當濃度較大時,則由于疏水基團互相作用而在金屬表面形成雙分子層吸附膜。表面活性劑濃(nong)度(du)(du)的(de)增大可以(yi)提高(gao)其(qi)緩蝕效率,當濃(nong)度(du)(du)增大到使(shi)其(qi)在金屬(shu)表(biao)面(mian)達到飽和吸(xi)附(fu)時,呈(cheng)現出(chu)佳的(de)緩蝕效率,對某系(xi)表(biao)面(mian)活性劑(ji)來(lai)說(shuo),緩蝕效率在臨界膠束濃(nong)度(du)(du)cmc附(fu)近達到大。?
疏水長(chang)鏈(lian)(lian)(lian)烷基(ji)對緩(huan)蝕(shi)作用的(de)(de)(de)影(ying)響比較(jiao)(jiao)復雜(za),當鏈(lian)(lian)(lian)長(chang)較(jiao)(jiao)短及(ji)雜(za)原(yuan)(yuan)(yuan)子(zi)(zi)(zi)上(shang)烷基(ji)較(jiao)(jiao)少時(shi),碳(tan)鏈(lian)(lian)(lian)的(de)(de)(de)加長(chang)及(ji)烷基(ji)的(de)(de)(de)增(zeng)加可(ke)使(shi)表面(mian)(mian)活(huo)性劑的(de)(de)(de)緩(huan)蝕(shi)作用提(ti)高(gao)。這是由(you)于(yu)表面(mian)(mian)活(huo)性劑在金(jin)(jin)屬表面(mian)(mian)的(de)(de)(de)吸(xi)附(fu)是由(you)雜(za)原(yuan)(yuan)(yuan)子(zi)(zi)(zi)提(ti)供孤電(dian)子(zi)(zi)(zi)對與金(jin)(jin)屬表面(mian)(mian)的(de)(de)(de)金(jin)(jin)屬離子(zi)(zi)(zi)形(xing)成(cheng)配(pei)位(wei)鍵,烷基(ji)是斥電(dian)子(zi)(zi)(zi)基(ji),碳(tan)鏈(lian)(lian)(lian)的(de)(de)(de)增(zeng)長(chang)及(ji)烷基(ji)的(de)(de)(de)增(zeng)多(duo)可(ke)提(ti)高(gao)斥電(dian)子(zi)(zi)(zi)效(xiao)應,使(shi)雜(za)原(yuan)(yuan)(yuan)子(zi)(zi)(zi)上(shang)的(de)(de)(de)電(dian)子(zi)(zi)(zi)云密度(du)增(zeng)大,使(shi)得形(xing)成(cheng)的(de)(de)(de)配(pei)位(wei)鍵更加穩固,有利于(yu)提(ti)高(gao)緩(huan)蝕(shi)效(xiao)率。但碳(tan)鏈(lian)(lian)(lian)太長(chang)的(de)(de)(de)表面(mian)(mian)活(huo)性劑溶(rong)解度(du)下降,使(shi)其在腐蝕(shi)介(jie)質中(zhong)的(de)(de)(de)濃(nong)度(du)達(da)不到飽和吸(xi)附(fu)所(suo)需的(de)(de)(de)濃(nong)度(du),所(suo)以達(da)到一(yi)定的(de)(de)(de)鏈(lian)(lian)(lian)長(chang)后,再進一(yi)步增(zeng)加碳(tan)原(yuan)(yuan)(yuan)子(zi)(zi)(zi)數,緩(huan)蝕(shi)效(xiao)率反(fan)而(er)下降。?
表(biao)(biao)面(mian)(mian)活性(xing)(xing)(xing)劑(ji)(ji)分(fen)子(zi)(zi)中具有(you)親(qin)(qin)油(you)基(ji)和親(qin)(qin)水(shui)基(ji),為兩(liang)親(qin)(qin)分(fen)子(zi)(zi)。水(shui)是強極(ji)(ji)性(xing)(xing)(xing)液(ye)體,當表(biao)(biao)面(mian)(mian)活性(xing)(xing)(xing)劑(ji)(ji)溶(rong)于水(shui)中時,根據(ju)極(ji)(ji)性(xing)(xing)(xing)相(xiang)似(si)相(xiang)引﹑極(ji)(ji)性(xing)(xing)(xing)相(xiang)異(yi)相(xiang)斥原(yuan)理,其(qi)親(qin)(qin)水(shui)基(ji)與(yu)水(shui)相(xiang)引而溶(rong)于水(shui),其(qi)親(qin)(qin)油(you)基(ji)與(yu)水(shui)相(xiang)斥而離開水(shui),結(jie)果表(biao)(biao)面(mian)(mian)活性(xing)(xing)(xing)劑(ji)(ji)分(fen)子(zi)(zi)(或(huo)離子(zi)(zi))吸附(fu)(fu)在(zai)兩(liang)相(xiang)界(jie)面(mian)(mian)上(shang)(shang),使兩(liang)相(xiang)間的界(jie)面(mian)(mian)張(zhang)(zhang)力降低。表(biao)(biao)面(mian)(mian)活性(xing)(xing)(xing)劑(ji)(ji)分(fen)子(zi)(zi)(或(huo)離子(zi)(zi))在(zai)界(jie)面(mian)(mian)上(shang)(shang)吸附(fu)(fu)越多,界(jie)面(mian)(mian)張(zhang)(zhang)力降低越大。
表(biao)(biao)面(mian)(mian)(mian)活性(xing)劑在(zai)金(jin)(jin)屬(shu)(shu)(shu)表(biao)(biao)面(mian)(mian)(mian)發生吸(xi)(xi)附(fu)時(shi),其(qi)親水(shui)基團吸(xi)(xi)附(fu)在(zai)金(jin)(jin)屬(shu)(shu)(shu)表(biao)(biao)面(mian)(mian)(mian)上,因親水(shui)集(ji)團的(de)性(xing)質不(bu)同,而(er)與(yu)金(jin)(jin)屬(shu)(shu)(shu)表(biao)(biao)面(mian)(mian)(mian)發生物理吸(xi)(xi)附(fu)或(huo)者化學吸(xi)(xi)附(fu)。不(bu)同的(de)表(biao)(biao)面(mian)(mian)(mian)活性(xing)劑在(zai)金(jin)(jin)屬(shu)(shu)(shu)表(biao)(biao)面(mian)(mian)(mian)上的(de)吸(xi)(xi)附(fu)遵循(xun)不(bu)同的(de)吸(xi)(xi)附(fu)等溫式,表(biao)(biao)面(mian)(mian)(mian)活性(xing)劑濃(nong)度低時(shi),在(zai)金(jin)(jin)屬(shu)(shu)(shu)表(biao)(biao)面(mian)(mian)(mian)形(xing)成(cheng)單分(fen)子吸(xi)(xi)附(fu)層(ceng),疏(shu)水(shui)的(de)非極性(xing)部分(fen)在(zai)水(shui)溶液中形(xing)成(cheng)一層(ceng)斥(chi)水(shui)的(de)屏障覆蓋(gai)著金(jin)(jin)屬(shu)(shu)(shu)表(biao)(biao)面(mian)(mian)(mian)。