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Zn中間層對TRIP鋼Zn-Mg鍍層結合強度和耐蝕性的影響

2019-11-22 00:48:10 hualin

韓國航空大學2018年在ISIJ International 發表的論文《Effect of a Zn Interlayer on the Adhesion Strength and Corrosion Resistance of Zn–Mg Coated TRIP Steel》。

使用電磁加熱沉積(ji)工(gong)藝(EMHD)在(zai)高(gao)強鋼上合成(cheng)(cheng)(cheng)了Mg成(cheng)(cheng)(cheng)分范圍為(wei)5 wt.%至15 wt.%的Zn-Mg涂(tu)層(ceng)(ceng)(ceng)(ceng),研(yan)究了厚度(du)(du)為(wei)1μm的Zn中間(jian)(jian)(jian)(jian)層(ceng)(ceng)(ceng)(ceng)對涂(tu)層(ceng)(ceng)(ceng)(ceng)的成(cheng)(cheng)(cheng)形(xing)(xing)性(xing)和附(fu)著(zhu)(zhu)力的影響(xiang)。與不帶鋅(xin)中間(jian)(jian)(jian)(jian)層(ceng)(ceng)(ceng)(ceng)的Zn-Mg涂(tu)層(ceng)(ceng)(ceng)(ceng)相比,具有(you)(you)Zn中間(jian)(jian)(jian)(jian)層(ceng)(ceng)(ceng)(ceng)的Zn-Mg涂(tu)層(ceng)(ceng)(ceng)(ceng)在(zai)微觀結(jie)(jie)構、晶體結(jie)(jie)構和耐(nai)腐(fu)蝕性(xing)方面幾(ji)乎沒(mei)有(you)(you)差(cha)異(yi)。但(dan)是,鋅(xin)中間(jian)(jian)(jian)(jian)層(ceng)(ceng)(ceng)(ceng)有(you)(you)助(zhu)于顯(xian)著(zhu)(zhu)改善Zn-Mg涂(tu)層(ceng)(ceng)(ceng)(ceng)的成(cheng)(cheng)(cheng)形(xing)(xing)性(xing)和附(fu)著(zhu)(zhu)力。帶有(you)(you)鋅(xin)中間(jian)(jian)(jian)(jian)層(ceng)(ceng)(ceng)(ceng)的Zn-Mg涂(tu)層(ceng)(ceng)(ceng)(ceng)變形(xing)(xing)后的剝(bo)離面積(ji)大大減小(xiao),并且搭(da)接(jie)剪切試驗的結(jie)(jie)果表明,帶有(you)(you)Zn中間(jian)(jian)(jian)(jian)層(ceng)(ceng)(ceng)(ceng)的Zn-Mg涂(tu)層(ceng)(ceng)(ceng)(ceng)的最大粘附(fu)強度(du)(du)大約是沒(mei)有(you)(you)Zn中間(jian)(jian)(jian)(jian)層(ceng)(ceng)(ceng)(ceng)的最大粘附(fu)強度(du)(du)的兩倍。 具有(you)(you)最大附(fu)著(zhu)(zhu)強度(du)(du)的Mg含量(liang)為(wei)15 wt.%的Zn / Zn-Mg涂(tu)層(ceng)(ceng)(ceng)(ceng)顯(xian)示出(chu)最佳的耐(nai)腐(fu)蝕性(xing),經測(ce)量(liang),其略高(gao)于10 MPa,有(you)(you)待對具有(you)(you)更(geng)高(gao)Mg含量(liang)的Zn-Mg涂(tu)層(ceng)(ceng)(ceng)(ceng)進行研(yan)究,使其附(fu)著(zhu)(zhu)強度(du)(du)必須超過20 MPa。

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Electro-magnetic heating deposition (EMHD) 的(de)沉積速率(lv)為1μm/min,是傳統濺射速率(lv)的(de)15倍。中間鋅層厚1μm,Zn-Mg層厚2μm。


1. 微(wei)觀組織結構

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Zn-5wt.%的Mg涂(tu)層(ceng)呈現出多(duo)孔微結構(gou)(gou),而Zn-10wt.%的Mg涂(tu)層(ceng)顯示(shi)出柱狀(zhuang)結構(gou)(gou)。具(ju)有15 wt.%的高鎂含量(liang)的Zn-Mg涂(tu)層(ceng)顯示(shi)出無特征(zheng)的結構(gou)(gou),該無特征(zheng)的微結構(gou)(gou)被確定為非晶結構(gou)(gou)。

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在(zai)(zai)Zn-5 wt.%Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)(de)XRD結果中,可以清(qing)楚地觀察(cha)到(dao)(dao)Zn相(xiang)的(de)(de)(de)(de)(de)(de)峰,而(er)由(you)(you)于(yu)(yu)Mg含量低,未檢測到(dao)(dao)其(qi)他相(xiang),表明為(Zn)固溶(rong)體(ti)(ti)(ti)。在(zai)(zai)Zn-10wt.%Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)中,觀察(cha)到(dao)(dao)來(lai)自金屬(shu)間(jian)相(xiang)如Mg2Zn11和(he)MgZn2的(de)(de)(de)(de)(de)(de)峰。然而(er),Zn-15wt.%的(de)(de)(de)(de)(de)(de)Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)(de)XRD圖(tu)譜表明涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)(de)晶(jing)體(ti)(ti)(ti)結構(gou)從晶(jing)體(ti)(ti)(ti)變為非(fei)晶(jing)。先前(qian)已經有(you)文獻報(bao)(bao)道(dao)了(le)高鎂含量的(de)(de)(de)(de)(de)(de)鋅鎂鍍層(ceng)(ceng)(ceng)(ceng)中無(wu)定形相(xiang)的(de)(de)(de)(de)(de)(de)形成。在(zai)(zai)Mg含量為0-15wt%的(de)(de)(de)(de)(de)(de)鎂鋅雙(shuang)元系統中,各(ge)種(zhong)金屬(shu)間(jian)相(xiang)(如Mg2Zn11和(he)MgZn2)會(hui)成為平(ping)衡相(xiang)。。但是,在(zai)(zai)PVD工藝(yi)中,Mg在(zai)(zai)(Zn)中的(de)(de)(de)(de)(de)(de)固溶(rong)度(du)以非(fei)常高的(de)(de)(de)(de)(de)(de)冷(leng)卻速(su)率(約1012 K/s)得(de)以擴展。Dai 等人還報(bao)(bao)道(dao)了(le)當Mg含量超(chao)過15 wt.%時,由(you)(you)于(yu)(yu)Mg和(he)Zn原子(zi)之間(jian)原子(zi)尺寸的(de)(de)(de)(de)(de)(de)差異,(Zn)的(de)(de)(de)(de)(de)(de)晶(jing)體(ti)(ti)(ti)結構(gou)能(neng)夠轉變為非(fei)晶(jing)態。如圖(tu)3(b)所示,在(zai)(zai)所有(you)帶有(you)Zn夾(jia)層(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)(de)Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)中,出(chu)(chu)現(xian)Zn峰的(de)(de)(de)(de)(de)(de)強度(du),這(zhe)是由(you)(you)于(yu)(yu)結晶(jing)Zn夾(jia)層(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)(de)影響(xiang)。在(zai)(zai)使用Zn / Zn-10 wt.%的(de)(de)(de)(de)(de)(de)Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)(de)情況下(xia),存在(zai)(zai)與(yu)Zn-10 wt.%Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)相(xiang)同的(de)(de)(de)(de)(de)(de)Zn-Mg合金金屬(shu)間(jian)峰,例(li)如Mg2Zn11(210),(222),(321), (410),(411)和(he)MgZn2(112),(104)。在(zai)(zai)Zn / Zn-15wt.%的(de)(de)(de)(de)(de)(de)Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)中,由(you)(you)于(yu)(yu)Zn-15wt.%的(de)(de)(de)(de)(de)(de)Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)(de)非(fei)晶(jing)態結構(gou),僅觀察(cha)到(dao)(dao)來(lai)自Zn中間(jian)層(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)(de)峰。除了(le)由(you)(you)于(yu)(yu)Zn中間(jian)層(ceng)(ceng)(ceng)(ceng)而(er)出(chu)(chu)現(xian)的(de)(de)(de)(de)(de)(de)Zn峰,插入Zn中間(jian)層(ceng)(ceng)(ceng)(ceng)不會(hui)帶來(lai)其(qi)他明顯差異。


2. 耐蝕性

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Zn-5wt.%的(de)(de)(de)Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)腐(fu)蝕(shi)電(dian)(dian)流密(mi)(mi)度(du)為6.96μA/ cm 2,并(bing)且隨著(zhu)涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)Mg含(han)量(liang)增加(jia)(jia)(jia)(jia)至(zhi)15wt.%,腐(fu)蝕(shi)電(dian)(dian)流密(mi)(mi)度(du)降低至(zhi)1.49μA/ cm 2。Zn-5%Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)腐(fu)蝕(shi)電(dian)(dian)位(wei)為-1.33VSCE,隨著(zhu)Mg含(han)量(liang)的(de)(de)(de)增加(jia)(jia)(jia)(jia),腐(fu)蝕(shi)電(dian)(dian)位(wei)也(ye)增加(jia)(jia)(jia)(jia)至(zhi)-0.76VSCE。鎂含(han)量(liang)增加(jia)(jia)(jia)(jia)的(de)(de)(de)鋅(xin)鎂涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)變得更加(jia)(jia)(jia)(jia)穩定,腐(fu)蝕(shi)速率降低。這些結(jie)果證實(shi)了(le)先前報(bao)(bao)道的(de)(de)(de)結(jie)果,即(ji)隨著(zhu)涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)中Mg含(han)量(liang)的(de)(de)(de)增加(jia)(jia)(jia)(jia),Zn–Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)耐(nai)(nai)蝕(shi)性(xing)增加(jia)(jia)(jia)(jia),這可能(neng)歸因(yin)于涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)微觀(guan)結(jie)構(gou)(gou)從(cong)(cong)多孔結(jie)構(gou)(gou)轉變為致密(mi)(mi)無(wu)特征的(de)(de)(de)無(wu)定形(xing)結(jie)構(gou)(gou)。Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)中耐(nai)(nai)蝕(shi)性(xing)隨Mg含(han)量(liang)的(de)(de)(de)增加(jia)(jia)(jia)(jia)可以(yi)用致密(mi)(mi)的(de)(de)(de)微觀(guan)結(jie)構(gou)(gou)和(he)金屬間相(xiang)(xiang)(xiang)(xiang)來解釋,如(ru)圖2和(he)3所(suo)示。據報(bao)(bao)道,與純Zn固溶體相(xiang)(xiang)(xiang)(xiang)相(xiang)(xiang)(xiang)(xiang)比(bi),單一(yi)(yi)金屬間相(xiang)(xiang)(xiang)(xiang)Mg2Zn11和(he)MgZn2改善(shan)了(le)腐(fu)蝕(shi)性(xing)能(neng),并(bing)且與Zn-5 wt%Mg相(xiang)(xiang)(xiang)(xiang)比(bi),在Zn-10 wt%Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)中的(de)(de)(de)這些相(xiang)(xiang)(xiang)(xiang)改善(shan)了(le)耐(nai)(nai)蝕(shi)性(xing)。由于涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)微觀(guan)結(jie)構(gou)(gou)是(shi)一(yi)(yi)個決定涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)腐(fu)蝕(shi)防護(hu)能(neng)力的(de)(de)(de)參數,它比(bi)Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)中的(de)(de)(de)金屬間化合(he)物更大(da),含(han)15 wt.%Mg的(de)(de)(de)Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)具有(you)(you)無(wu)定形(xing)的(de)(de)(de)顯(xian)(xian)微組織顯(xian)(xian)示出(chu)最(zui)佳的(de)(de)(de)耐(nai)(nai)腐(fu)蝕(shi)性(xing)。圖4(b)顯(xian)(xian)示Zn / Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)具有(you)(you)與Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)相(xiang)(xiang)(xiang)(xiang)似的(de)(de)(de)耐(nai)(nai)蝕(shi)性(xing),因(yin)為它們具有(you)(you)相(xiang)(xiang)(xiang)(xiang)同的(de)(de)(de)微觀(guan)結(jie)構(gou)(gou)和(he)金屬間相(xiang)(xiang)(xiang)(xiang)。Zn / Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)腐(fu)蝕(shi)電(dian)(dian)流密(mi)(mi)度(du)從(cong)(cong)5.89μA/ cm2變為1.55μA/ cm2,當Mg含(han)量(liang)從(cong)(cong)5 wt.%增加(jia)(jia)(jia)(jia)到15 wt。時,腐(fu)蝕(shi)電(dian)(dian)位(wei)從(cong)(cong)-1.39 VSCE增加(jia)(jia)(jia)(jia)到-0.59 VSCE。%。在基材和(he)Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)之間插入Zn中間層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)并(bing)沒有(you)(you)顯(xian)(xian)示出(chu)對(dui)Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)耐(nai)(nai)腐(fu)蝕(shi)性(xing)的(de)(de)(de)有(you)(you)害影響,但實(shi)際上,耐(nai)(nai)腐(fu)蝕(shi)性(xing)能(neng)略有(you)(you)提高(gao),如(ru)表(biao)1所(suo)示,這可以(yi)歸因(yin)于Zn / Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)(ceng)中附加(jia)(jia)(jia)(jia)的(de)(de)(de)相(xiang)(xiang)(xiang)(xiang)間邊界效應(ying)(additional interphase boundary effect )。


3. 結合強度

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全(quan)文(wen)結論(lun):Mg組(zu)成范(fan)圍從(cong)5 %到15 %的(de)(de)(de)(de)(de)Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)是通(tong)(tong)過(guo)EMHD工藝以1μ/ min的(de)(de)(de)(de)(de)高沉(chen)積速(su)率沉(chen)積的(de)(de)(de)(de)(de),并且在(zai)基(ji)底和(he)(he)基(ji)底之間沉(chen)積了厚度(du)(du)(du)為(wei)1μm的(de)(de)(de)(de)(de)Zn中間層(ceng)(ceng)(ceng)(ceng)(ceng)。Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)可(ke)改善涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)可(ke)成形性(xing)(xing)和(he)(he)附(fu)(fu)著(zhu)力(li)。當Zn–Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)Mg組(zu)成從(cong)5%增加到15%時,涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)微(wei)觀結構(gou)(gou)從(cong)多孔結構(gou)(gou)變為(wei)無(wu)特征結構(gou)(gou),而(er)晶(jing)體(ti)結構(gou)(gou)從(cong)晶(jing)體(ti)變為(wei)非晶(jing)結構(gou)(gou)。Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)耐(nai)(nai)蝕(shi)(shi)性(xing)(xing)隨(sui)Mg含(han)量的(de)(de)(de)(de)(de)增加而(er)增加。Zn / Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)與Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)具(ju)有相似的(de)(de)(de)(de)(de)化(hua)學組(zu)成,晶(jing)體(ti)結構(gou)(gou)和(he)(he)耐(nai)(nai)蝕(shi)(shi)性(xing)(xing),即使在(zai)沉(chen)積Zn中間層(ceng)(ceng)(ceng)(ceng)(ceng)時也是如此。附(fu)(fu)著(zhu)力(li)評(ping)估結果表明,Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)附(fu)(fu)著(zhu)力(li)和(he)(he)可(ke)成形性(xing)(xing)可(ke)通(tong)(tong)過(guo)Zn中間層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)沉(chen)積得到大幅度(du)(du)(du)改善,并且Zn / Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)最(zui)(zui)(zui)大附(fu)(fu)著(zhu)力(li)約(yue)為(wei)Zn-Mg的(de)(de)(de)(de)(de)兩倍。搭接(jie)剪(jian)切(qie)試驗中的(de)(de)(de)(de)(de)鎂涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)。然(ran)而(er),具(ju)有15%(重量)的(de)(de)(de)(de)(de)Mg的(de)(de)(de)(de)(de)Zn / Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)最(zui)(zui)(zui)大粘(zhan)附(fu)(fu)強(qiang)度(du)(du)(du)顯示出(chu)最(zui)(zui)(zui)佳的(de)(de)(de)(de)(de)耐(nai)(nai)腐蝕(shi)(shi)性(xing)(xing),據(ju)測得略(lve)高于(yu)10 MPa,這(zhe)遠低于(yu)汽(qi)車應用所需(xu)的(de)(de)(de)(de)(de)粘(zhan)附(fu)(fu)強(qiang)度(du)(du)(du)。根(gen)據(ju)先前報道的(de)(de)(de)(de)(de)論(lun)文(wen),通(tong)(tong)過(guo)傳統的(de)(de)(de)(de)(de)純鋅電鍍鋅(EG)涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)和(he)(he)熱浸鍍鋅(GI)涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)在(zai)鋼(gang)上(shang)的(de)(de)(de)(de)(de)搭接(jie)剪(jian)切(qie)試驗,其粘(zhan)合強(qiang)度(du)(du)(du)顯示為(wei)約(yue)16至19 MPa.因此,需(xu)要進行(xing)更多的(de)(de)(de)(de)(de)研究為(wei)了在(zai)工業(ye)上(shang)通(tong)(tong)過(guo)EMH PVD工藝用Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)代替EG和(he)(he)GI涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng),仍然(ran)需(xu)要增加含(han)鎂量獲得超過(guo)20 MPa的(de)(de)(de)(de)(de)Zn-Mg涂(tu)(tu)層(ceng)(ceng)(ceng)(ceng)(ceng)的(de)(de)(de)(de)(de)附(fu)(fu)著(zhu)強(qiang)度(du)(du)(du)。