圖3.7(a)~(d)為(wei)(wei)(wei)鐵(tie)(tie)素體和(he)奧(ao)氏體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni元(yuan)素含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)與(yu)固溶溫(wen)度的(de)(de)(de)關系圖。圖3.7(a)~(d)證實了鐵(tie)(tie)素體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr和(he)Mo含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)更高(gao)(gao),而(er)奧(ao)氏體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Ni和(he)Mn含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)更高(gao)(gao)。從(cong)圖中(zhong)(zhong)(zhong)可(ke)看出,鐵(tie)(tie)素體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)為(wei)(wei)(wei)23.77%~25.16%,比(bi)奧(ao)氏體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)高(gao)(gao)2%左右;鐵(tie)(tie)素體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Mo含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)為(wei)(wei)(wei)3.86%~4.37%,比(bi)奧(ao)氏體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Mo含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)高(gao)(gao)1.7%左右;奧(ao)氏體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Ni含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)為(wei)(wei)(wei)5.42%、6.7%,比(bi)鐵(tie)(tie)素體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Ni含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)高(gao)(gao)2%;當(dang)(dang)固溶處理溫(wen)度為(wei)(wei)(wei)1050℃時,鐵(tie)(tie)素體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo和(he)Ni含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)分別為(wei)(wei)(wei)23.77%、3.97%、4.24%,奧(ao)氏體相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo和(he)Ni含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)分別為(wei)(wei)(wei)23.53%、2.63%、5.42%.可(ke)見(jian)在1050℃溫(wen)度下(xia)進行固溶時,兩(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)差異最(zui)小,此時鐵(tie)(tie)素體含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)為(wei)(wei)(wei)51.9%,奧(ao)氏體含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)為(wei)(wei)(wei)48.1%.當(dang)(dang)固溶溫(wen)度改(gai)變(bian)時,鐵(tie)(tie)素體/奧(ao)氏體兩(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)比(bi)例相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)差變(bian)大,且兩(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)差異也變(bian)大。當(dang)(dang)固溶溫(wen)度為(wei)(wei)(wei)1000℃,兩(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr為(wei)(wei)(wei)3.69%、Mo為(wei)(wei)(wei)1.51%、Ni為(wei)(wei)(wei)3.37%;當(dang)(dang)固溶溫(wen)度為(wei)(wei)(wei)1150℃時,兩(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr為(wei)(wei)(wei)2.29%、Mo為(wei)(wei)(wei)1.34%、Ni為(wei)(wei)(wei)2.09%,可(ke)見(jian)1000℃固溶試(shi)樣(yang)的(de)(de)(de)兩(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni元(yuan)素含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)差大于1150℃固溶試(shi)樣(yang)的(de)(de)(de)兩(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr、Mo、Ni元(yuan)素含(han)(han)(han)(han)量(liang)(liang)(liang)(liang)(liang)(liang)(liang)差。


7.jpg


  由公(gong)式“PREN.=[Cr]+3.3[Mo]”計算(suan)鐵素體(ti)的(de)PREN值,由公(gong)式“PREN,=[Cr]+3.3[Mo]+16[N]-[Mn]”計算(suan)奧(ao)氏體(ti)的(de)PREN值,可(ke)得PREN值與固(gu)溶溫(wen)度的(de)關系圖,如圖3.7(e)所示。從圖3.7(e)可(ke)看(kan)出,在(zai)不(bu)同固(gu)溶狀態下,兩相(xiang)的(de)PREN值有所不(bu)同,但PRENa>PRENy.當固(gu)溶溫(wen)度為(wei)1050℃時,PREN.最小、PREN,最大,分別為(wei)36.9和(he)30.6,兩者相(xiang)差最小。


  圖3.8為不(bu)(bu)同固溶(rong)(rong)試樣的(de)極化曲線。可見,在自腐蝕(shi)(shi)電(dian)(dian)(dian)位下,材料開(kai)始發生(sheng)鈍(dun)化;當極化電(dian)(dian)(dian)位升(sheng)高到一定值時,不(bu)(bu)同固溶(rong)(rong)的(de)材料都(dou)發生(sheng)點(dian)蝕(shi)(shi),電(dian)(dian)(dian)流(liu)密度(du)急劇增大(da)。根據GB 4334.9-1984中電(dian)(dian)(dian)流(liu)密度(du)為0.1mA/c㎡所對應的(de)電(dian)(dian)(dian)位為點(dian)蝕(shi)(shi)電(dian)(dian)(dian)位和Tafel擬合,分(fen)別得到點(dian)蝕(shi)(shi)電(dian)(dian)(dian)位、自腐蝕(shi)(shi)電(dian)(dian)(dian)流(liu)密度(du)與固溶(rong)(rong)溫度(du)的(de)關系圖,如(ru)圖3.11(a)所示。


8.jpg


  圖(tu)(tu)3.9(a)、(b)分(fen)(fen)別為不同固溶(rong)試樣的(de)(de)Nyquist 圖(tu)(tu)和(he)Bode圖(tu)(tu)。從圖(tu)(tu)3.9(a)可(ke)見(jian),試樣在低頻(pin)(pin)和(he)高頻(pin)(pin)區分(fen)(fen)別存(cun)(cun)在一(yi)個(ge)(ge)容抗弧。從圖(tu)(tu)3.9(b)可(ke)見(jian),試樣在低頻(pin)(pin)和(he)高頻(pin)(pin)處分(fen)(fen)別存(cun)(cun)在一(yi)個(ge)(ge)時(shi)間(jian)常(chang)數。根據(ju)曹(cao)楚(chu)南的(de)(de)《電(dian)化學(xue)阻抗譜導論》可(ke)知。雙(shuang)相不銹(xiu)鋼在NaCl溶(rong)液(ye)中的(de)(de)阻抗譜中存(cun)(cun)在兩個(ge)(ge)時(shi)間(jian)常(chang)數,常(chang)以圖(tu)(tu)3.10所(suo)示的(de)(de)等效(xiao)電(dian)路(R1為電(dian)荷(he)轉移(yi)電(dian)阻,R2為鈍化膜電(dian)阻)進(jin)行(xing)阻抗擬合。經(jing)阻抗擬合,得到鈍化膜電(dian)阻、電(dian)荷(he)轉移(yi)電(dian)阻與固溶(rong)處理溫度的(de)(de)關(guan)系圖(tu)(tu),如圖(tu)(tu)3.11(b)所(suo)示。


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 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(xiu)鋼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。


12.jpg


  通過計算得到不(bu)同相(xiang)(xiang)比(bi)例(li)下(xia)的(de)鐵素體PREN值(zhi)(zhi)(zhi)和奧氏體PREN值(zhi)(zhi)(zhi),可(ke)(ke)見不(bu)同相(xiang)(xiang)比(bi)例(li)下(xia)的(de)PREN.都大于PREN,.雙相(xiang)(xiang)不(bu)銹(xiu)(xiu)(xiu)鋼的(de)耐(nai)(nai)點(dian)(dian)蝕(shi)性(xing)(xing)能可(ke)(ke)通過點(dian)(dian)蝕(shi)電(dian)(dian)位衡量。點(dian)(dian)蝕(shi)電(dian)(dian)位越(yue)高,耐(nai)(nai)點(dian)(dian)獨性(xing)(xing)能越(yue)好(hao)。前人(ren)認為雙相(xiang)(xiang)不(bu)銹(xiu)(xiu)(xiu)鋼的(de)耐(nai)(nai)點(dian)(dian)蝕(shi)性(xing)(xing)能由B能N值(zhi)(zhi)(zhi)較(jiao)區的(de)相(xiang)(xiang)決定,且PEN值(zhi)(zhi)(zhi)越(yue)高,耐(nai)(nai)點(dian)(dian)蝕(shi)性(xing)(xing)能越(yue)好(hao),從圖3.71e)可(ke)(ke)矩,不(bu)同海溶試樣的(de)PREN.都大于PREN,,當固溶溫度(du)為1050℃時(shi),PHEN,最大,材料的(de)耐(nai)(nai)點(dian)(dian)蝕(shi)性(xing)(xing)能應最好(hao)。從圖3.11(a)、(b)可(ke)(ke)知,1050℃固溶試樣的(de)點(dian)(dian)蝕(shi)電(dian)(dian)位最高,鈍化膜阻抗(kang)值(zhi)(zhi)(zhi)最大,電(dian)(dian)荷轉(zhuan)移電(dian)(dian)阻值(zhi)(zhi)(zhi)最商;且從圖3.12(b)可(ke)(ke)見,1050℃固溶試樣的(de)點(dian)(dian)蝕(shi)坑尺寸(cun)最小(xiao),表(biao)現(xian)出(chu)最好(hao)的(de)耐(nai)(nai)點(dian)(dian)蝕(shi)性(xing)(xing)能。綜上可(ke)(ke)知,雙相(xiang)(xiang)不(bu)銹(xiu)(xiu)(xiu)鋼的(de)耐(nai)(nai)點(dian)(dian)蝕(shi)性(xing)(xing)能由 PREN 值(zhi)(zhi)(zhi)較(jiao)小(xiao)相(xiang)(xiang)決定的(de)理論是有(you)實驗依(yi)據(ju)的(de)。


  從圖3.12(a)~(d)可(ke)見(jian),在(zai)(zai)不(bu)同固(gu)溶狀(zhuang)(zhuang)態(tai)下,鐵(tie)(tie)素體(ti)相(xiang)都更易發生點(dian)蝕;而從圖3.7(e)可(ke)見(jian),在(zai)(zai)不(bu)同固(gu)溶狀(zhuang)(zhuang)態(tai)下,PREN.都大于(yu)(yu)PREN,,鐵(tie)(tie)素體(ti)的耐點(dian)蝕性能(neng)應優于(yu)(yu)奧氏體(ti)相(xiang),可(ke)見(jian)兩者存在(zai)(zai)矛盾。


  隨(sui)固(gu)溶(rong)溫(wen)度(du)變(bian)(bian)化(hua),雙(shuang)相(xiang)(xiang)(xiang)(xiang)(xiang)不(bu)銹(xiu)鋼(gang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)鐵(tie)素(su)(su)(su)(su)(su)(su)體(ti)(ti)和(he)奧(ao)氏(shi)體(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)的(de)(de)(de)(de)(de)(de)比例改變(bian)(bian),且兩相(xiang)(xiang)(xiang)(xiang)(xiang)形態也(ye)發生(sheng)變(bian)(bian)化(hua)。Cr是(shi)鐵(tie)素(su)(su)(su)(su)(su)(su)體(ti)(ti)形成(cheng)(cheng)元(yuan)素(su)(su)(su)(su)(su)(su),可(ke)(ke)提(ti)高(gao)材(cai)(cai)料(liao)(liao)(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)耐蝕(shi)(shi)(shi)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng);Mo是(shi)鐵(tie)素(su)(su)(su)(su)(su)(su)體(ti)(ti)形成(cheng)(cheng)元(yuan)素(su)(su)(su)(su)(su)(su),可(ke)(ke)提(ti)高(gao)點(dian)蝕(shi)(shi)(shi)電(dian)位,降低腐蝕(shi)(shi)(shi)速率;Ni是(shi)奧(ao)氏(shi)體(ti)(ti)形成(cheng)(cheng)元(yuan)素(su)(su)(su)(su)(su)(su),可(ke)(ke)維持兩相(xiang)(xiang)(xiang)(xiang)(xiang)平(ping)衡,提(ti)高(gao)耐蝕(shi)(shi)(shi)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。并(bing)且材(cai)(cai)料(liao)(liao)(liao)(liao)(liao)中(zhong)(zhong)存(cun)(cun)在(zai)(zai)一定量(liang)的(de)(de)(de)(de)(de)(de)N,其為(wei)(wei)(wei)奧(ao)氏(shi)體(ti)(ti)形成(cheng)(cheng)元(yuan)素(su)(su)(su)(su)(su)(su),提(ti)高(gao)局部腐蝕(shi)(shi)(shi)抗力。從(cong)圖3.7(a)~(c)可(ke)(ke)見,隨(sui)固(gu)溶(rong)溫(wen)度(du)變(bian)(bian)化(hua),兩相(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)(su)(su)含量(liang)發生(sheng)變(bian)(bian)化(hua)。由(you)(you)于(yu)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)(su)(su)之間的(de)(de)(de)(de)(de)(de)腐蝕(shi)(shi)(shi)電(dian)位存(cun)(cun)在(zai)(zai)差(cha)(cha)異(yi)(yi)(yi),勢必造(zao)成(cheng)(cheng)兩相(xiang)(xiang)(xiang)(xiang)(xiang)之間存(cun)(cun)在(zai)(zai)電(dian)化(hua)學差(cha)(cha)異(yi)(yi)(yi),使腐蝕(shi)(shi)(shi)更(geng)易(yi)發生(sheng)。從(cong)圖3.7(e)可(ke)(ke)知(zhi),不(bu)同固(gu)溶(rong)狀態下材(cai)(cai)料(liao)(liao)(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)PREN,大(da)小關(guan)(guan)系為(wei)(wei)(wei)1050℃>1000℃>1150℃>1100℃,因(yin)此(ci)(ci)根(gen)據(ju)前人的(de)(de)(de)(de)(de)(de)研究(jiu),不(bu)同固(gu)溶(rong)態材(cai)(cai)料(liao)(liao)(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)耐點(dian)蝕(shi)(shi)(shi)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)優劣關(guan)(guan)系應為(wei)(wei)(wei):1050℃優于(yu)1000℃優于(yu)1150℃.當固(gu)溶(rong)溫(wen)度(du)為(wei)(wei)(wei)1050℃時(shi),PREN,值(zhi)較大(da),兩相(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)(su)(su)含量(liang)差(cha)(cha)異(yi)(yi)(yi)最小,材(cai)(cai)料(liao)(liao)(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)點(dian)蝕(shi)(shi)(shi)坑較小,材(cai)(cai)料(liao)(liao)(liao)(liao)(liao)的(de)(de)(de)(de)(de)(de)耐點(dian)蝕(shi)(shi)(shi)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)最優。1000℃固(gu)溶(rong)試(shi)樣(yang)(yang)的(de)(de)(de)(de)(de)(de)點(dian)蝕(shi)(shi)(shi)坑尺寸大(da)于(yu)1150℃固(gu)溶(rong)試(shi)樣(yang)(yang)的(de)(de)(de)(de)(de)(de)點(dian)蝕(shi)(shi)(shi)坑尺寸,因(yin)此(ci)(ci),前者的(de)(de)(de)(de)(de)(de)耐點(dian)蝕(shi)(shi)(shi)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)劣于(yu)后者的(de)(de)(de)(de)(de)(de)耐點(dian)蝕(shi)(shi)(shi)性(xing)(xing)(xing)(xing)(xing)(xing)能(neng)(neng)。由(you)(you)此(ci)(ci)可(ke)(ke)見,雙(shuang)相(xiang)(xiang)(xiang)(xiang)(xiang)不(bu)銹(xiu)鋼(gang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)相(xiang)(xiang)(xiang)(xiang)(xiang)腐蝕(shi)(shi)(shi)不(bu)能(neng)(neng)僅僅由(you)(you)PREN值(zhi)來解釋。由(you)(you)圖3.7(a)~(c)可(ke)(ke)知(zhi),1000℃固(gu)溶(rong)試(shi)樣(yang)(yang)的(de)(de)(de)(de)(de)(de)兩相(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)(su)(su)含量(liang)差(cha)(cha)大(da)于(yu)1150℃固(gu)溶(rong)試(shi)樣(yang)(yang)的(de)(de)(de)(de)(de)(de)兩相(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)Gr、Mo、Ni元(yuan)素(su)(su)(su)(su)(su)(su)含量(liang)差(cha)(cha),因(yin)此(ci)(ci),雙(shuang)相(xiang)(xiang)(xiang)(xiang)(xiang)不(bu)銹(xiu)鋼(gang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)相(xiang)(xiang)(xiang)(xiang)(xiang)腐蝕(shi)(shi)(shi)還與兩相(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)(de)(de)(de)(de)元(yuan)素(su)(su)(su)(su)(su)(su)分布(bu)有關(guan)(guan),并(bing)且還需考慮到材(cai)(cai)料(liao)(liao)(liao)(liao)(liao)中(zhong)(zhong)點(dian)蝕(shi)(shi)(shi)敏感(gan)性(xing)(xing)(xing)(xing)(xing)(xing)較強的(de)(de)(de)(de)(de)(de)區域(yu),如晶界和(he)相(xiang)(xiang)(xiang)(xiang)(xiang)界。


  點蝕是一種局(ju)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。


  影響雙相(xiang)不銹鋼相(xiang)腐蝕的因(yin)素(su)不僅包括PREN值,還包括各(ge)相(xiang)中的元素(su)分布和兩相(xiang)比例,并且(qie)三者互相(xiang)影響、關系復雜。因(yin)此,不能僅憑(ping)PREN值的大小來(lai)判斷耐點蝕能力,應該綜合考慮各(ge)因(yin)素(su)的影響。