金屬材料跟周邊環境間產生的電化學或者化學反應而導致材料被破壞或者使材料產生變質的現象稱為金屬材料腐蝕。金屬腐蝕產生的重要條件為所處環境中必須具有能夠讓金屬發生氧化的物質,這種物質能夠與金屬構成熱力學不穩定體系。金屬發生腐蝕的類型可以分局部腐蝕跟均勻腐蝕,其中局部腐蝕包括孔蝕、應力腐蝕、縫隙腐蝕等。對于雙相(xiang)不(bu)銹鋼來講,點(dian)蝕應力(li)腐(fu)蝕都具有沒有明顯預兆、不易被察覺、破壞性極大的特點,是在化工生產、海洋等行業中經常遇到的問題,所以雙相不銹鋼的應力腐蝕破裂和孔(kong)蝕受到了研究者的廣泛關注。


1. 均勻腐蝕(shi)


  均勻腐蝕(Uniform Corrosion)表(biao)(biao)示腐蝕環(huan)境中于(yu)(yu)金(jin)(jin)屬(shu)所(suo)有表(biao)(biao)面或(huo)者金(jin)(jin)屬(shu)表(biao)(biao)面絕(jue)大(da)多數區域進行的腐蝕,因(yin)而(er)也可稱為全(quan)面腐蝕,其往往能夠導致(zhi)(zhi)金(jin)(jin)屬(shu)變薄。從(cong)重量角度來(lai)說(shuo),均勻腐蝕是金(jin)(jin)屬(shu)材料最大(da)破壞程(cheng)度的代(dai)表(biao)(biao),導致(zhi)(zhi)的金(jin)(jin)屬(shu)損(sun)耗最為嚴重,但是由于(yu)(yu)其發生在金(jin)(jin)屬(shu)的全(quan)部表(biao)(biao)面,易(yi)于(yu)(yu)發現和控(kong)制,因(yin)而(er)從(cong)技術(shu)層面來(lai)說(shuo)其危害(hai)性不大(da)。


2.點蝕


  點(dian)(dian)蝕(shi)(shi)(shi)(shi)(shi)(shi)又稱小(xiao)(xiao)孔(kong)腐(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)、孔(kong)蝕(shi)(shi)(shi)(shi)(shi)(shi)或(huo)者點(dian)(dian)蝕(shi)(shi)(shi)(shi)(shi)(shi),是(shi)集(ji)中在金屬(shu)(shu)(shu)表(biao)面較小(xiao)(xiao)區域內、能夠向金屬(shu)(shu)(shu)內部(bu)發展(zhan)、直徑小(xiao)(xiao)而深(shen)(shen)的一(yi)類腐(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)狀態(tai)。小(xiao)(xiao)孔(kong)腐(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)的嚴(yan)重(zhong)程(cheng)度(du)一(yi)般用點(dian)(dian)蝕(shi)(shi)(shi)(shi)(shi)(shi)系數(shu)(蝕(shi)(shi)(shi)(shi)(shi)(shi)孔(kong)的最(zui)大深(shen)(shen)度(du)和金屬(shu)(shu)(shu)平(ping)均腐(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)深(shen)(shen)度(du)之間的比值)表(biao)征,點(dian)(dian)蝕(shi)(shi)(shi)(shi)(shi)(shi)系數(shu)越高,點(dian)(dian)蝕(shi)(shi)(shi)(shi)(shi)(shi)產生的程(cheng)度(du)越深(shen)(shen)。當氧化劑跟鹵素(su)離子同時存在時,就會導致金屬(shu)(shu)(shu)局(ju)部(bu)溶解進而形成孔(kong)穴(xue)促進點(dian)(dian)蝕(shi)(shi)(shi)(shi)(shi)(shi)的產生。


 a. 點蝕產生的主要條件


 ①. 一般情況下點蝕較容易發生(sheng)在表(biao)(biao)面具有陰極性鍍(du)層(ceng)或表(biao)(biao)面存在鈍化(hua)(hua)膜(mo)的金(jin)(jin)屬(shu)上。當金(jin)(jin)屬(shu)表(biao)(biao)面這些膜(mo)的局部(bu)位置(zhi)產生(sheng)破壞,裸(luo)露出的新表(biao)(biao)面(陽(yang)極)與(yu)該膜(mo)層(ceng)未被破壞區域(陰極)就會形成活化(hua)(hua)-鈍化(hua)(hua)腐蝕電池,進而導(dao)致腐蝕朝著金(jin)(jin)屬(shu)內(nei)部(bu)縱深處(chu)發展促(cu)進小孔(kong)的生(sheng)成。


 ②. 點蝕(shi)常(chang)發生(sheng)于(yu)含有(you)特殊離子(zi)(zi)的腐蝕(shi)環境中,例如,雙相不銹鋼(gang)(gang)對鹵素(su)離子(zi)(zi)比較(jiao)敏感,如氯(lv)離子(zi)(zi)、溴離子(zi)(zi)、碘(dian)離子(zi)(zi)等,這些鹵素(su)離子(zi)(zi)會不均勻吸(xi)附在雙相不銹鋼(gang)(gang)的表面(mian),進而促進材料表面(mian)膜發生(sheng)不均勻破壞(huai)。


 ③. 點蝕(shi)的發生存(cun)在一(yi)個臨界電(dian)(dian)位(wei),這(zhe)個電(dian)(dian)位(wei)被稱為點蝕(shi)電(dian)(dian)位(wei)或者擊(ji)穿電(dian)(dian)位(wei),一(yi)般情(qing)況下當電(dian)(dian)位(wei)高于點蝕(shi)電(dian)(dian)位(wei)時會發生點蝕(shi)。


 b. 點蝕機(ji)理


  點蝕的(de)發生(sheng)主(zhu)要有三(san)個階段:


 ①. 蝕孔成(cheng)核


     鈍化(hua)膜吸附(fu)(fu)(fu)跟(gen)破壞理論(lun)可以用來解(jie)釋蝕(shi)孔(kong)成(cheng)核的(de)(de)原(yuan)因(yin)。鈍化(hua)膜破壞理論(lun)認為(wei):因(yin)為(wei)腐蝕(shi)性陰離(li)(li)子半徑比較小(xiao),因(yin)而當(dang)(dang)(dang)其吸附(fu)(fu)(fu)在(zai)雙相不銹鋼表(biao)(biao)(biao)面鈍化(hua)膜上時就(jiu)會很容(rong)易穿透鈍化(hua)膜,進(jin)(jin)而導致(zhi)(zhi)“氧化(hua)膜受到(dao)污染(ran)”及(ji)促進(jin)(jin)強(qiang)烈的(de)(de)感應離(li)(li)子導電的(de)(de)形成(cheng),因(yin)此于一定點(dian)(dian)處該膜可以保持比較高的(de)(de)電流(liu)密度(du),導致(zhi)(zhi)陽離(li)(li)子無(wu)規律移動進(jin)(jin)而變(bian)得活躍,當(dang)(dang)(dang)溶(rong)液一膜之間的(de)(de)界(jie)面電場(chang)到(dao)達某個(ge)臨界(jie)值時就(jiu)會產(chan)生(sheng)點(dian)(dian)蝕(shi)。鈍化(hua)膜吸附(fu)(fu)(fu)理論(lun)指出點(dian)(dian)蝕(shi)的(de)(de)產(chan)生(sheng)是氧跟(gen)氯離(li)(li)子之間競爭吸附(fu)(fu)(fu)導致(zhi)(zhi)的(de)(de),因(yin)為(wei)當(dang)(dang)(dang)氯離(li)(li)子取代了(le)金(jin)屬(shu)表(biao)(biao)(biao)面氧的(de)(de)吸附(fu)(fu)(fu)點(dian)(dian)后(hou)就(jiu)會產(chan)生(sheng)可溶(rong)性的(de)(de)金(jin)屬(shu)-羥-氯絡合物,導致(zhi)(zhi)金(jin)屬(shu)表(biao)(biao)(biao)面膜發(fa)生(sheng)破壞進(jin)(jin)而促進(jin)(jin)了(le)點(dian)(dian)蝕(shi)的(de)(de)產(chan)生(sheng),蝕(shi)核產(chan)生(sheng)以后(hou)這個(ge)點(dian)(dian)依然有再(zai)鈍化(hua)的(de)(de)能(neng)力,如果該點(dian)(dian)的(de)(de)再(zai)鈍化(hua)能(neng)力很強(qiang),蝕(shi)核就(jiu)不會繼續變(bian)大。小(xiao)蝕(shi)孔(kong)表(biao)(biao)(biao)現為(wei)開放式的(de)(de)狀(zhuang)態,在(zai)晶(jing)(jing)界(jie)上碳(tan)化(hua)物沉積、金(jin)屬(shu)內部(bu)硫化(hua)物夾雜及(ji)晶(jing)(jing)界(jie)、金(jin)屬(shu)表(biao)(biao)(biao)面的(de)(de)劃痕、位(wei)錯露頭(tou)等缺陷(xian)處更(geng)容(rong)易形成(cheng)蝕(shi)核。


 ②. 蝕孔(kong)生長(chang)階(jie)段


   蝕(shi)(shi)(shi)孔(kong)(kong)(kong)(kong)(kong)(kong)生(sheng)(sheng)(sheng)(sheng)成之后,孔(kong)(kong)(kong)(kong)(kong)(kong)蝕(shi)(shi)(shi)的(de)(de)(de)發展是(shi)十分迅速(su)的(de)(de)(de),一(yi)般用(yong)自(zi)(zi)催化過(guo)程來解(jie)釋蝕(shi)(shi)(shi)孔(kong)(kong)(kong)(kong)(kong)(kong)的(de)(de)(de)生(sheng)(sheng)(sheng)(sheng)長,如圖所(suo)示。雙相不(bu)銹(xiu)鋼在存(cun)在氯(lv)離子(zi)的(de)(de)(de)溶液中,陰極處會發生(sheng)(sheng)(sheng)(sheng)吸氧(yang)反應使孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei)氧(yang)的(de)(de)(de)濃(nong)(nong)度降低,然(ran)而(er)孔(kong)(kong)(kong)(kong)(kong)(kong)外(wai)(wai)的(de)(de)(de)氧(yang)、氧(yang)濃(nong)(nong)度依然(ran)較高(gao),所(suo)以孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei)外(wai)(wai)的(de)(de)(de)“供養差(cha)異(yi)電池”較容易形成。在孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei)金(jin)(jin)屬離子(zi)連續(xu)變多的(de)(de)(de)情況下,蝕(shi)(shi)(shi)孔(kong)(kong)(kong)(kong)(kong)(kong)外(wai)(wai)的(de)(de)(de)氯(lv)離子(zi)會向(xiang)孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei)移動從而(er)達(da)到能夠維持溶液電中性的(de)(de)(de)目(mu)的(de)(de)(de)。此外(wai)(wai),孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei)金(jin)(jin)屬離子(zi)漸(jian)漸(jian)變多并(bing)發生(sheng)(sheng)(sheng)(sheng)水解(jie)導(dao)致(zhi)蝕(shi)(shi)(shi)孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei)部H+濃(nong)(nong)度不(bu)斷升高(gao),這(zhe)時蝕(shi)(shi)(shi)孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei)部酸化就(jiu)會造成孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei)的(de)(de)(de)金(jin)(jin)屬材料表(biao)現為活化溶解(jie)狀態;而(er)蝕(shi)(shi)(shi)孔(kong)(kong)(kong)(kong)(kong)(kong)外(wai)(wai)部的(de)(de)(de)表(biao)面膜(mo)由于依然(ran)保(bao)持鈍態進而(er)形成了(le)活化(蝕(shi)(shi)(shi)孔(kong)(kong)(kong)(kong)(kong)(kong)內(nei)(nei)(nei))-鈍化(蝕(shi)(shi)(shi)孔(kong)(kong)(kong)(kong)(kong)(kong)外(wai)(wai))電池,促使金(jin)(jin)屬不(bu)斷產(chan)生(sheng)(sheng)(sheng)(sheng)溶解(jie),進而(er)導(dao)致(zhi)孔(kong)(kong)(kong)(kong)(kong)(kong)蝕(shi)(shi)(shi)按(an)照自(zi)(zi)催化的(de)(de)(de)過(guo)程繼(ji)續(xu)發展,促使腐蝕(shi)(shi)(shi)產(chan)生(sheng)(sheng)(sheng)(sheng)。


圖1.jpg


 ③. 蝕孔(kong)再鈍化階段


  蝕(shi)孔(kong)(kong)內金屬(shu)(shu)發(fa)生(sheng)的(de)(de)再鈍(dun)(dun)化(hua)(hua)會導致孔(kong)(kong)蝕(shi)進行到某個深度之后就不會繼續進行了。造(zao)成蝕(shi)孔(kong)(kong)再鈍(dun)(dun)化(hua)(hua)的(de)(de)成因(yin)有三(san)種:一是(shi)蝕(shi)孔(kong)(kong)內電(dian)(dian)位朝著(zhu)負方向移動至小于(yu)保(bao)護電(dian)(dian)位(E.)時金屬(shu)(shu)就會進入(ru)到鈍(dun)(dun)化(hua)(hua)區(qu)域,金屬(shu)(shu)再鈍(dun)(dun)化(hua)(hua)的(de)(de)產生(sheng)也可能是(shi)周邊(bian)區(qu)域的(de)(de)孔(kong)(kong)蝕(shi)劇(ju)烈(lie)發(fa)展或腐蝕(shi)介質的(de)(de)氧化(hua)(hua)還原(yuan)電(dian)(dian)位降低所造(zao)成的(de)(de);二(er)是(shi)金屬(shu)(shu)表面鈍(dun)(dun)化(hua)(hua)膜比較脆弱(ruo)的(de)(de)區(qu)域被(bei)(bei)消(xiao)除(chu),如(ru)夾雜物及(ji)晶間沉淀,金屬(shu)(shu)的(de)(de)再鈍(dun)(dun)化(hua)(hua)有可能在其被(bei)(bei)消(xiao)除(chu)之后而(er)(er)產生(sheng);三(san)是(shi)蝕(shi)孔(kong)(kong)內部(bu)的(de)(de)歐姆電(dian)(dian)壓會隨著(zhu)孔(kong)(kong)蝕(shi)的(de)(de)生(sheng)長而(er)(er)漸(jian)漸(jian)變大,導致蝕(shi)孔(kong)(kong)內部(bu)的(de)(de)電(dian)(dian)位轉移到鈍(dun)(dun)化(hua)(hua)區(qu)域,從而(er)(er)使金屬(shu)(shu)發(fa)生(sheng)再鈍(dun)(dun)化(hua)(hua)現象。


 3. 縫隙腐蝕


    金(jin)(jin)屬(shu)跟(gen)非金(jin)(jin)屬(shu)或者金(jin)(jin)屬(shu)跟(gen)金(jin)(jin)屬(shu)表(biao)面具有縫(feng)隙,并(bing)且(qie)腐(fu)蝕(shi)介質(zhi)(zhi)也(ye)同時存在時產生(sheng)的(de)腐(fu)蝕(shi)稱(cheng)為縫(feng)隙腐(fu)蝕(shi)。通常情況下,縫(feng)隙腐(fu)蝕(shi)發(fa)生(sheng)的(de)縫(feng)寬為0.025~0.1mm,這個寬度(du)能夠讓電解質(zhi)(zhi)溶液(ye)進(jin)(jin)入,進(jin)(jin)而(er)導(dao)致縫(feng)隙內(nei)部(bu)(bu)跟(gen)外部(bu)(bu)的(de)金(jin)(jin)屬(shu)組成短路電池發(fa)生(sheng)強烈(lie)的(de)腐(fu)蝕(shi),并(bing)且(qie)縫(feng)隙內(nei)部(bu)(bu)金(jin)(jin)屬(shu)作為陽極(ji),縫(feng)隙外部(bu)(bu)金(jin)(jin)屬(shu)作為陰極(ji)。其擴展(zhan)機(ji)理(li)(li)與點(dian)蝕(shi)類似(si)都是自催化過程,但是始發(fa)的(de)機(ji)理(li)(li)是不一(yi)樣的(de),此(ci)外就(jiu)同一(yi)種(zhong)金(jin)(jin)屬(shu)而(er)言相,對于點(dian)蝕(shi)較易產生(sheng)縫(feng)隙腐(fu)蝕(shi)。


 4. 晶間腐蝕


   在(zai)特(te)定的(de)(de)腐(fu)(fu)蝕(shi)(shi)環境中,沿著(zhu)或者(zhe)緊挨著(zhu)金屬(shu)晶(jing)粒邊界(jie)產生(sheng)的(de)(de)腐(fu)(fu)蝕(shi)(shi)稱為晶(jing)間(jian)腐(fu)(fu)蝕(shi)(shi)。晶(jing)間(jian)腐(fu)(fu)蝕(shi)(shi)是一(yi)種(zhong)(zhong)局部破壞(huai)現象,可以讓金屬(shu)晶(jing)粒之間(jian)的(de)(de)結合力(li)(li)消失(shi)。當金屬(shu)發生(sheng)晶(jing)間(jian)腐(fu)(fu)蝕(shi)(shi)并且有應力(li)(li)對其(qi)進行作(zuo)用(yong)時,金屬(shu)的(de)(de)強度(du)就會幾乎全部喪失(shi)、會沿晶(jing)界(jie)發生(sheng)斷裂(lie),但(dan)是金屬(shu)發生(sheng)的(de)(de)這種(zhong)(zhong)破壞(huai)是不(bu)易被觀察(cha)到的(de)(de),因為在(zai)其(qi)表面依然會呈現出一(yi)定的(de)(de)金屬(shu)光(guang)澤,所(suo)以晶(jing)間(jian)腐(fu)(fu)蝕(shi)(shi)是一(yi)類比較危(wei)險的(de)(de)腐(fu)(fu)蝕(shi)(shi)。


 5. 應力(li)腐蝕(shi)


 應力(li)腐蝕(shi)破(po)裂(SCC)是(shi)(shi)指在腐蝕(shi)介質和拉伸應力(li)兩者共同影響(xiang)下造成(cheng)金屬發(fa)(fa)生脆性(xing)斷(duan)裂的(de)現象。材料與介質的(de)匹(pi)配性(xing)是(shi)(shi)應力(li)腐蝕(shi)破(po)裂的(de)一(yi)(yi)個(ge)主(zhu)要特點之一(yi)(yi)。應力(li)腐蝕(shi)破(po)裂是(shi)(shi)在無(wu)顯著征兆的(de)情況(kuang)下突然發(fa)(fa)生的(de),因(yin)而破(po)壞性(xing)及危險(xian)性(xing)極大,在不銹鋼腐蝕(shi)破(po)壞形式中,應力(li)腐蝕(shi)占(zhan)20%以(yi)上,因(yin)此,雙相不銹鋼的(de)應力(li)腐蝕(shi)是(shi)(shi)一(yi)(yi)個(ge)很重要的(de)實際問題。