JP5906633B2 - 塗装後耐食性に優れる合金化溶融亜鉛めっき鋼板 - Google Patents
塗装後耐食性に優れる合金化溶融亜鉛めっき鋼板 Download PDFInfo
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- JP5906633B2 JP5906633B2 JP2011208331A JP2011208331A JP5906633B2 JP 5906633 B2 JP5906633 B2 JP 5906633B2 JP 2011208331 A JP2011208331 A JP 2011208331A JP 2011208331 A JP2011208331 A JP 2011208331A JP 5906633 B2 JP5906633 B2 JP 5906633B2
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- less
- steel sheet
- corrosion resistance
- coating
- zinc
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- 238000005260 corrosion Methods 0.000 title claims description 31
- 230000007797 corrosion Effects 0.000 title claims description 30
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 13
- 239000008397 galvanized steel Substances 0.000 title claims description 13
- 238000010422 painting Methods 0.000 title description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 40
- 239000010959 steel Substances 0.000 claims description 40
- 238000007747 plating Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 33
- 239000011701 zinc Substances 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 238000001228 spectrum Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 12
- 238000005275 alloying Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint 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
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C22C—ALLOYS
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- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
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- C23C2/06—Zinc or cadmium or alloys based thereon
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
特許文献1には、溶融亜鉛めっき後めっき層の合金化処理を行わない溶融亜鉛めっき鋼板について、特許文献2には、溶融亜鉛めっき後めっき層の合金化処理を行う合金化溶融亜鉛めっき鋼板について、それぞれ、還元炉における加熱温度を水蒸気分圧で表される式で規定し露点を上げ、酸素ポテンシャルを上げることで、地鉄表層を内部酸化させる技術が開示されている。しかしながら、特許文献1、2のいずれも本発明で想定しているような塗装後耐食性の優れた特性を満たすことができない。
[1]化学成分として、質量%で、C:0.05〜0.15%、Si:0.1〜1.0%、Mn:0.5〜2.7%、Al:1.00%以下、P:0.025%以下、S:0.025%以下、Cr:0〜0.8%以下を含有し、かつ、下記式を満たし、残部がFeおよび不可避的不純物からなり、鋼板の表面に片面あたりのめっき付着量が20〜120g/m2の亜鉛めっき層を有し、該亜鉛めっき層表面の金属亜鉛露出率が20%以上80%未満であり、前記鋼板表面から5μm以内における鋼中内部酸化量が0.02g/m2以上0.1g/m2以下であることを特徴とする塗装後耐食性に優れる合金化溶融亜鉛めっき鋼板。
Si≦0.68%の場合:Cr≦−1.25Si+0.85
Si>0.68%の場合:Cr=0
ただし、Si、Crは含有量(質量%)を示す。
[2]さらに、質量%で、Mo:0.05〜1.00%、Nb:0.005〜0.050%、Ti:0.005〜0.050%、Cu:0.05〜1.00%、Ni:0.05〜1.00%、B:0.001〜0.005%の中から選ばれる1種以上の元素を含有することを特徴とする前記[1]に記載の塗装後耐食性に優れる合金化溶融亜鉛めっき鋼板。
Cは強化元素である。その効果を十分に得るためには0.05%以上必要である。一方、0.15%を超えると溶接性が劣化する。したがって、Cは0.05%以上0.15%以下とする。
Siは鋼を強化して良好な材質を得るのに有効な元素である。Siが0.1%未満では高強度化が困難である。一方、1.0%を超えるとめっき密着性が劣化し塗装後耐食性が劣化する。したがって、Siは0.1%以上1.0%以下とする。
Mnは鋼の高強度化に有効な元素である。強度を確保するためには0.5%以上含有することが必要である。一方、2.7%を超えると溶接性やめっき密着性の確保が困難になり塗装後耐食性が劣化する。したがって、Mnは0.5%以上2.7%以下とする。
Alは不可避的に混入する。しかし、1.00%を超えると溶接性が劣化する。したがって、Alは1.00%以下とする。
不可避的に含有される元素である。しかし、0.025%を超えると溶接性が劣化するだけでなく、表面品質が劣化する。また、非合金化処理時にはめっき密着性が劣化し、合金化処理時には合金化処理温度を上昇しないと所望の合金化度とすることができず、また所望の合金化度とするために合金化処理温度を上昇させると延性が劣化すると同時に合金化めっき皮膜の密着性が劣化する。このように、所望の合金化度と、良好な延性、合金化めっき皮膜を両立させることができず結果として塗装後耐食性が劣化することになる。したがって、Pは0.025%以下とする。
不可避的に含有される元素である。下限は規定しないが、多量に含有されると溶接性が劣化するため0.025%以下が好ましい。
Si≦0.68%の場合:Cr≦−1.25Si+0.85
Si>0.68%の場合:Cr=0
ただし、Si、Crは含有量(質量%)を示す。
Crは焼き入れ性を向上させて機械特性を向上させることに有効な元素である。しかし、CrはSiと複合添加すると塗装後耐食性が劣化する。裸材(冷延鋼板)としての耐食性ではこのような傾向はみられないが、合金化溶融亜鉛めっき鋼板に電着塗装するとこの傾向が発現する。原因については調査中だが、Cr、Siともに酸化しやすく、かつ酸化物が緻密な保護性形態を取ることに起因する可能性が高い。よって、Crは、Mn添加のみで焼き入れ性を確保できればかならずしも添加する必要はない。Crを添加するときは、まず、めっき密着性確保の点から0.8%以下とし、さらに、Si添加量とのバランスにおいて耐食性を確保する点から上記式を満足することとする。
20g/m2未満では耐食性確保が困難であり、120g/m2超えでは合金化処理やめっき密着性確保が困難である。
めっき層表面の金属状態の亜鉛の存在比率を規定することで塗装後耐食性が向上する。
合金化溶融亜鉛めっき鋼板の亜鉛めっき層表面にはめっき浴成分由来の薄いZn、Al酸化物層が形成されている。亜鉛めっき層表面の金属亜鉛露出率が20%未満ではZn、Al酸化物が化成処理性や塗料密着性を劣化させて塗装後耐食性を劣化させる。特に3コート後の耐食性に対して影響が大きい。亜鉛めっき層表面の金属亜鉛露出率が80%以上だと、プレス加工時にZn、Al酸化物が微細に砕けて加工性を向上させる効果が減る。
なお、亜鉛めっき層表面の金属亜鉛露出率は、AESスペクトルにおける亜鉛酸化物と金属亜鉛の強度比から評価することができる。具体的には、約992eV前後にある亜鉛酸化物のスペクトルに対して、996eV前後の亜鉛スペクトルについて、標準試料のスペクトルを元にピーク分離することで、金属亜鉛と酸化物との比を定量化し、金属亜鉛の比率を求め、これを金属亜鉛露出率とする。
本発明は高強度合金化溶融亜鉛めっき鋼板を対象とし、母材となる鋼板は高強度化のためにSiを比較的多く含む。そのためSi等を内部酸化させて鋼板表層のSi濃度を低減させることが必要である。内部酸化量が0.02g/m2より少ないとSi等の表面濃化が十分に抑制できない。内部酸化層が0.1g/m2より多いと、めっき層が腐食して地鉄が露出した後に、酸化物が生成している粒界などに塩水などが浸透しやすくなり塗装後耐食性が劣化する。
内部酸化量はめっき層を化学的に除去し、鋼板表層部の片面当たりの酸素量をインパルス炉―赤外吸収法で定量して求めることができる。めっき層除去方法は問わないが、インヒビター添加希塩酸、トリエタノールアミン(インヒビター)含有20wt%NaOH水溶液に過酸化水素水を少量添加させた溶液で除去する方法が上げられる。片面当たりの酸素量は、めっき層剥離後の試験片の鋼中酸素量から、表裏を0.1mm程度機械研削した同試験片の鋼中酸素量を差し引いて、片面単位面積当たりに換算することで定量出来る。
なお、0.02g/m2以上0.1g/m2以下の内部酸化層は、加熱炉での温度を600℃以上にすることで鋼板の酸化量を十分確保し、その酸化皮膜中の酸素を還元処理中に鋼板表層に拡散する酸化還元法、加熱帯での露点を高めに制御してオールラジアントチューブ加熱型(ART)CGLで焼鈍する方法、いずれの方法でも生成可能である。
本発明でのSi添加量は1.0%以下であるので、酸化還元処理型の直火炉(DFF)、無酸化炉(NOF)型CGLでもよいし、オールラジアントチューブ(ART)型CGLでもいい。DFF、NOF型では加熱炉での酸化条件をやや高くすると尚良いし、オールラジアントチューブ(ART)型CGLでは加熱帯露点を高めに制御してSi等の易酸化性元素を内部酸化状態にしてもよい。これらによって表面濃化が抑制されてめっき密着性、塗装後密着性が改善し結果として塗装後耐食性が向上する。
塗装後耐食性は市販の自動車用リン酸塩処理を行った後、膜厚20μmの電着塗装、膜厚30μmの中塗り、膜厚30μmの上塗りを実施した総合塗装材を作成し直径1〜2mmの鉄球50gを突出圧0.1MPaで−20℃に冷やした鋼板表面から50cm距離を置いて当て、その後塩水噴霧試験に240hr供し、塗膜疵部からの塗膜膨れが直径4mm以上のものを×(不良)、4mm未満の物を○(良好)とした。
蛍光X線Znカウント数 :ランク
0−500未満 :1(良)
500以上−1000未満 :2
1000以上−2000未満 :3
2000以上−3000未満 :4
3000以上 :5(劣)
めっき外観は目視により判断し、ムラが認められるものを×、ムラが認められないものを○と評価した。
一方、比較例は、密着性、めっき外観および塗装後耐食性のいずれか一つ以上が劣る。
Claims (2)
- 化学成分として、質量%で、C:0.05〜0.15%、Si:0.15〜1.0%、Mn:0.5〜2.7%、Al:1.00%以下、P:0.025%以下、S:0.025%以下、Cr:0〜0.8%以下を含有し、かつ、下記式を満たし、残部がFeおよび不可避的不純物からなり、
鋼板の表面に片面あたりのめっき付着量が20〜120g/m2の亜鉛めっき層を有し、該亜鉛めっき層表面の下記の方法で測定した金属亜鉛露出率が20%以上80%未満であり、
前記鋼板表面から5μm以内における鋼中内部酸化量が0.02g/m2以上0.1g/m2以下であることを特徴とする塗装後耐食性に優れる合金化溶融亜鉛めっき鋼板。
Si≦0.68%の場合:Cr≦−1.25Si+0.85
Si>0.68%の場合:Cr=0
ただし、Si、Crは含有量(質量%)を示す。
(方法)
約992eV前後にある亜鉛酸化物のスペクトルに対して、996eV前後の亜鉛スペクトルについて、標準試料のスペクトルを元にピーク分離することで、金属亜鉛と酸化物との比を定量化し、金属亜鉛の比率を求め、これを金属亜鉛露出率とする。 - さらに、質量%で、Mo:0.05〜1.00%、Nb:0.005〜0.050%、Cu:0.05〜1.00%、Ni:0.05〜1.00%、B:0.001〜0.005%の中から選ばれる1種以上の元素を含有することを特徴とする請求項1に記載の塗装後耐食性に優れる合金化溶融亜鉛めっき鋼板。
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EP12834811.7A EP2762599B1 (en) | 2011-09-26 | 2012-09-20 | Alloyed hot-dipped galvanized steel sheet having excellent corrosion resistance after coating |
CN201280046968.7A CN103827340B (zh) | 2011-09-26 | 2012-09-20 | 涂装后耐腐蚀性优良的合金化热镀锌钢板 |
PCT/JP2012/005958 WO2013046601A1 (ja) | 2011-09-26 | 2012-09-20 | 塗装後耐食性に優れる合金化溶融亜鉛めっき鋼板 |
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JP5593771B2 (ja) * | 2009-03-31 | 2014-09-24 | Jfeスチール株式会社 | 高強度溶融亜鉛めっき鋼板の製造方法 |
JP5434537B2 (ja) * | 2009-12-03 | 2014-03-05 | 新日鐵住金株式会社 | 溶接性に優れた高Si含有合金化溶融めっき鋼板およびその製造方法 |
JP5906628B2 (ja) * | 2011-09-20 | 2016-04-20 | Jfeスチール株式会社 | 塗装後耐食性に優れる合金化溶融亜鉛めっき鋼板 |
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CN103827340A (zh) | 2014-05-28 |
CN103827340B (zh) | 2016-03-02 |
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