圖(tu)3.7(a)~(d)為(wei)(wei)鐵(tie)(tie)(tie)素(su)體(ti)(ti)(ti)和奧(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni元素(su)含(han)(han)(han)(han)(han)量(liang)(liang)與固(gu)(gu)(gu)溶(rong)(rong)溫(wen)度(du)(du)的(de)(de)(de)關系圖(tu)。圖(tu)3.7(a)~(d)證實了鐵(tie)(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Cr和Mo含(han)(han)(han)(han)(han)量(liang)(liang)更(geng)高(gao),而奧(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Ni和Mn含(han)(han)(han)(han)(han)量(liang)(liang)更(geng)高(gao)。從(cong)圖(tu)中(zhong)(zhong)(zhong)(zhong)可看出(chu),鐵(tie)(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Cr含(han)(han)(han)(han)(han)量(liang)(liang)為(wei)(wei)23.77%~25.16%,比奧(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)Cr含(han)(han)(han)(han)(han)量(liang)(liang)高(gao)2%左(zuo)右(you);鐵(tie)(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)Mo含(han)(han)(han)(han)(han)量(liang)(liang)為(wei)(wei)3.86%~4.37%,比奧(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Mo含(han)(han)(han)(han)(han)量(liang)(liang)高(gao)1.7%左(zuo)右(you);奧(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Ni含(han)(han)(han)(han)(han)量(liang)(liang)為(wei)(wei)5.42%、6.7%,比鐵(tie)(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Ni含(han)(han)(han)(han)(han)量(liang)(liang)高(gao)2%;當(dang)固(gu)(gu)(gu)溶(rong)(rong)處理(li)溫(wen)度(du)(du)為(wei)(wei)1050℃時,鐵(tie)(tie)(tie)素(su)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo和Ni含(han)(han)(han)(han)(han)量(liang)(liang)分(fen)別為(wei)(wei)23.77%、3.97%、4.24%,奧(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo和Ni含(han)(han)(han)(han)(han)量(liang)(liang)分(fen)別為(wei)(wei)23.53%、2.63%、5.42%.可見在1050℃溫(wen)度(du)(du)下進行(xing)固(gu)(gu)(gu)溶(rong)(rong)時,兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni含(han)(han)(han)(han)(han)量(liang)(liang)差(cha)(cha)(cha)異最小,此時鐵(tie)(tie)(tie)素(su)體(ti)(ti)(ti)含(han)(han)(han)(han)(han)量(liang)(liang)為(wei)(wei)51.9%,奧(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)含(han)(han)(han)(han)(han)量(liang)(liang)為(wei)(wei)48.1%.當(dang)固(gu)(gu)(gu)溶(rong)(rong)溫(wen)度(du)(du)改變(bian)(bian)時,鐵(tie)(tie)(tie)素(su)體(ti)(ti)(ti)/奧(ao)(ao)氏(shi)(shi)體(ti)(ti)(ti)兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)比例相(xiang)(xiang)(xiang)(xiang)差(cha)(cha)(cha)變(bian)(bian)大,且兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni含(han)(han)(han)(han)(han)量(liang)(liang)差(cha)(cha)(cha)異也(ye)變(bian)(bian)大。當(dang)固(gu)(gu)(gu)溶(rong)(rong)溫(wen)度(du)(du)為(wei)(wei)1000℃,兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(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)(gu)溶(rong)(rong)溫(wen)度(du)(du)為(wei)(wei)1150℃時,兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)Cr為(wei)(wei)2.29%、Mo為(wei)(wei)1.34%、Ni為(wei)(wei)2.09%,可見1000℃固(gu)(gu)(gu)溶(rong)(rong)試(shi)樣(yang)的(de)(de)(de)兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)的(de)(de)(de)Cr、Mo、Ni元素(su)含(han)(han)(han)(han)(han)量(liang)(liang)差(cha)(cha)(cha)大于1150℃固(gu)(gu)(gu)溶(rong)(rong)試(shi)樣(yang)的(de)(de)(de)兩(liang)(liang)相(xiang)(xiang)(xiang)(xiang)中(zhong)(zhong)(zhong)(zhong)Cr、Mo、Ni元素(su)含(han)(han)(han)(han)(han)量(liang)(liang)差(cha)(cha)(cha)。
由公(gong)式“PREN.=[Cr]+3.3[Mo]”計(ji)算鐵素體的(de)PREN值(zhi),由公(gong)式“PREN,=[Cr]+3.3[Mo]+16[N]-[Mn]”計(ji)算奧氏體的(de)PREN值(zhi),可(ke)(ke)得PREN值(zhi)與固(gu)溶溫(wen)度(du)的(de)關系圖,如(ru)圖3.7(e)所示。從圖3.7(e)可(ke)(ke)看出,在不同(tong)固(gu)溶狀態下,兩相的(de)PREN值(zhi)有所不同(tong),但PRENa>PRENy.當固(gu)溶溫(wen)度(du)為1050℃時,PREN.最小、PREN,最大,分別為36.9和30.6,兩者相差最小。
圖(tu)3.8為不同固(gu)溶(rong)試樣(yang)的(de)極(ji)化(hua)(hua)曲線。可見,在自(zi)腐(fu)蝕(shi)電(dian)(dian)(dian)位下(xia),材料開(kai)始發生(sheng)鈍化(hua)(hua);當極(ji)化(hua)(hua)電(dian)(dian)(dian)位升高到(dao)一定值時,不同固(gu)溶(rong)的(de)材料都發生(sheng)點蝕(shi),電(dian)(dian)(dian)流(liu)密(mi)度急劇增(zeng)大。根據GB 4334.9-1984中(zhong)電(dian)(dian)(dian)流(liu)密(mi)度為0.1mA/c㎡所(suo)對(dui)應的(de)電(dian)(dian)(dian)位為點蝕(shi)電(dian)(dian)(dian)位和(he)Tafel擬合,分別得到(dao)點蝕(shi)電(dian)(dian)(dian)位、自(zi)腐(fu)蝕(shi)電(dian)(dian)(dian)流(liu)密(mi)度與固(gu)溶(rong)溫度的(de)關(guan)系圖(tu),如圖(tu)3.11(a)所(suo)示。
圖(tu)(tu)3.9(a)、(b)分(fen)別(bie)為不同(tong)固(gu)溶試(shi)樣的Nyquist 圖(tu)(tu)和(he)(he)Bode圖(tu)(tu)。從(cong)圖(tu)(tu)3.9(a)可(ke)見(jian),試(shi)樣在(zai)(zai)低頻(pin)和(he)(he)高頻(pin)區分(fen)別(bie)存(cun)在(zai)(zai)一個(ge)容抗(kang)(kang)弧。從(cong)圖(tu)(tu)3.9(b)可(ke)見(jian),試(shi)樣在(zai)(zai)低頻(pin)和(he)(he)高頻(pin)處分(fen)別(bie)存(cun)在(zai)(zai)一個(ge)時間(jian)常(chang)數(shu)。根據曹楚南的《電化(hua)學阻(zu)抗(kang)(kang)譜導論》可(ke)知。雙相不銹(xiu)鋼在(zai)(zai)NaCl溶液中的阻(zu)抗(kang)(kang)譜中存(cun)在(zai)(zai)兩個(ge)時間(jian)常(chang)數(shu),常(chang)以圖(tu)(tu)3.10所(suo)示的等(deng)效電路(R1為電荷轉移電阻(zu),R2為鈍(dun)化(hua)膜(mo)電阻(zu))進行(xing)阻(zu)抗(kang)(kang)擬(ni)合。經(jing)阻(zu)抗(kang)(kang)擬(ni)合,得(de)到鈍(dun)化(hua)膜(mo)電阻(zu)、電荷轉移電阻(zu)與固(gu)溶處理(li)溫度的關系圖(tu)(tu),如圖(tu)(tu)3.11(b)所(suo)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)過計算得到不(bu)同相(xiang)(xiang)比例(li)下(xia)的(de)(de)鐵素體PREN值和(he)奧氏體PREN值,可(ke)(ke)見(jian)不(bu)同相(xiang)(xiang)比例(li)下(xia)的(de)(de)PREN.都(dou)大于PREN,.雙(shuang)(shuang)(shuang)相(xiang)(xiang)不(bu)銹(xiu)鋼(gang)的(de)(de)耐(nai)(nai)(nai)(nai)點(dian)蝕(shi)(shi)(shi)性(xing)(xing)能(neng)(neng)可(ke)(ke)通(tong)過點(dian)蝕(shi)(shi)(shi)電(dian)(dian)(dian)位衡量(liang)。點(dian)蝕(shi)(shi)(shi)電(dian)(dian)(dian)位越高(gao)(gao),耐(nai)(nai)(nai)(nai)點(dian)獨性(xing)(xing)能(neng)(neng)越好(hao)(hao)。前人認為雙(shuang)(shuang)(shuang)相(xiang)(xiang)不(bu)銹(xiu)鋼(gang)的(de)(de)耐(nai)(nai)(nai)(nai)點(dian)蝕(shi)(shi)(shi)性(xing)(xing)能(neng)(neng)由B能(neng)(neng)N值較區的(de)(de)相(xiang)(xiang)決定,且(qie)PEN值越高(gao)(gao),耐(nai)(nai)(nai)(nai)點(dian)蝕(shi)(shi)(shi)性(xing)(xing)能(neng)(neng)越好(hao)(hao),從圖(tu)3.71e)可(ke)(ke)矩(ju),不(bu)同海溶試樣(yang)的(de)(de)PREN.都(dou)大于PREN,,當固溶溫度為1050℃時,PHEN,最(zui)大,材料的(de)(de)耐(nai)(nai)(nai)(nai)點(dian)蝕(shi)(shi)(shi)性(xing)(xing)能(neng)(neng)應最(zui)好(hao)(hao)。從圖(tu)3.11(a)、(b)可(ke)(ke)知(zhi),1050℃固溶試樣(yang)的(de)(de)點(dian)蝕(shi)(shi)(shi)電(dian)(dian)(dian)位最(zui)高(gao)(gao),鈍化膜阻抗值最(zui)大,電(dian)(dian)(dian)荷轉(zhuan)移電(dian)(dian)(dian)阻值最(zui)商(shang);且(qie)從圖(tu)3.12(b)可(ke)(ke)見(jian),1050℃固溶試樣(yang)的(de)(de)點(dian)蝕(shi)(shi)(shi)坑尺寸(cun)最(zui)小,表現出(chu)最(zui)好(hao)(hao)的(de)(de)耐(nai)(nai)(nai)(nai)點(dian)蝕(shi)(shi)(shi)性(xing)(xing)能(neng)(neng)。綜上可(ke)(ke)知(zhi),雙(shuang)(shuang)(shuang)相(xiang)(xiang)不(bu)銹(xiu)鋼(gang)的(de)(de)耐(nai)(nai)(nai)(nai)點(dian)蝕(shi)(shi)(shi)性(xing)(xing)能(neng)(neng)由 PREN 值較小相(xiang)(xiang)決定的(de)(de)理論是有實驗依據(ju)的(de)(de)。
從圖3.12(a)~(d)可見,在不同固(gu)溶狀(zhuang)態下,鐵素體(ti)相(xiang)(xiang)都(dou)更易發生(sheng)點蝕;而從圖3.7(e)可見,在不同固(gu)溶狀(zhuang)態下,PREN.都(dou)大于PREN,,鐵素體(ti)的(de)耐點蝕性能應(ying)優于奧(ao)氏體(ti)相(xiang)(xiang),可見兩者存在矛盾(dun)。
隨固(gu)(gu)溶(rong)(rong)溫度變化,雙(shuang)相(xiang)(xiang)(xiang)不銹鋼(gang)(gang)中(zhong)(zhong)的(de)(de)鐵素(su)(su)(su)(su)(su)體和奧氏體相(xiang)(xiang)(xiang)的(de)(de)比例改變,且兩相(xiang)(xiang)(xiang)形(xing)態也發(fa)生(sheng)變化。Cr是鐵素(su)(su)(su)(su)(su)體形(xing)成(cheng)(cheng)元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su),可(ke)(ke)(ke)提高材(cai)(cai)(cai)料(liao)(liao)的(de)(de)耐(nai)蝕(shi)(shi)性(xing)(xing)(xing)能;Mo是鐵素(su)(su)(su)(su)(su)體形(xing)成(cheng)(cheng)元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su),可(ke)(ke)(ke)提高點蝕(shi)(shi)電位(wei),降低腐(fu)蝕(shi)(shi)速率;Ni是奧氏體形(xing)成(cheng)(cheng)元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su),可(ke)(ke)(ke)維持兩相(xiang)(xiang)(xiang)平衡,提高耐(nai)蝕(shi)(shi)性(xing)(xing)(xing)能。并(bing)(bing)且材(cai)(cai)(cai)料(liao)(liao)中(zhong)(zhong)存在一定(ding)量(liang)的(de)(de)N,其(qi)為(wei)奧氏體形(xing)成(cheng)(cheng)元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su),提高局部(bu)腐(fu)蝕(shi)(shi)抗力。從圖3.7(a)~(c)可(ke)(ke)(ke)見,隨固(gu)(gu)溶(rong)(rong)溫度變化,兩相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)Cr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su)含(han)量(liang)發(fa)生(sheng)變化。由于(yu)Cr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su)之(zhi)(zhi)間的(de)(de)腐(fu)蝕(shi)(shi)電位(wei)存在差(cha)異,勢必造成(cheng)(cheng)兩相(xiang)(xiang)(xiang)之(zhi)(zhi)間存在電化學差(cha)異,使腐(fu)蝕(shi)(shi)更易發(fa)生(sheng)。從圖3.7(e)可(ke)(ke)(ke)知,不同固(gu)(gu)溶(rong)(rong)狀(zhuang)態下材(cai)(cai)(cai)料(liao)(liao)的(de)(de)PREN,大(da)小關(guan)系為(wei)1050℃>1000℃>1150℃>1100℃,因此(ci)根據前人的(de)(de)研究,不同固(gu)(gu)溶(rong)(rong)態材(cai)(cai)(cai)料(liao)(liao)的(de)(de)耐(nai)點蝕(shi)(shi)性(xing)(xing)(xing)能優劣關(guan)系應為(wei):1050℃優于(yu)1000℃優于(yu)1150℃.當(dang)固(gu)(gu)溶(rong)(rong)溫度為(wei)1050℃時,PREN,值(zhi)(zhi)較(jiao)大(da),兩相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)Cr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su)含(han)量(liang)差(cha)異最(zui)小,材(cai)(cai)(cai)料(liao)(liao)的(de)(de)點蝕(shi)(shi)坑(keng)較(jiao)小,材(cai)(cai)(cai)料(liao)(liao)的(de)(de)耐(nai)點蝕(shi)(shi)性(xing)(xing)(xing)能最(zui)優。1000℃固(gu)(gu)溶(rong)(rong)試(shi)(shi)樣的(de)(de)點蝕(shi)(shi)坑(keng)尺寸大(da)于(yu)1150℃固(gu)(gu)溶(rong)(rong)試(shi)(shi)樣的(de)(de)點蝕(shi)(shi)坑(keng)尺寸,因此(ci),前者(zhe)的(de)(de)耐(nai)點蝕(shi)(shi)性(xing)(xing)(xing)能劣于(yu)后(hou)者(zhe)的(de)(de)耐(nai)點蝕(shi)(shi)性(xing)(xing)(xing)能。由此(ci)可(ke)(ke)(ke)見,雙(shuang)相(xiang)(xiang)(xiang)不銹鋼(gang)(gang)中(zhong)(zhong)的(de)(de)相(xiang)(xiang)(xiang)腐(fu)蝕(shi)(shi)不能僅(jin)僅(jin)由PREN值(zhi)(zhi)來(lai)解(jie)釋。由圖3.7(a)~(c)可(ke)(ke)(ke)知,1000℃固(gu)(gu)溶(rong)(rong)試(shi)(shi)樣的(de)(de)兩相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)Cr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su)含(han)量(liang)差(cha)大(da)于(yu)1150℃固(gu)(gu)溶(rong)(rong)試(shi)(shi)樣的(de)(de)兩相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)Gr、Mo、Ni元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su)含(han)量(liang)差(cha),因此(ci),雙(shuang)相(xiang)(xiang)(xiang)不銹鋼(gang)(gang)中(zhong)(zhong)的(de)(de)相(xiang)(xiang)(xiang)腐(fu)蝕(shi)(shi)還(huan)與(yu)兩相(xiang)(xiang)(xiang)中(zhong)(zhong)的(de)(de)元(yuan)(yuan)(yuan)(yuan)素(su)(su)(su)(su)(su)分布有關(guan),并(bing)(bing)且還(huan)需考慮(lv)到材(cai)(cai)(cai)料(liao)(liao)中(zhong)(zhong)點蝕(shi)(shi)敏感性(xing)(xing)(xing)較(jiao)強(qiang)的(de)(de)區(qu)域,如晶界和相(xiang)(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)(ying)響雙(shuang)相(xiang)不銹鋼(gang)相(xiang)腐蝕的因(yin)(yin)(yin)素不僅包(bao)括PREN值,還包(bao)括各(ge)相(xiang)中的元素分布和兩相(xiang)比例,并且三(san)者互相(xiang)影(ying)(ying)響、關系(xi)復雜。因(yin)(yin)(yin)此,不能(neng)僅憑PREN值的大小(xiao)來判斷耐點蝕能(neng)力,應該綜合考慮各(ge)因(yin)(yin)(yin)素的影(ying)(ying)響。