圖3.7(a)~(d)為(wei)(wei)(wei)鐵(tie)(tie)素(su)體(ti)(ti)(ti)和(he)奧(ao)(ao)(ao)氏體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)含(han)(han)量(liang)(liang)(liang)(liang)與固(gu)溶(rong)(rong)(rong)溫(wen)(wen)度(du)(du)(du)的(de)(de)(de)關系圖。圖3.7(a)~(d)證(zheng)實了鐵(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr和(he)Mo含(han)(han)量(liang)(liang)(liang)(liang)更高,而奧(ao)(ao)(ao)氏體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Ni和(he)Mn含(han)(han)量(liang)(liang)(liang)(liang)更高。從圖中(zhong)(zhong)(zhong)可(ke)看(kan)出,鐵(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr含(han)(han)量(liang)(liang)(liang)(liang)為(wei)(wei)(wei)23.77%~25.16%,比奧(ao)(ao)(ao)氏體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr含(han)(han)量(liang)(liang)(liang)(liang)高2%左(zuo)右;鐵(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Mo含(han)(han)量(liang)(liang)(liang)(liang)為(wei)(wei)(wei)3.86%~4.37%,比奧(ao)(ao)(ao)氏體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Mo含(han)(han)量(liang)(liang)(liang)(liang)高1.7%左(zuo)右;奧(ao)(ao)(ao)氏體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Ni含(han)(han)量(liang)(liang)(liang)(liang)為(wei)(wei)(wei)5.42%、6.7%,比鐵(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Ni含(han)(han)量(liang)(liang)(liang)(liang)高2%;當(dang)固(gu)溶(rong)(rong)(rong)處理溫(wen)(wen)度(du)(du)(du)為(wei)(wei)(wei)1050℃時(shi),鐵(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo和(he)Ni含(han)(han)量(liang)(liang)(liang)(liang)分別為(wei)(wei)(wei)23.77%、3.97%、4.24%,奧(ao)(ao)(ao)氏體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo和(he)Ni含(han)(han)量(liang)(liang)(liang)(liang)分別為(wei)(wei)(wei)23.53%、2.63%、5.42%.可(ke)見在1050℃溫(wen)(wen)度(du)(du)(du)下進(jin)行固(gu)溶(rong)(rong)(rong)時(shi),兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni含(han)(han)量(liang)(liang)(liang)(liang)差異最小(xiao),此(ci)時(shi)鐵(tie)(tie)素(su)體(ti)(ti)(ti)含(han)(han)量(liang)(liang)(liang)(liang)為(wei)(wei)(wei)51.9%,奧(ao)(ao)(ao)氏體(ti)(ti)(ti)含(han)(han)量(liang)(liang)(liang)(liang)為(wei)(wei)(wei)48.1%.當(dang)固(gu)溶(rong)(rong)(rong)溫(wen)(wen)度(du)(du)(du)改變時(shi),鐵(tie)(tie)素(su)體(ti)(ti)(ti)/奧(ao)(ao)(ao)氏體(ti)(ti)(ti)兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)比例相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)差變大(da),且(qie)兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni含(han)(han)量(liang)(liang)(liang)(liang)差異也變大(da)。當(dang)固(gu)溶(rong)(rong)(rong)溫(wen)(wen)度(du)(du)(du)為(wei)(wei)(wei)1000℃,兩(liang)(liang)相(xiang)(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)固(gu)溶(rong)(rong)(rong)溫(wen)(wen)度(du)(du)(du)為(wei)(wei)(wei)1150℃時(shi),兩(liang)(liang)相(xiang)(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1000℃固(gu)溶(rong)(rong)(rong)試樣的(de)(de)(de)兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)含(han)(han)量(liang)(liang)(liang)(liang)差大(da)于1150℃固(gu)溶(rong)(rong)(rong)試樣的(de)(de)(de)兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)Cr、Mo、Ni元(yuan)素(su)含(han)(han)量(liang)(liang)(liang)(liang)差。


7.jpg


  由公(gong)式(shi)“PREN.=[Cr]+3.3[Mo]”計(ji)算鐵素體的(de)(de)PREN值(zhi)(zhi),由公(gong)式(shi)“PREN,=[Cr]+3.3[Mo]+16[N]-[Mn]”計(ji)算奧氏體的(de)(de)PREN值(zhi)(zhi),可(ke)得PREN值(zhi)(zhi)與(yu)固(gu)(gu)溶(rong)溫(wen)度的(de)(de)關(guan)系圖(tu),如圖(tu)3.7(e)所示。從圖(tu)3.7(e)可(ke)看出,在不同固(gu)(gu)溶(rong)狀態下,兩(liang)相的(de)(de)PREN值(zhi)(zhi)有所不同,但PRENa>PRENy.當固(gu)(gu)溶(rong)溫(wen)度為1050℃時,PREN.最(zui)小(xiao)、PREN,最(zui)大,分別為36.9和30.6,兩(liang)者相差最(zui)小(xiao)。


  圖3.8為(wei)不(bu)同固溶試樣的極化曲線。可見,在自腐蝕(shi)(shi)電(dian)(dian)位(wei)下,材料(liao)開始發生鈍化;當極化電(dian)(dian)位(wei)升高(gao)到(dao)一定(ding)值時,不(bu)同固溶的材料(liao)都發生點蝕(shi)(shi),電(dian)(dian)流(liu)密(mi)度(du)急劇(ju)增大。根據GB 4334.9-1984中電(dian)(dian)流(liu)密(mi)度(du)為(wei)0.1mA/c㎡所對應的電(dian)(dian)位(wei)為(wei)點蝕(shi)(shi)電(dian)(dian)位(wei)和Tafel擬(ni)合(he),分別(bie)得到(dao)點蝕(shi)(shi)電(dian)(dian)位(wei)、自腐蝕(shi)(shi)電(dian)(dian)流(liu)密(mi)度(du)與固溶溫度(du)的關系圖,如圖3.11(a)所示。


8.jpg


  圖(tu)(tu)3.9(a)、(b)分別(bie)(bie)為不同(tong)固(gu)溶(rong)(rong)試(shi)樣的Nyquist 圖(tu)(tu)和Bode圖(tu)(tu)。從圖(tu)(tu)3.9(a)可見(jian),試(shi)樣在(zai)低(di)頻(pin)和高頻(pin)區分別(bie)(bie)存在(zai)一個容抗(kang)(kang)(kang)(kang)弧。從圖(tu)(tu)3.9(b)可見(jian),試(shi)樣在(zai)低(di)頻(pin)和高頻(pin)處(chu)分別(bie)(bie)存在(zai)一個時(shi)間常數。根據曹楚南的《電化學阻(zu)(zu)(zu)抗(kang)(kang)(kang)(kang)譜導論》可知。雙相不銹鋼在(zai)NaCl溶(rong)(rong)液中的阻(zu)(zu)(zu)抗(kang)(kang)(kang)(kang)譜中存在(zai)兩個時(shi)間常數,常以(yi)圖(tu)(tu)3.10所示的等效電路(R1為電荷(he)轉移電阻(zu)(zu)(zu),R2為鈍化膜電阻(zu)(zu)(zu))進行阻(zu)(zu)(zu)抗(kang)(kang)(kang)(kang)擬合。經阻(zu)(zu)(zu)抗(kang)(kang)(kang)(kang)擬合,得到鈍化膜電阻(zu)(zu)(zu)、電荷(he)轉移電阻(zu)(zu)(zu)與固(gu)溶(rong)(rong)處(chu)理(li)溫度的關系(xi)圖(tu)(tu),如圖(tu)(tu)3.11(b)所示。


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(suan)得到(dao)不(bu)(bu)(bu)同相(xiang)(xiang)比例下的(de)(de)(de)(de)鐵素體PREN值(zhi)和奧(ao)氏體PREN值(zhi),可(ke)見不(bu)(bu)(bu)同相(xiang)(xiang)比例下的(de)(de)(de)(de)PREN.都(dou)大于PREN,.雙相(xiang)(xiang)不(bu)(bu)(bu)銹(xiu)鋼(gang)的(de)(de)(de)(de)耐(nai)點(dian)(dian)蝕性(xing)(xing)能(neng)(neng)可(ke)通過點(dian)(dian)蝕電(dian)位衡量。點(dian)(dian)蝕電(dian)位越(yue)高(gao),耐(nai)點(dian)(dian)獨性(xing)(xing)能(neng)(neng)越(yue)好。前人認為雙相(xiang)(xiang)不(bu)(bu)(bu)銹(xiu)鋼(gang)的(de)(de)(de)(de)耐(nai)點(dian)(dian)蝕性(xing)(xing)能(neng)(neng)由(you)B能(neng)(neng)N值(zhi)較區的(de)(de)(de)(de)相(xiang)(xiang)決定(ding),且PEN值(zhi)越(yue)高(gao),耐(nai)點(dian)(dian)蝕性(xing)(xing)能(neng)(neng)越(yue)好,從圖(tu)(tu)(tu)3.71e)可(ke)矩,不(bu)(bu)(bu)同海溶試樣(yang)的(de)(de)(de)(de)PREN.都(dou)大于PREN,,當(dang)固溶溫度為1050℃時,PHEN,最(zui)大,材料的(de)(de)(de)(de)耐(nai)點(dian)(dian)蝕性(xing)(xing)能(neng)(neng)應最(zui)好。從圖(tu)(tu)(tu)3.11(a)、(b)可(ke)知,1050℃固溶試樣(yang)的(de)(de)(de)(de)點(dian)(dian)蝕電(dian)位最(zui)高(gao),鈍化(hua)膜(mo)阻(zu)抗值(zhi)最(zui)大,電(dian)荷轉移電(dian)阻(zu)值(zhi)最(zui)商;且從圖(tu)(tu)(tu)3.12(b)可(ke)見,1050℃固溶試樣(yang)的(de)(de)(de)(de)點(dian)(dian)蝕坑尺寸最(zui)小(xiao)(xiao),表現出(chu)最(zui)好的(de)(de)(de)(de)耐(nai)點(dian)(dian)蝕性(xing)(xing)能(neng)(neng)。綜上可(ke)知,雙相(xiang)(xiang)不(bu)(bu)(bu)銹(xiu)鋼(gang)的(de)(de)(de)(de)耐(nai)點(dian)(dian)蝕性(xing)(xing)能(neng)(neng)由(you) PREN 值(zhi)較小(xiao)(xiao)相(xiang)(xiang)決定(ding)的(de)(de)(de)(de)理論是有實驗依(yi)據的(de)(de)(de)(de)。


  從圖3.12(a)~(d)可(ke)見(jian),在不同固溶狀(zhuang)態下,鐵(tie)素體相都(dou)更易發(fa)生點(dian)蝕;而從圖3.7(e)可(ke)見(jian),在不同固溶狀(zhuang)態下,PREN.都(dou)大于(yu)PREN,,鐵(tie)素體的耐點(dian)蝕性能應優于(yu)奧氏體相,可(ke)見(jian)兩(liang)者存在矛盾。


  隨(sui)固(gu)溶(rong)(rong)溫度(du)變化,雙相(xiang)(xiang)不(bu)銹鋼(gang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)鐵素(su)體和(he)奧氏體相(xiang)(xiang)的(de)(de)(de)(de)比例(li)改變,且(qie)(qie)兩(liang)相(xiang)(xiang)形態也發(fa)生變化。Cr是(shi)(shi)鐵素(su)體形成元(yuan)(yuan)素(su),可(ke)(ke)提高材(cai)料(liao)(liao)(liao)的(de)(de)(de)(de)耐蝕(shi)(shi)(shi)(shi)(shi)(shi)性能;Mo是(shi)(shi)鐵素(su)體形成元(yuan)(yuan)素(su),可(ke)(ke)提高點蝕(shi)(shi)(shi)(shi)(shi)(shi)電位,降低腐蝕(shi)(shi)(shi)(shi)(shi)(shi)速率(lv);Ni是(shi)(shi)奧氏體形成元(yuan)(yuan)素(su),可(ke)(ke)維持兩(liang)相(xiang)(xiang)平(ping)衡,提高耐蝕(shi)(shi)(shi)(shi)(shi)(shi)性能。并且(qie)(qie)材(cai)料(liao)(liao)(liao)中(zhong)(zhong)(zhong)存在一定量(liang)的(de)(de)(de)(de)N,其為奧氏體形成元(yuan)(yuan)素(su),提高局部(bu)腐蝕(shi)(shi)(shi)(shi)(shi)(shi)抗力。從圖3.7(a)~(c)可(ke)(ke)見,隨(sui)固(gu)溶(rong)(rong)溫度(du)變化,兩(liang)相(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)(yuan)素(su)含量(liang)發(fa)生變化。由(you)(you)(you)于(yu)Cr、Mo、Ni元(yuan)(yuan)素(su)之(zhi)間(jian)的(de)(de)(de)(de)腐蝕(shi)(shi)(shi)(shi)(shi)(shi)電位存在差異,勢必造成兩(liang)相(xiang)(xiang)之(zhi)間(jian)存在電化學差異,使腐蝕(shi)(shi)(shi)(shi)(shi)(shi)更易發(fa)生。從圖3.7(e)可(ke)(ke)知,不(bu)同(tong)固(gu)溶(rong)(rong)狀態下材(cai)料(liao)(liao)(liao)的(de)(de)(de)(de)PREN,大(da)小(xiao)關(guan)系為1050℃>1000℃>1150℃>1100℃,因(yin)此根據前(qian)人的(de)(de)(de)(de)研究,不(bu)同(tong)固(gu)溶(rong)(rong)態材(cai)料(liao)(liao)(liao)的(de)(de)(de)(de)耐點蝕(shi)(shi)(shi)(shi)(shi)(shi)性能優(you)劣(lie)關(guan)系應為:1050℃優(you)于(yu)1000℃優(you)于(yu)1150℃.當固(gu)溶(rong)(rong)溫度(du)為1050℃時,PREN,值(zhi)(zhi)較大(da),兩(liang)相(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)(yuan)素(su)含量(liang)差異最(zui)小(xiao),材(cai)料(liao)(liao)(liao)的(de)(de)(de)(de)點蝕(shi)(shi)(shi)(shi)(shi)(shi)坑較小(xiao),材(cai)料(liao)(liao)(liao)的(de)(de)(de)(de)耐點蝕(shi)(shi)(shi)(shi)(shi)(shi)性能最(zui)優(you)。1000℃固(gu)溶(rong)(rong)試(shi)(shi)(shi)樣(yang)的(de)(de)(de)(de)點蝕(shi)(shi)(shi)(shi)(shi)(shi)坑尺寸(cun)大(da)于(yu)1150℃固(gu)溶(rong)(rong)試(shi)(shi)(shi)樣(yang)的(de)(de)(de)(de)點蝕(shi)(shi)(shi)(shi)(shi)(shi)坑尺寸(cun),因(yin)此,前(qian)者的(de)(de)(de)(de)耐點蝕(shi)(shi)(shi)(shi)(shi)(shi)性能劣(lie)于(yu)后者的(de)(de)(de)(de)耐點蝕(shi)(shi)(shi)(shi)(shi)(shi)性能。由(you)(you)(you)此可(ke)(ke)見,雙相(xiang)(xiang)不(bu)銹鋼(gang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)相(xiang)(xiang)腐蝕(shi)(shi)(shi)(shi)(shi)(shi)不(bu)能僅僅由(you)(you)(you)PREN值(zhi)(zhi)來(lai)解釋。由(you)(you)(you)圖3.7(a)~(c)可(ke)(ke)知,1000℃固(gu)溶(rong)(rong)試(shi)(shi)(shi)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)(yuan)素(su)含量(liang)差大(da)于(yu)1150℃固(gu)溶(rong)(rong)試(shi)(shi)(shi)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)(yuan)素(su)含量(liang)差,因(yin)此,雙相(xiang)(xiang)不(bu)銹鋼(gang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)相(xiang)(xiang)腐蝕(shi)(shi)(shi)(shi)(shi)(shi)還(huan)與兩(liang)相(xiang)(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)元(yuan)(yuan)素(su)分布有關(guan),并且(qie)(qie)還(huan)需考(kao)慮到材(cai)料(liao)(liao)(liao)中(zhong)(zhong)(zhong)點蝕(shi)(shi)(shi)(shi)(shi)(shi)敏感性較強(qiang)的(de)(de)(de)(de)區域,如晶(jing)界和(he)相(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)不銹鋼相(xiang)腐蝕(shi)的(de)因(yin)素(su)不僅包括(kuo)PREN值(zhi),還(huan)包括(kuo)各相(xiang)中的(de)元素(su)分布和兩相(xiang)比例,并且三(san)者互(hu)相(xiang)影響、關(guan)系復雜(za)。因(yin)此,不能僅憑PREN值(zhi)的(de)大小來判斷耐點蝕(shi)能力(li),應該綜合考慮各因(yin)素(su)的(de)影響。