는데 그 목적이 있다. 이러한 목적을 달성하기 위해 도금욕 내 Fe수화물 및 Sb2O3을 첨가하여 도금층내에 전착시키고 합금화된 적정량의 Fe 및 Sb는 도금층의 결정방위 및 조직의 변화를 통해 마찰특성에 의한 가공성 및 경도가 우수한 전기아연도금강판이 되도록 한다.The present invention relates to a method of manufacturing an electro zinc coating having improved surface properties by adding an inorganic additive having an inorganic element to an electro zinc plating bath. The processability and friction characteristics are obtained by adding an appropriate amount of Fe and Sb to an electro zinc plated steel sheet produced in a sulfuric acid bath. The purpose is to improve. In order to achieve this purpose, Fe hydrate and Sb 2 O 3 in the plating bath are added and electrodeposited in the plating layer, and the appropriate amounts of Fe and Sb alloyed are excellent in workability and hardness due to friction characteristics through the change of crystal orientation and structure of the plating layer. It shall be an electro galvanized steel sheet.
황화아연도금욕, 무기첨가제, Fe 수화물, 산화안티몬 Zinc Sulfide Plating Bath, Inorganic Additive, Fe Hydrate, Antimony Oxide
Description
도 1은 Fe 및 Sb 함량에 따른 전류효율 변화도1 is a change in current efficiency according to the Fe and Sb content
도 2는 Fe 및 Sb 함량에 따른 표면마찰 특성 변화도2 is a change in the surface friction characteristics according to the Fe and Sb content
도 3은 Fe 및 Sb 함량에 따른 경도값의 변화도3 is a change in hardness value according to the Fe and Sb content
본 발명은 마찰특성 및 가공성이 우수한 전기아연도금강판의 제조방법에 관한 것으로 더욱 상세하게는 불용성 양극의 황산욕에 Fe 및 Sb를 미량 첨가하여 도금층의 마찰특성을 개선하여 가공성을 향상시킨 도금욕 및 전기아연도금강판의 제조방법에 관한 것이다. The present invention relates to a method for manufacturing an electrogalvanized steel sheet having excellent friction characteristics and workability, and more particularly, a plating bath in which a small amount of Fe and Sb are added to a sulfuric acid bath of an insoluble anode to improve workability by improving friction characteristics of a plating layer. It relates to a method for producing an electrogalvanized steel sheet.
일반적으로 전기아연도금강판은 도금효율이 좋고 비용이 싸며 표면외관 및 아연의 희생방식 효과에 의한 내식성이 우수하기 때문에 가전제품, 건자재, 자동차 소재 등에 널리 사용되고 있다. 특히 자동차용 아연계 합금도금 및 크로메이트 처리, 인산염 처리, 기능성 수지 처리, 도장 등 각종 후처리가 가능하여 다양한 제품으로 많은 분야에 적용되고 있다. In general, electro-galvanized steel sheet is widely used in home appliances, construction materials, automobile materials, etc. because the plating efficiency, low cost and excellent corrosion resistance due to the surface appearance and the sacrificial method effect of zinc. In particular, various post-treatments such as zinc-based alloy plating and chromate treatment, phosphate treatment, functional resin treatment, and coating for automobiles are possible and are applied to many fields as various products.
도금욕은 통상 염산욕 및 황산욕이 주로 채택되고 있으며 황산욕 도금액은 염산욕 대비 전기 전도도가 낮아 도금시 과전압이 많이 걸리므로, 고속도금에 필요한 고 전류밀도 작업이 가능하기 위해서는 염산욕 도금과 대비하여 볼 때 보다 극간 거리를 짧게 해 주어야 한다. 극간 거리를 줄이기 위해서는 먼저 양극의 용해가 일어나지 않는 불용성 양극을 사용해야 한다. 이러한 불용성 양극은 염산욕의 가용성 양극에 비해 자주 교체할 필요가 없는 장점이 있으나 전기도금층 특성 향상을 위한 첨가제 사용시 제한을 받는 것으로 알려져 있다. 특히 유기물을 투입할 경우 IrO2양극판에 흡착되어 전착을 방해하여 도금강판 물성을 저하시키기 때문에 염산욕에 첨가되는 다양한 유기첨가제를 그대로 적용할 수 없다. Hydrochloric acid baths and sulfuric acid baths are commonly adopted in plating baths. Sulfuric acid bath plating solutions have a lower electrical conductivity than hydrochloric acid baths, so they require a lot of overvoltage during plating. You should shorten the distance between the poles. In order to reduce the distance between the electrodes, an insoluble anode that does not dissolve in the anode must first be used. Such insoluble anodes do not need to be replaced frequently compared to soluble anodes in hydrochloric acid baths, but are known to be limited when using additives to improve the electroplating layer properties. In particular, when the organic material is added, various organic additives added to the hydrochloric acid bath cannot be applied as it is adsorbed on the IrO 2 positive electrode plate, which prevents electrodeposition and degrades the properties of the plated steel sheet.
따라서, 본 발명은 염산욕에 비해 적용시기가 늦은 불용성 양극을 사용하는 황산욕에서는 전류효율을 높이는 전기전도 보조제 이외 물성개선에 영향을 줄 수 있는 첨가제에 관한 연구 실적이 미진한 것에 착안하여 연구를 거듭해 왔다.Therefore, the present invention is focused on the fact that in the sulfuric acid bath using an insoluble anode, which is late in application compared to the hydrochloric acid bath, the research results on the additives that may affect the improvement of physical properties in addition to the conduction aid to increase the current efficiency is repeated. come.
지금까지 도금액내 첨가제를 사용하지 않는 경우 표면백색도 및 광택도가 작아 표면외관이 떨어지고 마찰계수가 커서 가공시 도금층 박리가 일어나고 또한 스크래치성이 떨어져 수요가들로부터 불만사항이 제기되어 왔다. 종래 EG제품의 표면외관의 경우 특허출원번호 10-2002-41116과 같이 에칭공정 및 린스공정을 강화하여 외관을 개선하여 수요가들로부터 좋은 평가를 받고 있으나 마찰특성 및 도금층 경도에 관해서는 여전히 불만족스러운 것으로 알려져 있다. Until now, when the additives in the plating solution are not used, the surface whiteness and gloss are small, the surface appearance is low, and the friction coefficient is large, resulting in peeling of the plating layer during processing, and scratch resistance, which has caused complaints from the demanders. The surface appearance of the conventional EG products has been well received by customers by improving the appearance by strengthening the etching process and the rinse process as in Patent Application No. 10-2002-41116, but they are still unsatisfactory with regard to friction characteristics and plating hardness. It is known.
따라서 본 발명에서는 상술한 연속전기도금라인에서 마찰특성을 개선하여 가 공성이 우수하고 경도를 증가시켜 스크래치성 및 일종의 파우더링성을 개선한 전기아연도금강판의 제조방법을 제공하는데 그 목적이 있다. 이러한 목적을 달성하기 위하여 본 발명에서는 통상적으로 황산욕에 투입이 용이하고 첨가에 따른 결함 발생이 거의 없는 무기첨가제의 영향을 우선적으로 고려하여 물성을 비교하였으며 그중에서 가장 마찰특성 및 가공성에 양호한 특성을 나타낸 Fe 및 Sb 첨가에 대한 조성을 제시하여도금층내 Fe 및 Sb 성분비 및 전류밀도조건을 제어함으로써 가공성 및 경도가 우수한 전기아연도금강판을 제조하는 것을 특징으로 한다.Accordingly, an object of the present invention is to provide a method for manufacturing an electro-galvanized steel sheet having improved workability and hardness by improving friction characteristics in the aforementioned continuous electroplating line, thereby improving scratchability and a kind of powdering property. In order to achieve this purpose, the present invention compares the physical properties in consideration of the effects of inorganic additives that are easily added to a sulfuric acid bath and have almost no defects. By presenting the composition for the Fe and Sb addition shown, it is characterized by producing an electro-zinc plated steel sheet excellent in workability and hardness by controlling the Fe and Sb component ratio and current density conditions in the plated layer.
상기 목적을 달성하기 위한 본 발명은 황화아연도금용액에 무기첨가제로서 Fe2SO4·7H2O 및 Sb2O3을 상기 황화아연도금용액에 철이온이 100~1500mg/l 첨가하고 전류효율 및 물성을 보완하기 위하여 안티몬 이온함량이 1~15mg/l의 범위에서 적정량 첨가하도록 한 것을 특징으로 하는 마찰특성 및 도금층 경도가 우수한 전기아연도금강판 제조방법에 관한 것이다. In order to achieve the above object, the present invention adds Fe 2 SO 4 · 7H 2 O and Sb 2 O 3 to the zinc sulfide plating solution as an inorganic additive to zinc sulfide plating solution, and adds 100 ~ 1500 mg / l of iron ion to current efficiency and The present invention relates to a method for producing an electro-zinc plated steel sheet having excellent friction characteristics and plating layer hardness, wherein the antimony ion content is added in an appropriate amount in the range of 1 to 15 mg / l.
여기에서 철이온이 100mg/l 미만으로 첨가되면 백색도, 광택도가 나빠지고 도금스크랫치가 용이하게 되며 도금조직의 방향성을 얻을 수 없게 된다. 1500mg/l 초과되게 첨가하면 도금금속의 전착성과 전류효율 등을 떨어뜨린다. 또한, 안티몬이온함량도 1mg/l 미만에서는 효력을 발휘하지 못하고 15mg/l 초과시 그 효과가 포화되고 고가의 재료소비만 초래된다.If iron ions are added below 100 mg / l, the whiteness and gloss will be worse, the plating scratch will be easy, and the orientation of the plating structure will not be obtained. Adding more than 1500mg / l reduces the electrodeposition and current efficiency of the plated metal. In addition, the antimony ion content is not effective at less than 1 mg / l, the effect is saturated when more than 15 mg / l and only expensive material consumption is caused.
본 발명은 아연도금용액중에 첨가되는 무기첨가제인 철의 경우 아연도금층내 미량 공석이 되면 백색도 및 광택도에 큰 영향이 없으며 도금조직을 방향성이 없게 하여 마찰계수를 증가시켜 가공성을 양호하게 하고 순수아연에 비해 경도를 높이는 장점이 있다. 그러나 철은 아연에 비해 전착성이 떨어져 전류효율을 감소시키는 문제점이 있으므로 제품의 품질 뿐만 아니라 원단위를 상승시킬 수 있다. 여기에 안티몬(Sb)을 적정량 첨가하면 거의공석이 되지 않으면서 철의 전착성 증가시키는 역할을 하여 전류효율을 증가시킬 뿐만 아니라 도금층의 결정방위 및 조직변화를 통해 도금조직의 응집력을 양호하게 하여 도금층 경도 및 마찰특성에 의한 가공성을 개선하는데 보조역할을 하는 것으로 판단된다. In the present invention, in the case of iron, an inorganic additive added to the zinc plating solution, when there is a small amount of vacancies in the zinc plating layer, there is no significant effect on the whiteness and glossiness. Compared with the hardness increase. However, iron has a problem of reducing current efficiency due to poor electrodeposition compared with zinc, which can increase not only product quality but also basic unit. Addition of an appropriate amount of antimony (Sb) increases the current efficiency by increasing the electrodeposition property of iron with little or no vacancy, and improves the cohesiveness of the plating structure through the crystal orientation and structure change of the plating layer. It is believed to play a role in improving workability due to hardness and friction characteristics.
일반적으로 전기도금시 아연의 경우 비정상적인 전착거동(anomalous deposition)으로 인해 자신보다 표준전극전위가 낮은 금속에 비해 전착특성이 우수한데 이것은 음극전극 표면에 아연수산화물(Zn(OH)-)의 생성으로 합금도금시 다른 원소의 진행을 방해하기 때문이며 여기에 안티몬이 첨가되면 비정상적인 전착거동 (anomalous deposition)을 감소시켜 철이온의 전착효율을 증가시키는 것으로 생각된다. 즉, 본 발명은 전기도금시 도금액에 안티몬(Sb)을 첨가하므로써 전기아연도금액내에 첨가된 철이온이 도금층에 양호하게전착되어 결정조직 변화를 통해 가공성 및 경도를 향상시키고 안티몬은 철이온 첨가에 따른 전류효율을 보완하면서 물성개선에 상승효과를 일으키도록 한 것이다. In general, in electroplating, zinc has better electrodeposition characteristics than metals with lower standard electrode potentials due to abnormal electrodeposition. This is due to the formation of zinc hydroxide (Zn (OH)-) on the surface of the cathode electrode. This is because it prevents the progress of other elements during plating, and it is thought that the addition of antimony to this increases the electrodeposition efficiency of iron ions by reducing abnormal electrodeposition. That is, in the present invention, by adding antimony (Sb) to the plating solution during electroplating, the iron ions added in the electro zinc plating solution are well electrodeposited on the plating layer, thereby improving the processability and hardness through the change of crystal structure, and the antimony is added to the iron ion. It is to make synergy effect on property improvement while compensating for current efficiency.
[실시예]EXAMPLE
냉연강판을 150×200mm로 절단하여 알칼리 탈지 및 산화물 제거를 위해 8~10%의 염산용액에 산세를 거친 후, 전기도금 시뮬레이터를 이용하여 아래와 같은 용액조성과 전해조건으로 전기아연도금을 실시하였다. The cold rolled steel sheet was cut to 150 × 200mm, pickled in 8 ~ 10% hydrochloric acid solution for alkali degreasing and oxide removal, and then electrogalvanized using electroplating simulator under the following solution composition and electrolytic conditions.
1) 도금액 온도 : 55℃ 1) Plating solution temperature: 55 ℃
2) 도금부착량 : 20g/㎡2) Plating amount: 20g / ㎡
3) 양극과 음극 간격 : 10mm3) anode and cathode gap: 10mm
4) pH : 1.84) pH: 1.8
5) 아연이온농도 : 110g/l5) Zinc ion concentration: 110g / l
6) 무기첨가제인 철 이온농도 : 100~1500mg/l 6) Iron ion concentration as inorganic additive: 100 ~ 1500mg / l
7) 무기첨가제인 안티몬 이온농도 : 5mg/l 7) Antimony ion concentration as inorganic additive: 5mg / l
8) 전류밀도 : 10, 40, 70A/d㎡8) Current Density: 10, 40, 70A / d㎡
도금액내의 아연이온농도를 110g/l로 일정하게 유지하고, 무기첨가제 Fe2SO4·7H2O 및 Sb2O3의 이온농도를 상기와 같이 변화시키면서 40A/d㎡의 전류밀도, 55℃ 온도에서 20g/㎡부착시킨 후 도금층 경도 및 마찰특성을 평가하였다. The zinc ion concentration in the plating liquid is kept constant at 110 g / l, and the ion density of the inorganic additives Fe 2 SO 4 · 7H 2 O and Sb 2 O 3 is changed as described above, with a current density of 40 A / dm 2 and a temperature of 55 ° C. After attaching at 20g / ㎡ at and evaluated the coating layer hardness and friction characteristics.
첨가제에 따른 표면외관 변화를 관찰하기 위해 사용된 기기 중에 광택도는 광택도계(Tri-Microgloss-60-85)를 이용하여 입사각 60°에서 측정하였고, 백색도는 색차계(Color Quest Ⅱ Hunter Lab.)를 사용하여 각각 측정하였다. 도금층의 가공성 평가를 위한 방법으로 마찰계수를 측정하였으며 시험조건은 시편을 300×20mm로 절단한 후, 가장자리의 거친 표면을 제거한 다음 드로비드시험기를 이용하여 다이 하중 5KN, 인발속도 초당 100mm로 인발하여 마찰계수를 구하였다. 또한 도금층 경도는 극미소경도기인 나노인덴터(nano-indenter)를 이용하여 측정하였다. 아래의 표1은 그 결과를 나타낸 것이다. Glossiness was measured at the incidence angle 60 ° by using a glossmeter (Tri-Microgloss-60-85), and the whiteness was measured by the color difference meter (Color Quest II Hunter Lab.). Each was measured using. The coefficient of friction was measured as a method for evaluating the workability of the plated layer, and the test conditions were to cut the specimen to 300 × 20mm, remove the rough surface of the edge, and then draw a die load of 5KN and a drawing speed of 100mm per second using a draw bead tester. The coefficient of friction was obtained. In addition, the plated layer hardness was measured using a nano-indenter (micro-indenter). Table 1 below shows the results.
표 1과 도 1~도 3에서 볼 수 있는 바와 같이, 전해액내의 철(Fe)함량(mg/l)은 1500mg/l 초과시부터는 전류효율변화가 거의 없음을 알 수 있다. 또한, 마찰계수 또한 철함유량 1500mg/l 초과되면 거의 변함이 없음을 도 2로부터 알 수 있으며, 안티몬(Sb) 또한 15mg/l 초과시에는 마찰계수에 거의 변화가 없게 됨을 알 수 있다.As can be seen from Table 1 and Figures 1 to 3, it can be seen that the iron (Fe) content in the electrolyte (mg / l) is almost no change in current efficiency from more than 1500mg / l. In addition, it can be seen from Figure 2 that the friction coefficient is also almost unchanged when the iron content is more than 1500mg / l, it can be seen that the antimony (Sb) also has little change in the friction coefficient when it exceeds 15mg / l.
한편, 도 3의 (a), (b)를 보면 철함량은 1500mg/l 초과되더라도 계속 도금층경도가 증가됨을 알 수 있으며, 안티몬은 15mg/l 초과시에는 그리 큰 도금층경도증 가가 없음을 알 수 있다.On the other hand, Figure 3 (a), (b) it can be seen that even if the iron content is more than 1500mg / l plated layer hardness continues to increase, and when antimony exceeds 15mg / l it can be seen that there is no significant increase in the plated layer hardness. .
상술한 바의 결과로부터 철함유량의 상한치를 1500mg/l로 설정하였다. 한편 철함유량은 100mg/l 미만의 경우는 제어하기도 용이하지 않을 뿐 아니라 도금층경도가 지나치게 낮아져 스크래치 발생이 용이하게 되고, 마찰계수가 너무 높아져 도금층박리 등의 문제가 발생된다.From the result as mentioned above, the upper limit of iron content was set to 1500 mg / l. On the other hand, the iron content of less than 100mg / l is not only easy to control, but also the plating layer hardness is too low to easily scratch, and the friction coefficient is too high to cause problems such as peeling of the plating layer.
안티몬(Sb)의 경우에도 도 2(b), 도 3(b)에서와 같이 1mg/l 미만의 경우 마찰계수와 도금층경도 변화가 심하므로, 1mg/l 이상으로 설정하였다.In the case of antimony (Sb), as shown in Fig. 2 (b), 3 (b) is less than 1 mg / l friction coefficient and plated layer hardness change, so it was set to more than 1 mg / l.
상술한 바와 같이 본 발명에서는 전기아연도금 용액중에 무기첨가제인 Fe2SO4·7H2O을 적정량 첨가하여 도금층에 철을 공석시키고 Sb2O 3를 첨가하여 철이온 공석에 따른 전류효율을 보완하므로써 물성이 우수한 전기아연도금강판을 제조할 수 있게 되었다. 또한 본 발명상의 전기아연도금강판은 기존강판에 비해 도금층의 마찰계수가 작아 가공성이 우수하며 경도를 향상시켜 아연도금층의 취약한 물성을 개선시켰음을 알 수 있었다. As described above, in the present invention, by adding an appropriate amount of an inorganic additive Fe 2 SO 4 · 7H 2 O in the electrogalvanizing solution, vacancy of iron in the plating layer and Sb 2 O 3 are added to compensate for the current efficiency according to the iron ion vacancies. It is possible to manufacture an electro galvanized steel sheet excellent in physical properties. In addition, the electro-galvanized steel sheet according to the present invention was found to have a low coefficient of friction of the plated layer compared to the existing steel sheet, thereby improving the workability and improving the vulnerable physical properties of the zinc plated layer.
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