圖(tu)3.7(a)~(d)為(wei)(wei)(wei)(wei)鐵(tie)(tie)(tie)(tie)素(su)(su)(su)(su)體(ti)和(he)奧(ao)氏(shi)(shi)(shi)(shi)(shi)(shi)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)含(han)量(liang)(liang)與固(gu)溶(rong)(rong)溫(wen)(wen)度(du)(du)的(de)(de)(de)(de)關系圖(tu)。圖(tu)3.7(a)~(d)證實了鐵(tie)(tie)(tie)(tie)素(su)(su)(su)(su)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr和(he)Mo含(han)量(liang)(liang)更高,而(er)奧(ao)氏(shi)(shi)(shi)(shi)(shi)(shi)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Ni和(he)Mn含(han)量(liang)(liang)更高。從圖(tu)中(zhong)(zhong)(zhong)(zhong)可看出,鐵(tie)(tie)(tie)(tie)素(su)(su)(su)(su)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr含(han)量(liang)(liang)為(wei)(wei)(wei)(wei)23.77%~25.16%,比奧(ao)氏(shi)(shi)(shi)(shi)(shi)(shi)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)Cr含(han)量(liang)(liang)高2%左右(you);鐵(tie)(tie)(tie)(tie)素(su)(su)(su)(su)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)Mo含(han)量(liang)(liang)為(wei)(wei)(wei)(wei)3.86%~4.37%,比奧(ao)氏(shi)(shi)(shi)(shi)(shi)(shi)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Mo含(han)量(liang)(liang)高1.7%左右(you);奧(ao)氏(shi)(shi)(shi)(shi)(shi)(shi)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Ni含(han)量(liang)(liang)為(wei)(wei)(wei)(wei)5.42%、6.7%,比鐵(tie)(tie)(tie)(tie)素(su)(su)(su)(su)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Ni含(han)量(liang)(liang)高2%;當固(gu)溶(rong)(rong)處理(li)溫(wen)(wen)度(du)(du)為(wei)(wei)(wei)(wei)1050℃時,鐵(tie)(tie)(tie)(tie)素(su)(su)(su)(su)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo和(he)Ni含(han)量(liang)(liang)分別為(wei)(wei)(wei)(wei)23.77%、3.97%、4.24%,奧(ao)氏(shi)(shi)(shi)(shi)(shi)(shi)體(ti)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo和(he)Ni含(han)量(liang)(liang)分別為(wei)(wei)(wei)(wei)23.53%、2.63%、5.42%.可見在1050℃溫(wen)(wen)度(du)(du)下進行固(gu)溶(rong)(rong)時,兩(liang)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni含(han)量(liang)(liang)差異最(zui)小,此時鐵(tie)(tie)(tie)(tie)素(su)(su)(su)(su)體(ti)含(han)量(liang)(liang)為(wei)(wei)(wei)(wei)51.9%,奧(ao)氏(shi)(shi)(shi)(shi)(shi)(shi)體(ti)含(han)量(liang)(liang)為(wei)(wei)(wei)(wei)48.1%.當固(gu)溶(rong)(rong)溫(wen)(wen)度(du)(du)改(gai)變時,鐵(tie)(tie)(tie)(tie)素(su)(su)(su)(su)體(ti)/奧(ao)氏(shi)(shi)(shi)(shi)(shi)(shi)體(ti)兩(liang)相(xiang)比例(li)相(xiang)差變大,且兩(liang)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni含(han)量(liang)(liang)差異也(ye)變大。當固(gu)溶(rong)(rong)溫(wen)(wen)度(du)(du)為(wei)(wei)(wei)(wei)1000℃,兩(liang)相(xiang)中(zhong)(zhong)(zhong)(zhong)Cr為(wei)(wei)(wei)(wei)3.69%、Mo為(wei)(wei)(wei)(wei)1.51%、Ni為(wei)(wei)(wei)(wei)3.37%;當固(gu)溶(rong)(rong)溫(wen)(wen)度(du)(du)為(wei)(wei)(wei)(wei)1150℃時,兩(liang)相(xiang)中(zhong)(zhong)(zhong)(zhong)Cr為(wei)(wei)(wei)(wei)2.29%、Mo為(wei)(wei)(wei)(wei)1.34%、Ni為(wei)(wei)(wei)(wei)2.09%,可見1000℃固(gu)溶(rong)(rong)試樣的(de)(de)(de)(de)兩(liang)相(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)(de)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)含(han)量(liang)(liang)差大于1150℃固(gu)溶(rong)(rong)試樣的(de)(de)(de)(de)兩(liang)相(xiang)中(zhong)(zhong)(zhong)(zhong)Cr、Mo、Ni元(yuan)素(su)(su)(su)(su)含(han)量(liang)(liang)差。


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  由公式“PREN.=[Cr]+3.3[Mo]”計算鐵素(su)體(ti)的(de)PREN值(zhi),由公式“PREN,=[Cr]+3.3[Mo]+16[N]-[Mn]”計算奧氏體(ti)的(de)PREN值(zhi),可得(de)PREN值(zhi)與固溶(rong)溫度(du)的(de)關(guan)系圖,如(ru)圖3.7(e)所(suo)示。從圖3.7(e)可看出,在(zai)不同固溶(rong)狀態下,兩(liang)相(xiang)的(de)PREN值(zhi)有所(suo)不同,但PRENa>PRENy.當固溶(rong)溫度(du)為1050℃時,PREN.最(zui)(zui)小(xiao)、PREN,最(zui)(zui)大,分別為36.9和(he)30.6,兩(liang)者相(xiang)差最(zui)(zui)小(xiao)。


  圖(tu)(tu)3.8為不同固(gu)溶試(shi)樣的極化曲線(xian)。可見,在自腐蝕(shi)(shi)電(dian)位(wei)下(xia),材(cai)料開始發(fa)生(sheng)鈍化;當極化電(dian)位(wei)升高(gao)到一定值時(shi),不同固(gu)溶的材(cai)料都(dou)發(fa)生(sheng)點蝕(shi)(shi),電(dian)流(liu)密(mi)(mi)度急(ji)劇增(zeng)大。根(gen)據GB 4334.9-1984中電(dian)流(liu)密(mi)(mi)度為0.1mA/c㎡所對應的電(dian)位(wei)為點蝕(shi)(shi)電(dian)位(wei)和Tafel擬合,分別(bie)得到點蝕(shi)(shi)電(dian)位(wei)、自腐蝕(shi)(shi)電(dian)流(liu)密(mi)(mi)度與固(gu)溶溫度的關系圖(tu)(tu),如圖(tu)(tu)3.11(a)所示。


8.jpg


  圖(tu)3.9(a)、(b)分別(bie)為不同固溶試樣(yang)的(de)Nyquist 圖(tu)和(he)Bode圖(tu)。從(cong)圖(tu)3.9(a)可(ke)見,試樣(yang)在低(di)頻和(he)高頻區(qu)分別(bie)存(cun)(cun)在一個(ge)(ge)容抗弧。從(cong)圖(tu)3.9(b)可(ke)見,試樣(yang)在低(di)頻和(he)高頻處分別(bie)存(cun)(cun)在一個(ge)(ge)時間(jian)常數。根據曹(cao)楚南的(de)《電(dian)(dian)(dian)化學阻(zu)抗譜導論》可(ke)知。雙相不銹鋼在NaCl溶液中的(de)阻(zu)抗譜中存(cun)(cun)在兩個(ge)(ge)時間(jian)常數,常以圖(tu)3.10所示的(de)等效電(dian)(dian)(dian)路(lu)(R1為電(dian)(dian)(dian)荷轉移電(dian)(dian)(dian)阻(zu),R2為鈍(dun)化膜(mo)電(dian)(dian)(dian)阻(zu))進行阻(zu)抗擬合。經(jing)阻(zu)抗擬合,得(de)到鈍(dun)化膜(mo)電(dian)(dian)(dian)阻(zu)、電(dian)(dian)(dian)荷轉移電(dian)(dian)(dian)阻(zu)與固溶處理溫度(du)的(de)關系(xi)圖(tu),如圖(tu)3.11(b)所示。


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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(shuang)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。


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  通過計算得到不(bu)同(tong)相比(bi)例下(xia)的(de)(de)鐵素(su)體PREN值和奧氏體PREN值,可(ke)見不(bu)同(tong)相比(bi)例下(xia)的(de)(de)PREN.都大(da)(da)于(yu)PREN,.雙相不(bu)銹鋼的(de)(de)耐(nai)(nai)點(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)可(ke)通過點(dian)蝕(shi)(shi)(shi)(shi)電位衡量。點(dian)蝕(shi)(shi)(shi)(shi)電位越(yue)高,耐(nai)(nai)點(dian)獨性(xing)能(neng)(neng)越(yue)好(hao)(hao)(hao)。前(qian)人認為雙相不(bu)銹鋼的(de)(de)耐(nai)(nai)點(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)由B能(neng)(neng)N值較(jiao)(jiao)區(qu)的(de)(de)相決(jue)定,且PEN值越(yue)高,耐(nai)(nai)點(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)越(yue)好(hao)(hao)(hao),從圖(tu)3.71e)可(ke)矩,不(bu)同(tong)海溶(rong)試樣(yang)(yang)的(de)(de)PREN.都大(da)(da)于(yu)PREN,,當(dang)固溶(rong)溫度為1050℃時,PHEN,最(zui)大(da)(da),材料的(de)(de)耐(nai)(nai)點(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)應最(zui)好(hao)(hao)(hao)。從圖(tu)3.11(a)、(b)可(ke)知(zhi)(zhi),1050℃固溶(rong)試樣(yang)(yang)的(de)(de)點(dian)蝕(shi)(shi)(shi)(shi)電位最(zui)高,鈍化膜阻抗(kang)值最(zui)大(da)(da),電荷(he)轉移(yi)電阻值最(zui)商;且從圖(tu)3.12(b)可(ke)見,1050℃固溶(rong)試樣(yang)(yang)的(de)(de)點(dian)蝕(shi)(shi)(shi)(shi)坑尺寸最(zui)小(xiao),表現出最(zui)好(hao)(hao)(hao)的(de)(de)耐(nai)(nai)點(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)。綜(zong)上可(ke)知(zhi)(zhi),雙相不(bu)銹鋼的(de)(de)耐(nai)(nai)點(dian)蝕(shi)(shi)(shi)(shi)性(xing)能(neng)(neng)由 PREN 值較(jiao)(jiao)小(xiao)相決(jue)定的(de)(de)理論是有實驗依據(ju)的(de)(de)。


  從圖(tu)(tu)3.12(a)~(d)可見(jian),在不(bu)同固(gu)溶(rong)狀態(tai)下(xia),鐵素體相都(dou)(dou)更易發生(sheng)點(dian)蝕(shi);而從圖(tu)(tu)3.7(e)可見(jian),在不(bu)同固(gu)溶(rong)狀態(tai)下(xia),PREN.都(dou)(dou)大于PREN,,鐵素體的耐點(dian)蝕(shi)性能應優于奧氏體相,可見(jian)兩(liang)者存在矛盾。


  隨(sui)固(gu)溶(rong)(rong)(rong)(rong)溫度變化(hua),雙相(xiang)不銹鋼中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)(de)鐵(tie)(tie)素(su)(su)(su)體(ti)(ti)和(he)奧氏體(ti)(ti)相(xiang)的(de)(de)(de)(de)(de)(de)(de)(de)(de)比例改變,且(qie)(qie)兩(liang)(liang)相(xiang)形(xing)(xing)態(tai)也(ye)發(fa)生變化(hua)。Cr是鐵(tie)(tie)素(su)(su)(su)體(ti)(ti)形(xing)(xing)成(cheng)(cheng)(cheng)元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su),可(ke)(ke)(ke)(ke)(ke)提(ti)(ti)高材(cai)(cai)(cai)料(liao)的(de)(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)(nai)(nai)蝕(shi)(shi)(shi)(shi)性能(neng);Mo是鐵(tie)(tie)素(su)(su)(su)體(ti)(ti)形(xing)(xing)成(cheng)(cheng)(cheng)元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su),可(ke)(ke)(ke)(ke)(ke)提(ti)(ti)高點(dian)(dian)蝕(shi)(shi)(shi)(shi)電位,降低腐(fu)(fu)蝕(shi)(shi)(shi)(shi)速率;Ni是奧氏體(ti)(ti)形(xing)(xing)成(cheng)(cheng)(cheng)元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su),可(ke)(ke)(ke)(ke)(ke)維持兩(liang)(liang)相(xiang)平衡,提(ti)(ti)高耐(nai)(nai)(nai)蝕(shi)(shi)(shi)(shi)性能(neng)。并(bing)且(qie)(qie)材(cai)(cai)(cai)料(liao)中(zhong)(zhong)(zhong)存在一定量(liang)的(de)(de)(de)(de)(de)(de)(de)(de)(de)N,其(qi)為(wei)奧氏體(ti)(ti)形(xing)(xing)成(cheng)(cheng)(cheng)元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su),提(ti)(ti)高局部腐(fu)(fu)蝕(shi)(shi)(shi)(shi)抗力(li)。從圖(tu)(tu)3.7(a)~(c)可(ke)(ke)(ke)(ke)(ke)見(jian)(jian),隨(sui)固(gu)溶(rong)(rong)(rong)(rong)溫度變化(hua),兩(liang)(liang)相(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)含(han)(han)量(liang)發(fa)生變化(hua)。由于Cr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)之間的(de)(de)(de)(de)(de)(de)(de)(de)(de)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)電位存在差(cha)(cha)異,勢(shi)必造(zao)成(cheng)(cheng)(cheng)兩(liang)(liang)相(xiang)之間存在電化(hua)學差(cha)(cha)異,使腐(fu)(fu)蝕(shi)(shi)(shi)(shi)更易(yi)發(fa)生。從圖(tu)(tu)3.7(e)可(ke)(ke)(ke)(ke)(ke)知(zhi),不同固(gu)溶(rong)(rong)(rong)(rong)狀態(tai)下材(cai)(cai)(cai)料(liao)的(de)(de)(de)(de)(de)(de)(de)(de)(de)PREN,大(da)(da)(da)小關(guan)(guan)系(xi)為(wei)1050℃>1000℃>1150℃>1100℃,因(yin)(yin)此根據前人的(de)(de)(de)(de)(de)(de)(de)(de)(de)研究,不同固(gu)溶(rong)(rong)(rong)(rong)態(tai)材(cai)(cai)(cai)料(liao)的(de)(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)(nai)(nai)點(dian)(dian)蝕(shi)(shi)(shi)(shi)性能(neng)優(you)劣(lie)關(guan)(guan)系(xi)應為(wei):1050℃優(you)于1000℃優(you)于1150℃.當固(gu)溶(rong)(rong)(rong)(rong)溫度為(wei)1050℃時,PREN,值較大(da)(da)(da),兩(liang)(liang)相(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)含(han)(han)量(liang)差(cha)(cha)異最(zui)小,材(cai)(cai)(cai)料(liao)的(de)(de)(de)(de)(de)(de)(de)(de)(de)點(dian)(dian)蝕(shi)(shi)(shi)(shi)坑(keng)較小,材(cai)(cai)(cai)料(liao)的(de)(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)(nai)(nai)點(dian)(dian)蝕(shi)(shi)(shi)(shi)性能(neng)最(zui)優(you)。1000℃固(gu)溶(rong)(rong)(rong)(rong)試樣的(de)(de)(de)(de)(de)(de)(de)(de)(de)點(dian)(dian)蝕(shi)(shi)(shi)(shi)坑(keng)尺寸大(da)(da)(da)于1150℃固(gu)溶(rong)(rong)(rong)(rong)試樣的(de)(de)(de)(de)(de)(de)(de)(de)(de)點(dian)(dian)蝕(shi)(shi)(shi)(shi)坑(keng)尺寸,因(yin)(yin)此,前者的(de)(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)(nai)(nai)點(dian)(dian)蝕(shi)(shi)(shi)(shi)性能(neng)劣(lie)于后(hou)者的(de)(de)(de)(de)(de)(de)(de)(de)(de)耐(nai)(nai)(nai)點(dian)(dian)蝕(shi)(shi)(shi)(shi)性能(neng)。由此可(ke)(ke)(ke)(ke)(ke)見(jian)(jian),雙相(xiang)不銹鋼中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)(de)相(xiang)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)不能(neng)僅僅由PREN值來解釋。由圖(tu)(tu)3.7(a)~(c)可(ke)(ke)(ke)(ke)(ke)知(zhi),1000℃固(gu)溶(rong)(rong)(rong)(rong)試樣的(de)(de)(de)(de)(de)(de)(de)(de)(de)兩(liang)(liang)相(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)(de)Cr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)含(han)(han)量(liang)差(cha)(cha)大(da)(da)(da)于1150℃固(gu)溶(rong)(rong)(rong)(rong)試樣的(de)(de)(de)(de)(de)(de)(de)(de)(de)兩(liang)(liang)相(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)(de)Gr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)含(han)(han)量(liang)差(cha)(cha),因(yin)(yin)此,雙相(xiang)不銹鋼中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)(de)相(xiang)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)還(huan)與兩(liang)(liang)相(xiang)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)(de)(de)(de)(de)元(yuan)(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)分布有關(guan)(guan),并(bing)且(qie)(qie)還(huan)需考慮到材(cai)(cai)(cai)料(liao)中(zhong)(zhong)(zhong)點(dian)(dian)蝕(shi)(shi)(shi)(shi)敏(min)感性較強的(de)(de)(de)(de)(de)(de)(de)(de)(de)區域,如晶界和(he)相(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(ying)響雙相(xiang)(xiang)不銹鋼(gang)相(xiang)(xiang)腐蝕的(de)因素不僅包括(kuo)PREN值(zhi)(zhi),還包括(kuo)各(ge)相(xiang)(xiang)中的(de)元(yuan)素分布(bu)和兩相(xiang)(xiang)比例,并且三者(zhe)互相(xiang)(xiang)影(ying)響、關系復雜。因此(ci),不能僅憑PREN值(zhi)(zhi)的(de)大(da)小來判斷耐點蝕能力,應該綜合(he)考慮各(ge)因素的(de)影(ying)響。