圖(tu)3.7(a)~(d)為(wei)(wei)鐵(tie)素體(ti)(ti)(ti)和(he)奧(ao)(ao)(ao)氏(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素含(han)(han)量(liang)(liang)(liang)與固(gu)(gu)溶(rong)溫度(du)(du)的(de)(de)(de)(de)關系圖(tu)。圖(tu)3.7(a)~(d)證實了鐵(tie)素體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr和(he)Mo含(han)(han)量(liang)(liang)(liang)更(geng)高(gao),而奧(ao)(ao)(ao)氏(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Ni和(he)Mn含(han)(han)量(liang)(liang)(liang)更(geng)高(gao)。從(cong)圖(tu)中(zhong)(zhong)(zhong)可看(kan)出(chu),鐵(tie)素體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr含(han)(han)量(liang)(liang)(liang)為(wei)(wei)23.77%~25.16%,比奧(ao)(ao)(ao)氏(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr含(han)(han)量(liang)(liang)(liang)高(gao)2%左右;鐵(tie)素體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Mo含(han)(han)量(liang)(liang)(liang)為(wei)(wei)3.86%~4.37%,比奧(ao)(ao)(ao)氏(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Mo含(han)(han)量(liang)(liang)(liang)高(gao)1.7%左右;奧(ao)(ao)(ao)氏(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Ni含(han)(han)量(liang)(liang)(liang)為(wei)(wei)5.42%、6.7%,比鐵(tie)素體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Ni含(han)(han)量(liang)(liang)(liang)高(gao)2%;當(dang)固(gu)(gu)溶(rong)處(chu)理溫度(du)(du)為(wei)(wei)1050℃時(shi)(shi),鐵(tie)素體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo和(he)Ni含(han)(han)量(liang)(liang)(liang)分(fen)別為(wei)(wei)23.77%、3.97%、4.24%,奧(ao)(ao)(ao)氏(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo和(he)Ni含(han)(han)量(liang)(liang)(liang)分(fen)別為(wei)(wei)23.53%、2.63%、5.42%.可見(jian)在(zai)1050℃溫度(du)(du)下進行固(gu)(gu)溶(rong)時(shi)(shi),兩相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni含(han)(han)量(liang)(liang)(liang)差(cha)(cha)(cha)(cha)異最(zui)小,此(ci)時(shi)(shi)鐵(tie)素體(ti)(ti)(ti)含(han)(han)量(liang)(liang)(liang)為(wei)(wei)51.9%,奧(ao)(ao)(ao)氏(shi)體(ti)(ti)(ti)含(han)(han)量(liang)(liang)(liang)為(wei)(wei)48.1%.當(dang)固(gu)(gu)溶(rong)溫度(du)(du)改變(bian)時(shi)(shi),鐵(tie)素體(ti)(ti)(ti)/奧(ao)(ao)(ao)氏(shi)體(ti)(ti)(ti)兩相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)比例相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)差(cha)(cha)(cha)(cha)變(bian)大(da),且兩相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni含(han)(han)量(liang)(liang)(liang)差(cha)(cha)(cha)(cha)異也變(bian)大(da)。當(dang)固(gu)(gu)溶(rong)溫度(du)(du)為(wei)(wei)1000℃,兩相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr為(wei)(wei)3.69%、Mo為(wei)(wei)1.51%、Ni為(wei)(wei)3.37%;當(dang)固(gu)(gu)溶(rong)溫度(du)(du)為(wei)(wei)1150℃時(shi)(shi),兩相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr為(wei)(wei)2.29%、Mo為(wei)(wei)1.34%、Ni為(wei)(wei)2.09%,可見(jian)1000℃固(gu)(gu)溶(rong)試(shi)樣的(de)(de)(de)(de)兩相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素含(han)(han)量(liang)(liang)(liang)差(cha)(cha)(cha)(cha)大(da)于1150℃固(gu)(gu)溶(rong)試(shi)樣的(de)(de)(de)(de)兩相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr、Mo、Ni元(yuan)素含(han)(han)量(liang)(liang)(liang)差(cha)(cha)(cha)(cha)。


7.jpg


  由公式“PREN.=[Cr]+3.3[Mo]”計(ji)算鐵素體(ti)的(de)(de)PREN值,由公式“PREN,=[Cr]+3.3[Mo]+16[N]-[Mn]”計(ji)算奧氏(shi)體(ti)的(de)(de)PREN值,可得PREN值與(yu)固溶溫度(du)的(de)(de)關系圖,如圖3.7(e)所示。從圖3.7(e)可看(kan)出(chu),在不(bu)同固溶狀(zhuang)態下(xia),兩相的(de)(de)PREN值有所不(bu)同,但(dan)PRENa>PRENy.當固溶溫度(du)為(wei)1050℃時,PREN.最(zui)小(xiao)、PREN,最(zui)大,分別(bie)為(wei)36.9和30.6,兩者相差最(zui)小(xiao)。


  圖3.8為(wei)不同固(gu)溶試(shi)樣的(de)極化曲線。可見,在自腐蝕(shi)(shi)電(dian)(dian)位(wei)下,材料開始發生鈍化;當(dang)極化電(dian)(dian)位(wei)升(sheng)高到一定值時,不同固(gu)溶的(de)材料都發生點(dian)蝕(shi)(shi),電(dian)(dian)流密度急劇(ju)增大。根據GB 4334.9-1984中電(dian)(dian)流密度為(wei)0.1mA/c㎡所(suo)對應的(de)電(dian)(dian)位(wei)為(wei)點(dian)蝕(shi)(shi)電(dian)(dian)位(wei)和Tafel擬合,分別得(de)到點(dian)蝕(shi)(shi)電(dian)(dian)位(wei)、自腐蝕(shi)(shi)電(dian)(dian)流密度與固(gu)溶溫度的(de)關系圖,如(ru)圖3.11(a)所(suo)示。


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  圖3.9(a)、(b)分別為不同(tong)固溶(rong)試樣的(de)Nyquist 圖和Bode圖。從圖3.9(a)可(ke)見(jian),試樣在低頻和高頻區分別存(cun)(cun)在一個容抗(kang)弧。從圖3.9(b)可(ke)見(jian),試樣在低頻和高頻處分別存(cun)(cun)在一個時間(jian)常(chang)數(shu)。根據曹(cao)楚南的(de)《電(dian)化(hua)(hua)學阻(zu)抗(kang)譜導論(lun)》可(ke)知。雙相(xiang)不銹鋼(gang)在NaCl溶(rong)液中的(de)阻(zu)抗(kang)譜中存(cun)(cun)在兩個時間(jian)常(chang)數(shu),常(chang)以(yi)圖3.10所(suo)示的(de)等效電(dian)路(R1為電(dian)荷(he)轉(zhuan)移電(dian)阻(zu),R2為鈍化(hua)(hua)膜電(dian)阻(zu))進行阻(zu)抗(kang)擬合(he)。經(jing)阻(zu)抗(kang)擬合(he),得到鈍化(hua)(hua)膜電(dian)阻(zu)、電(dian)荷(he)轉(zhuan)移電(dian)阻(zu)與固溶(rong)處理(li)溫度的(de)關系(xi)圖,如圖3.11(b)所(suo)示。


9.jpg


 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


  通過計算得到不同相(xiang)(xiang)(xiang)(xiang)比例下(xia)的(de)鐵素體(ti)PREN值(zhi)(zhi)和奧氏體(ti)PREN值(zhi)(zhi),可(ke)(ke)(ke)見(jian)不同相(xiang)(xiang)(xiang)(xiang)比例下(xia)的(de)PREN.都大于PREN,.雙相(xiang)(xiang)(xiang)(xiang)不銹(xiu)(xiu)鋼的(de)耐點蝕(shi)(shi)(shi)性能(neng)可(ke)(ke)(ke)通過點蝕(shi)(shi)(shi)電位衡量。點蝕(shi)(shi)(shi)電位越(yue)高(gao),耐點獨性能(neng)越(yue)好(hao)(hao)。前人認為(wei)雙相(xiang)(xiang)(xiang)(xiang)不銹(xiu)(xiu)鋼的(de)耐點蝕(shi)(shi)(shi)性能(neng)由B能(neng)N值(zhi)(zhi)較(jiao)區(qu)的(de)相(xiang)(xiang)(xiang)(xiang)決定,且(qie)PEN值(zhi)(zhi)越(yue)高(gao),耐點蝕(shi)(shi)(shi)性能(neng)越(yue)好(hao)(hao),從圖(tu)3.71e)可(ke)(ke)(ke)矩(ju),不同海溶(rong)(rong)試(shi)(shi)樣的(de)PREN.都大于PREN,,當固溶(rong)(rong)溫度為(wei)1050℃時,PHEN,最(zui)(zui)大,材料的(de)耐點蝕(shi)(shi)(shi)性能(neng)應最(zui)(zui)好(hao)(hao)。從圖(tu)3.11(a)、(b)可(ke)(ke)(ke)知,1050℃固溶(rong)(rong)試(shi)(shi)樣的(de)點蝕(shi)(shi)(shi)電位最(zui)(zui)高(gao),鈍化(hua)膜阻(zu)抗值(zhi)(zhi)最(zui)(zui)大,電荷(he)轉移電阻(zu)值(zhi)(zhi)最(zui)(zui)商(shang);且(qie)從圖(tu)3.12(b)可(ke)(ke)(ke)見(jian),1050℃固溶(rong)(rong)試(shi)(shi)樣的(de)點蝕(shi)(shi)(shi)坑尺(chi)寸最(zui)(zui)小(xiao),表現出最(zui)(zui)好(hao)(hao)的(de)耐點蝕(shi)(shi)(shi)性能(neng)。綜上可(ke)(ke)(ke)知,雙相(xiang)(xiang)(xiang)(xiang)不銹(xiu)(xiu)鋼的(de)耐點蝕(shi)(shi)(shi)性能(neng)由 PREN 值(zhi)(zhi)較(jiao)小(xiao)相(xiang)(xiang)(xiang)(xiang)決定的(de)理論是(shi)有實驗依據的(de)。


  從圖3.12(a)~(d)可見(jian),在不同固(gu)溶狀態下,鐵(tie)素(su)體(ti)相都(dou)更(geng)易發生點蝕;而從圖3.7(e)可見(jian),在不同固(gu)溶狀態下,PREN.都(dou)大(da)于PREN,,鐵(tie)素(su)體(ti)的耐點蝕性(xing)能應優于奧氏體(ti)相,可見(jian)兩(liang)者存在矛盾。


  隨(sui)固(gu)(gu)(gu)溶溫(wen)(wen)度(du)變(bian)化,雙相(xiang)(xiang)不(bu)銹鋼(gang)(gang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)鐵(tie)(tie)素(su)(su)(su)(su)體(ti)和(he)奧氏(shi)體(ti)相(xiang)(xiang)的(de)(de)(de)(de)比例改變(bian),且兩(liang)相(xiang)(xiang)形(xing)(xing)態也發生(sheng)(sheng)變(bian)化。Cr是鐵(tie)(tie)素(su)(su)(su)(su)體(ti)形(xing)(xing)成元(yuan)素(su)(su)(su)(su),可(ke)(ke)提(ti)(ti)高(gao)材料(liao)的(de)(de)(de)(de)耐(nai)蝕(shi)(shi)性(xing)(xing)(xing)能(neng)(neng);Mo是鐵(tie)(tie)素(su)(su)(su)(su)體(ti)形(xing)(xing)成元(yuan)素(su)(su)(su)(su),可(ke)(ke)提(ti)(ti)高(gao)點(dian)蝕(shi)(shi)電(dian)(dian)(dian)位,降低腐(fu)(fu)(fu)蝕(shi)(shi)速率(lv);Ni是奧氏(shi)體(ti)形(xing)(xing)成元(yuan)素(su)(su)(su)(su),可(ke)(ke)維持兩(liang)相(xiang)(xiang)平衡(heng),提(ti)(ti)高(gao)耐(nai)蝕(shi)(shi)性(xing)(xing)(xing)能(neng)(neng)。并(bing)且材料(liao)中(zhong)(zhong)(zhong)存(cun)在(zai)一(yi)定(ding)量(liang)(liang)的(de)(de)(de)(de)N,其(qi)為(wei)(wei)(wei)奧氏(shi)體(ti)形(xing)(xing)成元(yuan)素(su)(su)(su)(su),提(ti)(ti)高(gao)局部腐(fu)(fu)(fu)蝕(shi)(shi)抗力(li)。從圖3.7(a)~(c)可(ke)(ke)見(jian),隨(sui)固(gu)(gu)(gu)溶溫(wen)(wen)度(du)變(bian)化,兩(liang)相(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)含量(liang)(liang)發生(sheng)(sheng)變(bian)化。由(you)于Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)之間(jian)(jian)的(de)(de)(de)(de)腐(fu)(fu)(fu)蝕(shi)(shi)電(dian)(dian)(dian)位存(cun)在(zai)差異,勢必(bi)造成兩(liang)相(xiang)(xiang)之間(jian)(jian)存(cun)在(zai)電(dian)(dian)(dian)化學(xue)差異,使腐(fu)(fu)(fu)蝕(shi)(shi)更易發生(sheng)(sheng)。從圖3.7(e)可(ke)(ke)知(zhi),不(bu)同固(gu)(gu)(gu)溶狀態下材料(liao)的(de)(de)(de)(de)PREN,大(da)小(xiao)(xiao)(xiao)關(guan)系(xi)為(wei)(wei)(wei)1050℃>1000℃>1150℃>1100℃,因此(ci)根據前人的(de)(de)(de)(de)研究,不(bu)同固(gu)(gu)(gu)溶態材料(liao)的(de)(de)(de)(de)耐(nai)點(dian)蝕(shi)(shi)性(xing)(xing)(xing)能(neng)(neng)優(you)(you)劣關(guan)系(xi)應為(wei)(wei)(wei):1050℃優(you)(you)于1000℃優(you)(you)于1150℃.當固(gu)(gu)(gu)溶溫(wen)(wen)度(du)為(wei)(wei)(wei)1050℃時,PREN,值較大(da),兩(liang)相(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)含量(liang)(liang)差異最(zui)小(xiao)(xiao)(xiao),材料(liao)的(de)(de)(de)(de)點(dian)蝕(shi)(shi)坑較小(xiao)(xiao)(xiao),材料(liao)的(de)(de)(de)(de)耐(nai)點(dian)蝕(shi)(shi)性(xing)(xing)(xing)能(neng)(neng)最(zui)優(you)(you)。1000℃固(gu)(gu)(gu)溶試樣(yang)的(de)(de)(de)(de)點(dian)蝕(shi)(shi)坑尺寸(cun)大(da)于1150℃固(gu)(gu)(gu)溶試樣(yang)的(de)(de)(de)(de)點(dian)蝕(shi)(shi)坑尺寸(cun),因此(ci),前者的(de)(de)(de)(de)耐(nai)點(dian)蝕(shi)(shi)性(xing)(xing)(xing)能(neng)(neng)劣于后者的(de)(de)(de)(de)耐(nai)點(dian)蝕(shi)(shi)性(xing)(xing)(xing)能(neng)(neng)。由(you)此(ci)可(ke)(ke)見(jian),雙相(xiang)(xiang)不(bu)銹鋼(gang)(gang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)相(xiang)(xiang)腐(fu)(fu)(fu)蝕(shi)(shi)不(bu)能(neng)(neng)僅僅由(you)PREN值來解釋。由(you)圖3.7(a)~(c)可(ke)(ke)知(zhi),1000℃固(gu)(gu)(gu)溶試樣(yang)的(de)(de)(de)(de)兩(liang)相(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)含量(liang)(liang)差大(da)于1150℃固(gu)(gu)(gu)溶試樣(yang)的(de)(de)(de)(de)兩(liang)相(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Gr、Mo、Ni元(yuan)素(su)(su)(su)(su)含量(liang)(liang)差,因此(ci),雙相(xiang)(xiang)不(bu)銹鋼(gang)(gang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)相(xiang)(xiang)腐(fu)(fu)(fu)蝕(shi)(shi)還與兩(liang)相(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)元(yuan)素(su)(su)(su)(su)分布有關(guan),并(bing)且還需考慮到(dao)材料(liao)中(zhong)(zhong)(zhong)點(dian)蝕(shi)(shi)敏感性(xing)(xing)(xing)較強的(de)(de)(de)(de)區域,如晶界和(he)相(xiang)(xiang)界。


  點蝕(shi)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(ying)響雙相不銹鋼相腐蝕的(de)因素(su)不僅包(bao)括(kuo)PREN值(zhi),還包(bao)括(kuo)各(ge)相中的(de)元素(su)分布和(he)兩相比例,并且三者互相影(ying)響、關(guan)系復雜。因此,不能僅憑PREN值(zhi)的(de)大(da)小來判斷耐點蝕能力,應該綜合(he)考(kao)慮(lv)各(ge)因素(su)的(de)影(ying)響。