圖(tu)3.7(a)~(d)為(wei)鐵(tie)素(su)(su)體(ti)(ti)(ti)和(he)奧(ao)(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni元素(su)(su)含(han)(han)(han)(han)量(liang)(liang)與固溶(rong)(rong)(rong)(rong)溫(wen)(wen)度的(de)(de)(de)關系圖(tu)。圖(tu)3.7(a)~(d)證實了鐵(tie)素(su)(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Cr和(he)Mo含(han)(han)(han)(han)量(liang)(liang)更高(gao)(gao),而奧(ao)(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Ni和(he)Mn含(han)(han)(han)(han)量(liang)(liang)更高(gao)(gao)。從(cong)圖(tu)中(zhong)(zhong)可看出,鐵(tie)素(su)(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Cr含(han)(han)(han)(han)量(liang)(liang)為(wei)23.77%~25.16%,比(bi)奧(ao)(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)Cr含(han)(han)(han)(han)量(liang)(liang)高(gao)(gao)2%左右(you);鐵(tie)素(su)(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)Mo含(han)(han)(han)(han)量(liang)(liang)為(wei)3.86%~4.37%,比(bi)奧(ao)(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Mo含(han)(han)(han)(han)量(liang)(liang)高(gao)(gao)1.7%左右(you);奧(ao)(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Ni含(han)(han)(han)(han)量(liang)(liang)為(wei)5.42%、6.7%,比(bi)鐵(tie)素(su)(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Ni含(han)(han)(han)(han)量(liang)(liang)高(gao)(gao)2%;當固溶(rong)(rong)(rong)(rong)處理溫(wen)(wen)度為(wei)1050℃時(shi)(shi),鐵(tie)素(su)(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Cr、Mo和(he)Ni含(han)(han)(han)(han)量(liang)(liang)分別為(wei)23.77%、3.97%、4.24%,奧(ao)(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Cr、Mo和(he)Ni含(han)(han)(han)(han)量(liang)(liang)分別為(wei)23.53%、2.63%、5.42%.可見在1050℃溫(wen)(wen)度下進行固溶(rong)(rong)(rong)(rong)時(shi)(shi),兩(liang)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni含(han)(han)(han)(han)量(liang)(liang)差(cha)異(yi)(yi)最(zui)小(xiao),此時(shi)(shi)鐵(tie)素(su)(su)體(ti)(ti)(ti)含(han)(han)(han)(han)量(liang)(liang)為(wei)51.9%,奧(ao)(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)含(han)(han)(han)(han)量(liang)(liang)為(wei)48.1%.當固溶(rong)(rong)(rong)(rong)溫(wen)(wen)度改變時(shi)(shi),鐵(tie)素(su)(su)體(ti)(ti)(ti)/奧(ao)(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)兩(liang)相(xiang)(xiang)(xiang)比(bi)例相(xiang)(xiang)(xiang)差(cha)變大(da),且兩(liang)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni含(han)(han)(han)(han)量(liang)(liang)差(cha)異(yi)(yi)也變大(da)。當固溶(rong)(rong)(rong)(rong)溫(wen)(wen)度為(wei)1000℃,兩(liang)相(xiang)(xiang)(xiang)中(zhong)(zhong)Cr為(wei)3.69%、Mo為(wei)1.51%、Ni為(wei)3.37%;當固溶(rong)(rong)(rong)(rong)溫(wen)(wen)度為(wei)1150℃時(shi)(shi),兩(liang)相(xiang)(xiang)(xiang)中(zhong)(zhong)Cr為(wei)2.29%、Mo為(wei)1.34%、Ni為(wei)2.09%,可見1000℃固溶(rong)(rong)(rong)(rong)試樣的(de)(de)(de)兩(liang)相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni元素(su)(su)含(han)(han)(han)(han)量(liang)(liang)差(cha)大(da)于1150℃固溶(rong)(rong)(rong)(rong)試樣的(de)(de)(de)兩(liang)相(xiang)(xiang)(xiang)中(zhong)(zhong)Cr、Mo、Ni元素(su)(su)含(han)(han)(han)(han)量(liang)(liang)差(cha)。

由(you)公式“PREN.=[Cr]+3.3[Mo]”計算(suan)鐵素體的(de)PREN值,由(you)公式“PREN,=[Cr]+3.3[Mo]+16[N]-[Mn]”計算(suan)奧氏體的(de)PREN值,可(ke)得PREN值與固溶(rong)溫(wen)度的(de)關系圖(tu),如圖(tu)3.7(e)所示。從圖(tu)3.7(e)可(ke)看出,在不同(tong)固溶(rong)狀態下,兩(liang)相的(de)PREN值有所不同(tong),但(dan)PRENa>PRENy.當固溶(rong)溫(wen)度為(wei)1050℃時,PREN.最小、PREN,最大,分(fen)別為(wei)36.9和30.6,兩(liang)者相差最小。
圖(tu)3.8為不同(tong)固(gu)溶試樣的(de)(de)極化(hua)曲線。可見,在自腐蝕電(dian)(dian)(dian)位(wei)(wei)(wei)下,材料開始發生鈍化(hua);當(dang)極化(hua)電(dian)(dian)(dian)位(wei)(wei)(wei)升高(gao)到一定值(zhi)時,不同(tong)固(gu)溶的(de)(de)材料都發生點蝕,電(dian)(dian)(dian)流密度(du)急劇增大。根據(ju)GB 4334.9-1984中電(dian)(dian)(dian)流密度(du)為0.1mA/c㎡所對應的(de)(de)電(dian)(dian)(dian)位(wei)(wei)(wei)為點蝕電(dian)(dian)(dian)位(wei)(wei)(wei)和Tafel擬合(he),分別(bie)得(de)到點蝕電(dian)(dian)(dian)位(wei)(wei)(wei)、自腐蝕電(dian)(dian)(dian)流密度(du)與固(gu)溶溫度(du)的(de)(de)關系圖(tu),如圖(tu)3.11(a)所示。

圖(tu)(tu)3.9(a)、(b)分(fen)別為(wei)不(bu)(bu)同固(gu)溶試樣(yang)的(de)Nyquist 圖(tu)(tu)和Bode圖(tu)(tu)。從圖(tu)(tu)3.9(a)可(ke)見(jian),試樣(yang)在(zai)(zai)低頻(pin)(pin)(pin)和高(gao)頻(pin)(pin)(pin)區分(fen)別存在(zai)(zai)一(yi)個(ge)容抗(kang)(kang)弧。從圖(tu)(tu)3.9(b)可(ke)見(jian),試樣(yang)在(zai)(zai)低頻(pin)(pin)(pin)和高(gao)頻(pin)(pin)(pin)處(chu)分(fen)別存在(zai)(zai)一(yi)個(ge)時(shi)間(jian)(jian)常數(shu)。根據(ju)曹(cao)楚南(nan)的(de)《電(dian)(dian)化學(xue)阻(zu)抗(kang)(kang)譜導(dao)論》可(ke)知。雙相(xiang)不(bu)(bu)銹鋼在(zai)(zai)NaCl溶液中(zhong)的(de)阻(zu)抗(kang)(kang)譜中(zhong)存在(zai)(zai)兩個(ge)時(shi)間(jian)(jian)常數(shu),常以圖(tu)(tu)3.10所示的(de)等(deng)效電(dian)(dian)路(R1為(wei)電(dian)(dian)荷轉移(yi)電(dian)(dian)阻(zu),R2為(wei)鈍化膜(mo)電(dian)(dian)阻(zu))進行阻(zu)抗(kang)(kang)擬合。經阻(zu)抗(kang)(kang)擬合,得(de)到(dao)鈍化膜(mo)電(dian)(dian)阻(zu)、電(dian)(dian)荷轉移(yi)電(dian)(dian)阻(zu)與固(gu)溶處(chu)理溫度的(de)關(guan)系圖(tu)(tu),如圖(tu)(tu)3.11(b)所示。

從圖3.11(a)可見,1050℃固溶試樣的點蝕電位最高,約為0.89V,且1050℃固溶試樣的自腐蝕電流密度最低,約為2.34×10-6A/c㎡,說明該狀態下試樣的耐點蝕性能最好。由圖3.11(b)可知,1050℃固溶試樣的鈍化膜電阻值最高,約為1300Ω,且其電荷轉移電阻值也最高,約為9500Ω,說明該狀態下試樣的鈍化膜較穩定,耐點蝕性能較好。
圖3.12為不同固溶的2205雙相不銹鋼(gang)極化后的點蝕形貌圖,圖中黑色為蝕坑,深色為鐵素體,淡色為奧氏體。從圖3.12可見,四種固溶試樣的點蝕都發生于鐵素體與奧氏體相界面處,且易向鐵素體相中長大。當固溶溫度為1050℃時,試樣的點蝕尺寸最小,點蝕敏感性最低。

通(tong)過計算(suan)得到(dao)不(bu)同相(xiang)比例(li)(li)下的(de)(de)(de)鐵素體PREN值和(he)奧氏體PREN值,可(ke)(ke)(ke)見(jian)不(bu)同相(xiang)比例(li)(li)下的(de)(de)(de)PREN.都大(da)于PREN,.雙(shuang)相(xiang)不(bu)銹鋼(gang)的(de)(de)(de)耐(nai)點(dian)(dian)蝕(shi)性能可(ke)(ke)(ke)通(tong)過點(dian)(dian)蝕(shi)電位衡量。點(dian)(dian)蝕(shi)電位越高,耐(nai)點(dian)(dian)獨(du)性能越好(hao)。前人認為雙(shuang)相(xiang)不(bu)銹鋼(gang)的(de)(de)(de)耐(nai)點(dian)(dian)蝕(shi)性能由B能N值較區的(de)(de)(de)相(xiang)決定,且PEN值越高,耐(nai)點(dian)(dian)蝕(shi)性能越好(hao),從圖(tu)3.71e)可(ke)(ke)(ke)矩,不(bu)同海溶試(shi)(shi)樣(yang)的(de)(de)(de)PREN.都大(da)于PREN,,當固溶溫度為1050℃時(shi),PHEN,最大(da),材(cai)料的(de)(de)(de)耐(nai)點(dian)(dian)蝕(shi)性能應最好(hao)。從圖(tu)3.11(a)、(b)可(ke)(ke)(ke)知(zhi)(zhi),1050℃固溶試(shi)(shi)樣(yang)的(de)(de)(de)點(dian)(dian)蝕(shi)電位最高,鈍(dun)化膜阻抗值最大(da),電荷轉(zhuan)移電阻值最商;且從圖(tu)3.12(b)可(ke)(ke)(ke)見(jian),1050℃固溶試(shi)(shi)樣(yang)的(de)(de)(de)點(dian)(dian)蝕(shi)坑尺寸最小,表現出(chu)最好(hao)的(de)(de)(de)耐(nai)點(dian)(dian)蝕(shi)性能。綜上可(ke)(ke)(ke)知(zhi)(zhi),雙(shuang)相(xiang)不(bu)銹鋼(gang)的(de)(de)(de)耐(nai)點(dian)(dian)蝕(shi)性能由 PREN 值較小相(xiang)決定的(de)(de)(de)理論是有(you)實驗(yan)依據的(de)(de)(de)。
從圖3.12(a)~(d)可(ke)見(jian),在(zai)不(bu)同固(gu)溶(rong)狀態下,鐵素體相都(dou)(dou)更易發生點蝕;而從圖3.7(e)可(ke)見(jian),在(zai)不(bu)同固(gu)溶(rong)狀態下,PREN.都(dou)(dou)大(da)于(yu)PREN,,鐵素體的耐點蝕性能(neng)應優于(yu)奧氏體相,可(ke)見(jian)兩者存在(zai)矛盾。
隨固溶(rong)溫(wen)度變(bian)(bian)化(hua),雙相(xiang)(xiang)(xiang)(xiang)不(bu)(bu)銹鋼(gang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)鐵素(su)(su)體和奧(ao)氏體相(xiang)(xiang)(xiang)(xiang)的(de)(de)(de)(de)(de)(de)(de)(de)比例(li)改(gai)變(bian)(bian),且兩(liang)相(xiang)(xiang)(xiang)(xiang)形態(tai)也(ye)發(fa)生變(bian)(bian)化(hua)。Cr是鐵素(su)(su)體形成(cheng)(cheng)元(yuan)(yuan)素(su)(su),可提(ti)高材料(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng);Mo是鐵素(su)(su)體形成(cheng)(cheng)元(yuan)(yuan)素(su)(su),可提(ti)高點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)電位,降低腐蝕(shi)(shi)(shi)(shi)速(su)率;Ni是奧(ao)氏體形成(cheng)(cheng)元(yuan)(yuan)素(su)(su),可維持(chi)兩(liang)相(xiang)(xiang)(xiang)(xiang)平衡,提(ti)高耐(nai)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)。并且材料(liao)(liao)(liao)中(zhong)(zhong)存(cun)在(zai)一定量(liang)的(de)(de)(de)(de)(de)(de)(de)(de)N,其為(wei)奧(ao)氏體形成(cheng)(cheng)元(yuan)(yuan)素(su)(su),提(ti)高局部腐蝕(shi)(shi)(shi)(shi)抗力。從圖3.7(a)~(c)可見(jian),隨固溶(rong)溫(wen)度變(bian)(bian)化(hua),兩(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)(yuan)素(su)(su)含(han)量(liang)發(fa)生變(bian)(bian)化(hua)。由于(yu)Cr、Mo、Ni元(yuan)(yuan)素(su)(su)之(zhi)間的(de)(de)(de)(de)(de)(de)(de)(de)腐蝕(shi)(shi)(shi)(shi)電位存(cun)在(zai)差異,勢必造成(cheng)(cheng)兩(liang)相(xiang)(xiang)(xiang)(xiang)之(zhi)間存(cun)在(zai)電化(hua)學差異,使(shi)腐蝕(shi)(shi)(shi)(shi)更易發(fa)生。從圖3.7(e)可知(zhi),不(bu)(bu)同(tong)固溶(rong)狀態(tai)下材料(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)(de)(de)PREN,大(da)小(xiao)關(guan)系為(wei)1050℃>1000℃>1150℃>1100℃,因此(ci)(ci)根據前人的(de)(de)(de)(de)(de)(de)(de)(de)研究,不(bu)(bu)同(tong)固溶(rong)態(tai)材料(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)優(you)(you)(you)劣關(guan)系應為(wei):1050℃優(you)(you)(you)于(yu)1000℃優(you)(you)(you)于(yu)1150℃.當固溶(rong)溫(wen)度為(wei)1050℃時,PREN,值(zhi)較大(da),兩(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)(yuan)素(su)(su)含(han)量(liang)差異最小(xiao),材料(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)(de)(de)點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)坑(keng)較小(xiao),材料(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)最優(you)(you)(you)。1000℃固溶(rong)試(shi)(shi)樣(yang)的(de)(de)(de)(de)(de)(de)(de)(de)點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)坑(keng)尺(chi)寸大(da)于(yu)1150℃固溶(rong)試(shi)(shi)樣(yang)的(de)(de)(de)(de)(de)(de)(de)(de)點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)坑(keng)尺(chi)寸,因此(ci)(ci),前者的(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)劣于(yu)后者的(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)。由此(ci)(ci)可見(jian),雙相(xiang)(xiang)(xiang)(xiang)不(bu)(bu)銹鋼(gang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)相(xiang)(xiang)(xiang)(xiang)腐蝕(shi)(shi)(shi)(shi)不(bu)(bu)能(neng)(neng)僅僅由PREN值(zhi)來解釋。由圖3.7(a)~(c)可知(zhi),1000℃固溶(rong)試(shi)(shi)樣(yang)的(de)(de)(de)(de)(de)(de)(de)(de)兩(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)(yuan)素(su)(su)含(han)量(liang)差大(da)于(yu)1150℃固溶(rong)試(shi)(shi)樣(yang)的(de)(de)(de)(de)(de)(de)(de)(de)兩(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)Gr、Mo、Ni元(yuan)(yuan)素(su)(su)含(han)量(liang)差,因此(ci)(ci),雙相(xiang)(xiang)(xiang)(xiang)不(bu)(bu)銹鋼(gang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)相(xiang)(xiang)(xiang)(xiang)腐蝕(shi)(shi)(shi)(shi)還(huan)與兩(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)元(yuan)(yuan)素(su)(su)分布有關(guan),并且還(huan)需(xu)考慮(lv)到(dao)材料(liao)(liao)(liao)中(zhong)(zhong)點(dian)(dian)(dian)(dian)蝕(shi)(shi)(shi)(shi)敏感性(xing)較強的(de)(de)(de)(de)(de)(de)(de)(de)區域,如晶界和相(xiang)(xiang)(xiang)(xiang)界。
點蝕是一種局部腐蝕現象,是由氯離子破壞鈍化膜而導致的。點蝕產生后,蝕坑處的基體被暴露在溶液中,導致材料進一步發生腐蝕,蝕坑長大。蝕坑前長大速率由材料的均勻溶解速率決定,溶解越快,蝕坑長大速度越大。因此,雙相不銹鋼的耐點蝕性能由兩部分構成:控制點蝕萌生和控制蝕坑長大的能力。本書中的點蝕電位意味著點蝕已長大。影響點蝕萌生的因素不僅包括PREN 值,還包括兩相中的元素分布和兩相的比例。從本書的分析可見,點蝕的長大與元素分布有關,兩相中的元素分布越均勻,蝕坑的長大速度越慢。因此在1050℃固溶狀態下,兩相中的元素分布最均勻,PREN,最高,合金的點蝕電位最高,材料的耐點蝕性能最好。而1000℃固溶試樣兩相中的元素分布不均勻,導致點蝕電位較低,點蝕坑尺寸較大,降低材料的耐點蝕性能。
影響雙(shuang)相(xiang)不(bu)銹(xiu)鋼相(xiang)腐蝕的因素不(bu)僅(jin)包括(kuo)PREN值,還(huan)包括(kuo)各相(xiang)中的元素分布(bu)和兩(liang)相(xiang)比例,并且三者(zhe)互相(xiang)影響、關系復雜。因此,不(bu)能(neng)僅(jin)憑PREN值的大(da)小來判斷耐點蝕能(neng)力,應該綜合考慮各因素的影響。

