JP7312142B2 - 溶接性及び加工部耐食性に優れた亜鉛合金めっき鋼材及びその製造方法 - Google Patents
溶接性及び加工部耐食性に優れた亜鉛合金めっき鋼材及びその製造方法 Download PDFInfo
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- JP7312142B2 JP7312142B2 JP2020092037A JP2020092037A JP7312142B2 JP 7312142 B2 JP7312142 B2 JP 7312142B2 JP 2020092037 A JP2020092037 A JP 2020092037A JP 2020092037 A JP2020092037 A JP 2020092037A JP 7312142 B2 JP7312142 B2 JP 7312142B2
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- zinc alloy
- plated steel
- layer
- base iron
- interfacial layer
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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
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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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
- B32B15/012—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 aluminium or an aluminium alloy
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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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
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- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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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
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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
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Description
したがって、亜鉛合金めっき層内のMgの含有量の下限は、0.1重量%であることが好ましく、0.5重量%であることがより好ましく、0.8重量%であることがさらに好ましい。但し、Mgの含有量が高すぎる場合は、めっき浴内にMg酸化によるドロスが発生するという問題がある。したがって、亜鉛合金めっき層内のMgの含有量の上限は、5.0重量%であることが好ましく、3.0重量%であることがより好ましく、2.0重量%であることがさらに好ましい。
上部界面層の面積率が10%未満の場合は、上部界面層の面積が小さすぎるため、亜鉛合金めっき鋼材の溶接性及び加工部耐食性が劣化するおそれがある。一方、90%を超えると、加工時の脆性が原因でクラックが発生するおそれがある。
素地鉄を設けた後、上記素地鉄の表面活性化を行う。本段階は、素地鉄と亜鉛合金めっき層の間に二重構造のFe-Al系合金層をより容易に形成するために行う段階である。
素地鉄を熱処理してその表面に表面酸化物層を形成する。但し、本段階は、素地鉄が、重量%で、Si、Mn、及びNiからなる群より選択された1種または2種以上を合計0.1%以上含む場合、上記Si、Mn、及びNiの表面濃化を誘導して、後工程により形成される界面層内に上記Si、Mn、及びNiが十分に固溶されるようにするためのものである。但し、本段階は必須ではない。
表面活性化した素地鉄、または表面が活性化し、表面酸化物層が形成された素地鉄を、重量%で、Al:0.1~5.0%、Mg:0.1~5.0%、残部Zn及び不可避不純物を含む亜鉛合金めっき浴に浸漬し、めっきを行って亜鉛合金めっき鋼材を得る。
めっき用試験片として厚さ0.8mm、幅100mm、及び長さ200mmの低炭素冷延鋼板を設けた後、その表面をプラズマ処理して表面活性化した。ここで、表面活性化した素地鉄のRa、Rz、及びRmaxは下記表1に示した。その後、上記表面活性化した素地鉄を下記表1の組成を有する亜鉛合金めっき浴に浸漬して亜鉛合金めっき鋼材を製造した。続いて、上記亜鉛合金めっき鋼材をガスワイピングしてめっき付着量を片面当たり70g/m2に調節し、10℃/secの平均冷却速度で常温(約25℃)まで冷却した。
先端径6mmであるCu-Cr電極を用いて溶接電流7kAを流し、加圧力2.1kNで11 Cycles(ここで、1 Cycleとは1/60秒を意味する、下同)の通電時間及び11 Cyclesの保持時間の条件で溶接を行った。それぞれの実施例において、合計5つの試験片を製作し、5つの試験片で発生したすべてのLME割れの長さを測定し、平均LME割れの長さ及び最高LME割れの長さを導出した。その結果、平均LME割れの長さが20μm以下の場合を「合格」、20μmを超えた場合を「不合格」と評価した。また、最高LME割れの長さが100μm以下の場合を「合格」、100μmを超えた場合を「不合格」と評価した。
それぞれのめっき鋼材を180℃曲げ加工(0T曲げ)した後、曲げ加した個々のめっき鋼板を塩水噴霧試験機に装入し、国際規格(ASTM B117-11)により赤青の発生時間を測定した。この際、塩水5%(温度35℃、pH 6.8)を用いており、1時間当たり2ml/80cm2の塩水を噴霧した。赤青の発生時間が500時間以上の場合を「合格」、500時間未満の場合を「不合格」と評価した。
プラズマ処理条件による上部界面層の面積率などの変化、及びそれに伴う亜鉛合金めっき鋼材の溶接性及び加工部耐食性を評価するために、他の条件は実施例1と同一にし、めっき浴の組成(Al:1.4重量%、Mg:1.4重量%、及び残部Zn)及びプラズマ処理条件だけを異ならせて亜鉛合金めっき鋼材を製造した。それぞれの例におけるプラズマ処理条件は表3に示した。
Claims (9)
- 素地鉄及び亜鉛合金めっき層を含む亜鉛合金めっき鋼材であって、
前記亜鉛合金めっき層は、重量%で、Al:0.1~5.0%、Mg:0.1~5.0%、残部Zn及び不可避不純物を含み、
前記素地鉄と前記亜鉛合金めっき層の間には、前記素地鉄上に形成され、緻密な構造を有する下部界面層と、前記下部界面層上に形成され、ネットワーク型またはアイランド型構造を有し、厚さが75~450nmである上部界面層と、を含み、
前記下部界面層に対する前記上部界面層の面積率は10~70%であり、
前記上部界面層及び前記下部界面層は、FeAl系合金を含み、前記FeAl系合金は、Fe2Al5、FeAl3、及びFeAlからなる群より選択された1種または2種以上であり、
前記上部界面層及び前記下部界面層は、互いに異なる組成を有し、
前記下部界面層の厚さは500nm以下(0nmを除く)である、亜鉛合金めっき鋼材。 - 前記下部界面層に対する前記上部界面層の面積率は40~70%である、請求項1に記載の亜鉛合金めっき鋼材。
- 前記上部界面層は、重量%で、Al:15~80%、Fe:20~85%、及びZn:10%以下(0%を含む)を含む、請求項1又は2に記載の亜鉛合金めっき鋼材。
- 前記素地鉄は、重量%で、Si、Mn、及びNiからなる群より選択された1種または2種以上を合計0.1%以上含み、
前記上部界面層及び下部界面層は、重量%で、Si、Mn、及びNiからなる群より選択された1種または2種以上を0.001%以上さらに含む、請求項1から3のいずれか1項に記載の亜鉛合金めっき鋼材。 - 素地鉄を設ける段階と、
前記素地鉄の中心線平均粗さ(Ra)が0.8~1.2μmであり、10点平均粗さ(Rz)が7.5~15.5μmであり、最大高さ粗さ(Rmax)が8~16.5μmとなるように、前記素地鉄を不活性ガス雰囲気でRF電源150~200Wの条件下においてプラズマ処理を用いて表面活性化する段階と、
前記表面活性化した素地鉄を、重量%で、Al:0.1~5.0%、Mg:0.1~5.0%、残部Zn及び不可避不純物を含む亜鉛合金めっき浴に浸漬し、めっきを行って亜鉛合金めっき鋼材を得る段階と、
前記亜鉛合金めっき鋼材をガスワイピングしてから冷却する段階と、を含み、
前記冷却する段階後の前記亜鉛合金めっき鋼材は、前記素地鉄と前記亜鉛合金めっき層の間に、前記素地鉄上に形成され、緻密な構造を有する下部界面層と、前記下部界面層上に形成され、ネットワーク型またはアイランド型構造を有する上部界面層とを含み、前記下部界面層の面積に対する前記上部界面層の面積率は10~70%であり、前記上部界面層及び前記下部界面層は、互いに異なる組成を有する、亜鉛合金めっき鋼材の製造方法。 - 前記不活性ガス雰囲気は、窒素ガス雰囲気、アルゴンガス雰囲気、及び窒素とアルゴンの混合ガス雰囲気のいずれかである、請求項5に記載の亜鉛合金めっき鋼材の製造方法。
- 前記素地鉄は、重量%で、Si、Mn、及びNiからなる群より選択された1種または2種以上を合計0.1%以上含む、請求項5又は6に記載の亜鉛合金めっき鋼材の製造方法。
- 前記素地鉄を表面活性化する前に、前記素地鉄を熱処理して、表面酸化物層を形成する段階をさらに含む、請求項7に記載の亜鉛合金めっき鋼材の製造方法。
- 前記熱処理時の熱処理温度は700~900℃である、請求項8に記載の亜鉛合金めっき鋼材の製造方法。
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EP3561138B1 (en) | 2023-11-15 |
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EP3239347B1 (en) | 2019-08-07 |
US20200157672A1 (en) | 2020-05-21 |
US10584407B2 (en) | 2020-03-10 |
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