无码精品人妻一区二区三区影院_国产乱子经典视频在线观看_亚洲国产精品sss在线观看av_国产国语在线播放视频

銅鋁層狀復合板中性鹽霧腐蝕行為研究

2021-03-04 01:18:16 hualin

摘(zhai)要

采取模擬大(da)(da)氣環(huan)境的(de)(de)室內中(zhong)性(xing)鹽(yan)霧(wu)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)實(shi)驗,探討了銅(tong)鋁(lv)(lv)(lv)層狀復(fu)合材料的(de)(de)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)行為(wei)(wei)。通(tong)過(guo)掃描電(dian)(dian)鏡 (SEM) 觀察(cha)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)后銅(tong)鋁(lv)(lv)(lv)界(jie)面(mian)(mian)形貌,結合X射線衍(yan)射儀(yi) (XRD) 和(he)能譜儀(yi) (EDS) 分(fen)析腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)產(chan)物成(cheng)分(fen),并通(tong)過(guo)電(dian)(dian)化(hua)學(xue)檢測分(fen)析試(shi)樣經過(guo)不(bu)同(tong)時間鹽(yan)霧(wu)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)后的(de)(de)表面(mian)(mian)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)狀態,探討銅(tong)鋁(lv)(lv)(lv)復(fu)合板在(zai)服役環(huan)境下的(de)(de)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)機制。結果表明:銅(tong)鋁(lv)(lv)(lv)復(fu)合板在(zai)鹽(yan)霧(wu)環(huan)境下銅(tong)鋁(lv)(lv)(lv)構成(cheng)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)原電(dian)(dian)池,Al為(wei)(wei)陽極(ji)銅(tong)為(wei)(wei)陰極(ji),陰陽極(ji)面(mian)(mian)積比越大(da)(da),腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)速率越大(da)(da)。隨著腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)的(de)(de)不(bu)斷進行,銅(tong)鋁(lv)(lv)(lv)界(jie)面(mian)(mian)的(de)(de)Cu一側發生腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi),且靠近(jin)界(jie)面(mian)(mian)的(de)(de)位置腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)最(zui)為(wei)(wei)嚴(yan)重,隨著腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)時間延長,鋁(lv)(lv)(lv)基體出現嚴(yan)重的(de)(de)剝蝕(shi)(shi)(shi)(shi)(shi)現象,Cu幾(ji)乎無變(bian)化(hua)。腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)產(chan)物成(cheng)分(fen)為(wei)(wei)Al2O3,Al(OH)3和(he)AlO(OH),電(dian)(dian)化(hua)學(xue)結果顯示:銅(tong)鋁(lv)(lv)(lv)復(fu)合板在(zai)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)的(de)(de)過(guo)程中(zhong),腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)速率呈現先(xian)增(zeng)加(jia)(jia)后減小再增(zeng)加(jia)(jia)的(de)(de)趨勢。


關鍵詞(ci): 銅鋁層狀復合(he)板; 鹽霧腐(fu)蝕; 電(dian)化學(xue); 失重; 腐(fu)蝕產物


本文引用格式


張藝凡, 袁曉光, 黃宏(hong)軍(jun), 左曉姣, 程(cheng)禹霖(lin)。 銅鋁(lv)層狀復合板中性鹽(yan)霧腐(fu)蝕(shi)行為研究[J]. 中國腐(fu)蝕(shi)與(yu)防(fang)護學報, 2021, 41(2): 241-247 doi:

ZHANG Yifan, YUAN Xiaoguang, HUANG Hongjun, ZUO Xiaojiao, CHENG Yulin. Corrosion Behavior of Cu-Al Laminated Board in Neutral Salt Fog Environment[J]. Journal of Chinese Society for Corrosion and Protection, 2021, 41(2): 241-247 doi:

DOI 10.11902/1005.4537.2020.217


銅(tong)(tong)鋁(lv)(lv)復(fu)合(he)(he)(he)板材(cai)作(zuo)為(wei)(wei)一(yi)種新型復(fu)合(he)(he)(he)材(cai)料(liao)(liao),兼具(ju)(ju)了(le)鋁(lv)(lv)的(de)(de)(de)(de)(de)質輕、經濟和銅(tong)(tong)的(de)(de)(de)(de)(de)接觸電(dian)(dian)阻低、外表(biao)美觀(guan)、導(dao)電(dian)(dian)性(xing)好、導(dao)熱率高等(deng)優點,其(qi)廣泛應(ying)(ying)用(yong)(yong)(yong)(yong)于(yu)汽車、電(dian)(dian)子、電(dian)(dian)力、電(dian)(dian)器、石油(you)、化(hua)(hua)(hua)(hua)工、造(zao)船、冶(ye)金(jin)(jin)、機械、航空航天(tian)、生(sheng)(sheng)活(huo)用(yong)(yong)(yong)(yong)具(ju)(ju)、原子能(neng)等(deng)工業領域(yu)[1-3]。銅(tong)(tong)鋁(lv)(lv)復(fu)合(he)(he)(he)板長(chang)期服役于(yu)大氣(qi)環境(jing)中(zhong)(zhong)(zhong),發生(sheng)(sheng)的(de)(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)類型常常具(ju)(ju)有(you)多(duo)(duo)樣性(xing),由于(yu)不同(tong)的(de)(de)(de)(de)(de)材(cai)料(liao)(liao)之(zhi)間(jian)會形(xing)(xing)成(cheng)電(dian)(dian)偶(ou)(ou)對,且(qie)在(zai)(zai)(zai)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)的(de)(de)(de)(de)(de)過(guo)程中(zhong)(zhong)(zhong)往(wang)(wang)往(wang)(wang)還(huan)會受到(dao)介質中(zhong)(zhong)(zhong)侵蝕(shi)(shi)(shi)(shi)(shi)性(xing)離子的(de)(de)(de)(de)(de)作(zuo)用(yong)(yong)(yong)(yong),因(yin)(yin)此其(qi)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)機理相對復(fu)雜(za),其(qi)中(zhong)(zhong)(zhong)常見涉及的(de)(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)類型包括電(dian)(dian)偶(ou)(ou)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)、點蝕(shi)(shi)(shi)(shi)(shi)、縫隙(xi)(xi)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)、全面(mian)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)、化(hua)(hua)(hua)(hua)學(xue)(xue)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)及電(dian)(dian)化(hua)(hua)(hua)(hua)學(xue)(xue)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)等(deng)[4-6],而且(qie)表(biao)面(mian)往(wang)(wang)往(wang)(wang)具(ju)(ju)有(you)鈍(dun)化(hua)(hua)(hua)(hua)膜(mo)(mo),對其(qi)具(ju)(ju)有(you)保護(hu)作(zuo)用(yong)(yong)(yong)(yong),但表(biao)面(mian)常常存在(zai)(zai)(zai)局部(bu)缺陷,當存在(zai)(zai)(zai)破(po)(po)壞鈍(dun)化(hua)(hua)(hua)(hua)膜(mo)(mo)的(de)(de)(de)(de)(de)活(huo)性(xing)離子 (主要是鹵素原子Cl,F,Br,I,At) 與配位(wei)體(ti) (水中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)OH-) 時,容易(yi)造(zao)成(cheng)鈍(dun)化(hua)(hua)(hua)(hua)膜(mo)(mo)的(de)(de)(de)(de)(de)局部(bu)破(po)(po)壞,隨著(zhu)服役時間(jian)的(de)(de)(de)(de)(de)延長(chang),銅(tong)(tong)鋁(lv)(lv)材(cai)料(liao)(liao)遭受很強的(de)(de)(de)(de)(de)破(po)(po)壞作(zuo)用(yong)(yong)(yong)(yong)[7-9]。此外,銅(tong)(tong)板和鋁(lv)(lv)板結(jie)合(he)(he)(he)的(de)(de)(de)(de)(de)界(jie)面(mian)處在(zai)(zai)(zai)制備(bei)過(guo)程中(zhong)(zhong)(zhong)由于(yu)元(yuan)素之(zhi)間(jian)的(de)(de)(de)(de)(de)擴散作(zuo)用(yong)(yong)(yong)(yong),形(xing)(xing)成(cheng)了(le)金(jin)(jin)屬(shu)(shu)(shu)間(jian)化(hua)(hua)(hua)(hua)合(he)(he)(he)物(wu),這(zhe)些金(jin)(jin)屬(shu)(shu)(shu)間(jian)化(hua)(hua)(hua)(hua)合(he)(he)(he)物(wu)對復(fu)合(he)(he)(he)板的(de)(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)具(ju)(ju)有(you)一(yi)定(ding)的(de)(de)(de)(de)(de)影響作(zuo)用(yong)(yong)(yong)(yong)。研究表(biao)明,在(zai)(zai)(zai)銅(tong)(tong)鋁(lv)(lv)界(jie)面(mian)處存在(zai)(zai)(zai)著(zhu)多(duo)(duo)種金(jin)(jin)屬(shu)(shu)(shu)間(jian)化(hua)(hua)(hua)(hua)合(he)(he)(he)物(wu),例如CuAl、CuAl2、CuAl4和Cu9Al4,這(zhe)些金(jin)(jin)屬(shu)(shu)(shu)間(jian)化(hua)(hua)(hua)(hua)合(he)(he)(he)物(wu)雖然會增強異種金(jin)(jin)屬(shu)(shu)(shu)的(de)(de)(de)(de)(de)結(jie)合(he)(he)(he)力,但同(tong)時會削(xue)弱材(cai)料(liao)(liao)的(de)(de)(de)(de)(de)力學(xue)(xue)性(xing)能(neng)[10-12]。馮立臣等(deng)[13]認(ren)為(wei)(wei)在(zai)(zai)(zai)金(jin)(jin)屬(shu)(shu)(shu)間(jian)化(hua)(hua)(hua)(hua)合(he)(he)(he)物(wu)層邊(bian)緣容易(yi)產生(sheng)(sheng)應(ying)(ying)力集(ji)中(zhong)(zhong)(zhong),從而萌生(sheng)(sheng)裂紋源,通過(guo)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)性(xing)離子的(de)(de)(de)(de)(de)侵蝕(shi)(shi)(shi)(shi)(shi)加速(su)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)的(de)(de)(de)(de)(de)發生(sheng)(sheng)。殷(yin)祚炷等(deng)[14]卻發現銅(tong)(tong)鋁(lv)(lv)釬焊接頭(tou)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)金(jin)(jin)屬(shu)(shu)(shu)間(jian)化(hua)(hua)(hua)(hua)合(he)(he)(he)物(wu)是高電(dian)(dian)位(wei)陰極(ji)相,不易(yi)發生(sheng)(sheng)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)。尤其(qi)當銅(tong)(tong)鋁(lv)(lv)之(zhi)間(jian)構成(cheng)了(le)電(dian)(dian)偶(ou)(ou)對,產生(sheng)(sheng)的(de)(de)(de)(de)(de)電(dian)(dian)偶(ou)(ou)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)對其(qi)他腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)類型也具(ju)(ju)有(you)一(yi)定(ding)的(de)(de)(de)(de)(de)促進作(zuo)用(yong)(yong)(yong)(yong)。趙巖等(deng)[15]認(ren)為(wei)(wei)覆銅(tong)(tong)板 (CCL) 比純銅(tong)(tong)耐蝕(shi)(shi)(shi)(shi)(shi)性(xing)能(neng)差,因(yin)(yin)為(wei)(wei)發生(sheng)(sheng)了(le)電(dian)(dian)偶(ou)(ou)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)。陳國宏(hong)等(deng)[16]研究了(le)220 kV變電(dian)(dian)站(zhan)銅(tong)(tong)鋁(lv)(lv)過(guo)渡(du)線(xian)夾(jia)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)與斷裂的(de)(de)(de)(de)(de)問(wen)題(ti),研究認(ren)為(wei)(wei)銅(tong)(tong)鋁(lv)(lv)過(guo)渡(du)線(xian)夾(jia)底部(bu)產生(sheng)(sheng)的(de)(de)(de)(de)(de)焊縫腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)產物(wu)是由于(yu)Cu、Al兩種金(jin)(jin)屬(shu)(shu)(shu)之(zhi)間(jian)發生(sheng)(sheng)了(le)電(dian)(dian)化(hua)(hua)(hua)(hua)學(xue)(xue)反應(ying)(ying),從而形(xing)(xing)成(cheng)了(le)以鋁(lv)(lv)為(wei)(wei)負極(ji)、銅(tong)(tong)為(wei)(wei)正極(ji)的(de)(de)(de)(de)(de)原電(dian)(dian)池,加速(su)鋁(lv)(lv)發生(sheng)(sheng)縫隙(xi)(xi)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)。Davovdi等(deng)[17,18]將AFM和SECM相結(jie)合(he)(he)(he)觀(guan)察了(le)鋁(lv)(lv)合(he)(he)(he)金(jin)(jin)在(zai)(zai)(zai)NaCl溶液(ye)中(zhong)(zhong)(zhong)的(de)(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)行為(wei)(wei),發現鋁(lv)(lv)合(he)(he)(he)金(jin)(jin)最初發生(sheng)(sheng)的(de)(de)(de)(de)(de)點蝕(shi)(shi)(shi)(shi)(shi)是因(yin)(yin)為(wei)(wei)基體(ti)中(zhong)(zhong)(zhong)陽極(ji)性(xing)金(jin)(jin)屬(shu)(shu)(shu)間(jian)化(hua)(hua)(hua)(hua)合(he)(he)(he)物(wu)的(de)(de)(de)(de)(de)優先腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)或與金(jin)(jin)屬(shu)(shu)(shu)間(jian)化(hua)(hua)(hua)(hua)合(he)(he)(he)物(wu)鄰(lin)近局域(yu)的(de)(de)(de)(de)(de)金(jin)(jin)屬(shu)(shu)(shu)本體(ti)的(de)(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)造(zao)成(cheng)的(de)(de)(de)(de)(de),隨著(zhu)逐漸上升的(de)(de)(de)(de)(de)陽極(ji)電(dian)(dian)極(ji)電(dian)(dian)位(wei),腐(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)進一(yi)步加深(shen)。


大氣暴露腐(fu)(fu)蝕(shi)(shi)實(shi)驗(yan)是研究大氣腐(fu)(fu)蝕(shi)(shi)最精確、最可靠的(de)方法,但區域性強、實(shi)驗(yan)周期(qi)長,實(shi)驗(yan)結(jie)(jie)果(guo)不利(li)于廣(guang)泛(fan)推(tui)廣(guang)[19-22]。本文通過模擬(ni)大氣腐(fu)(fu)蝕(shi)(shi)進行室內中性鹽霧實(shi)驗(yan)以縮短(duan)實(shi)驗(yan)周期(qi),來探討在氯離子的(de)作用下不同陰陽極面(mian)積比的(de)銅鋁復合板材腐(fu)(fu)蝕(shi)(shi)行為(wei),判(pan)斷腐(fu)(fu)蝕(shi)(shi)對界(jie)面(mian)層(ceng)結(jie)(jie)合的(de)影響,進而獲得界(jie)面(mian)層(ceng)腐(fu)(fu)蝕(shi)(shi)對結(jie)(jie)合失(shi)效(xiao)的(de)影響機制,為(wei)以后得到腐(fu)(fu)蝕(shi)(shi)條(tiao)件(jian)下的(de)復合板服役條(tiao)件(jian)約(yue)束標(biao)準(zhun)奠定理論基礎。


1 實驗方法


實(shi)驗材料選用(yong)銅鋁層狀復合(he)板(ban)材,將其加工成20 mm×20 mm×6.6 m和20 mm×20 mm×3 mm的(de)試(shi)樣(yang),如圖1所(suo)示。兩板(ban)通過(guo)鑄(zhu)軋工藝(yi)形成冶金結(jie)合(he),在(zai)界面(mian)處存在(zai)三層擴(kuo)散(san)層,成分為AlCu、Al2Cu和Al4Cu9。將銅鋁結(jie)合(he)界面(mian)用(yong)600號到(dao)2000號砂(sha)紙逐(zhu)級打磨(mo)并拋光至(zhi)表面(mian)光亮(liang)均勻,用(yong)酒精(jing)擦洗后吹(chui)干(gan)并放(fang)在(zai)干(gan)燥(zao)皿(min)里干(gan)燥(zao)48 h后,使(shi)用(yong)游標卡尺(chi)測量試(shi)樣(yang)實(shi)際尺(chi)寸,并用(yong)精(jing)度為0.001 mg的(de)電子(zi)天平稱稱量試(shi)樣(yang)原始質量記錄下來。

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F001.png

圖(tu)1   銅鋁(lv)復合板結構圖(tu)


中性鹽(yan)(yan)霧(wu)(wu)(wu)(wu)腐(fu)(fu)蝕(shi)(shi)實驗按照(zhao)GB 6458-86在DG-170211鹽(yan)(yan)霧(wu)(wu)(wu)(wu)腐(fu)(fu)蝕(shi)(shi)機上(shang)進(jin)(jin)(jin)(jin)行(xing)(xing)。用(yong)棉繩將試樣懸掛在鹽(yan)(yan)霧(wu)(wu)(wu)(wu)腐(fu)(fu)蝕(shi)(shi)箱(xiang)工(gong)作室(shi)內,實驗溫度為(wei)(wei)(wei)35 ℃,選取不同(tong)時(shi)間進(jin)(jin)(jin)(jin)行(xing)(xing)濃度為(wei)(wei)(wei)5% (質量(liang)(liang)分(fen)數) NaCl溶液的連續(xu)鹽(yan)(yan)霧(wu)(wu)(wu)(wu)實驗,選取鹽(yan)(yan)霧(wu)(wu)(wu)(wu)腐(fu)(fu)蝕(shi)(shi)時(shi)間分(fen)別為(wei)(wei)(wei)24,144和240 h。鹽(yan)(yan)霧(wu)(wu)(wu)(wu)實驗后(hou),刮下表面(mian)腐(fu)(fu)蝕(shi)(shi)產物及(ji)表面(mian)附著的沉積(ji)鹽(yan)(yan),酒精(jing)清洗(xi)吹干后(hou),干燥48 h再(zai)進(jin)(jin)(jin)(jin)行(xing)(xing)稱(cheng)重,最后(hou)進(jin)(jin)(jin)(jin)行(xing)(xing)相關(guan)計算(suan)和檢測。在VSP300電化學(xue)工(gong)作站進(jin)(jin)(jin)(jin)行(xing)(xing)電化學(xue)實驗,飽和甘汞為(wei)(wei)(wei)參比電極(ji),鉑絲(si)為(wei)(wei)(wei)對(dui)電極(ji),工(gong)作電極(ji)即銅(tong)鋁復合(he)板(ban)使(shi)用(yong)熱熔膠將除了被(bei)測面(mian)以外均(jun)涂(tu)封好,被(bei)測面(mian)為(wei)(wei)(wei)銅(tong)鋁的結合(he)界面(mian),極(ji)化曲線掃描(miao)(miao)范圍(wei)(wei)是-1~1 V,掃描(miao)(miao)速度為(wei)(wei)(wei)10 mV/s,電化學(xue)阻(zu)抗頻率范圍(wei)(wei)為(wei)(wei)(wei)105~10-2 Hz,等效電路圖通過ZSIMPWIN軟件分(fen)析擬合(he),采(cai)用(yong)S-3400掃描(miao)(miao)電鏡 (SEM) 對(dui)銅(tong)鋁復合(he)板(ban)表面(mian)及(ji)腐(fu)(fu)蝕(shi)(shi)產物進(jin)(jin)(jin)(jin)行(xing)(xing)微觀形貌及(ji)132-1D EDX能譜(pu) (EDS) 分(fen)析成(cheng)分(fen),使(shi)用(yong)XRD-7000型X射線衍射儀 (XRD) 檢測腐(fu)(fu)蝕(shi)(shi)產物成(cheng)分(fen),掃描(miao)(miao)角度為(wei)(wei)(wei)10°~90°,掃描(miao)(miao)速度為(wei)(wei)(wei)8°/min。腐(fu)(fu)蝕(shi)(shi)失重采(cai)用(yong)公式(shi)W0?W1S計算(suan)得到,其中W1為(wei)(wei)(wei)腐(fu)(fu)蝕(shi)(shi)后(hou)重量(liang)(liang),g,W0為(wei)(wei)(wei)腐(fu)(fu)蝕(shi)(shi)前重量(liang)(liang),g,S為(wei)(wei)(wei)試樣暴露(lu)在鹽(yan)(yan)霧(wu)(wu)(wu)(wu)環(huan)境下的面(mian)積(ji),m2。


2 結(jie)果與分析


2.1 電化(hua)學檢測


為(wei)(wei)(wei)了研究陰陽(yang)極(ji)(ji)(ji)(ji)(ji)面(mian)(mian)(mian)積(ji)(ji)(ji)比(bi) (被(bei)測(ce)面(mian)(mian)(mian)上陰極(ji)(ji)(ji)(ji)(ji)銅(tong)面(mian)(mian)(mian)積(ji)(ji)(ji)與(yu)陽(yang)極(ji)(ji)(ji)(ji)(ji)鋁(lv)(lv)面(mian)(mian)(mian)積(ji)(ji)(ji)的(de)(de)(de)(de)比(bi)值) 對(dui)銅(tong)鋁(lv)(lv)復(fu)合(he)(he)板(ban)(ban)(ban)腐(fu)(fu)(fu)(fu)(fu)蝕(shi)性(xing)(xing)能(neng)的(de)(de)(de)(de)影響,將陰陽(yang)極(ji)(ji)(ji)(ji)(ji)面(mian)(mian)(mian)積(ji)(ji)(ji)比(bi)分別(bie)為(wei)(wei)(wei)0.16和0.18的(de)(de)(de)(de)銅(tong)鋁(lv)(lv)復(fu)合(he)(he)板(ban)(ban)(ban)浸泡在NaCl溶液中進行(xing)電(dian)化(hua)學檢測(ce),得(de)到極(ji)(ji)(ji)(ji)(ji)化(hua)曲線圖和電(dian)化(hua)學阻(zu)抗譜。圖2為(wei)(wei)(wei)測(ce)得(de)的(de)(de)(de)(de)極(ji)(ji)(ji)(ji)(ji)化(hua)曲線圖,通過Tafel外推法(fa)計算得(de)出的(de)(de)(de)(de)自腐(fu)(fu)(fu)(fu)(fu)蝕(shi)電(dian)流(liu)(liu)(liu)(liu)密(mi)(mi)度和自腐(fu)(fu)(fu)(fu)(fu)蝕(shi)電(dian)位(wei)如(ru)表(biao)1所(suo)示。自腐(fu)(fu)(fu)(fu)(fu)蝕(shi)電(dian)流(liu)(liu)(liu)(liu)密(mi)(mi)度可以反映材料(liao)的(de)(de)(de)(de)耐(nai)(nai)腐(fu)(fu)(fu)(fu)(fu)蝕(shi)性(xing)(xing)能(neng),自腐(fu)(fu)(fu)(fu)(fu)蝕(shi)電(dian)流(liu)(liu)(liu)(liu)密(mi)(mi)度越大(da)(da),說明材料(liao)的(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)蝕(shi)速率越快,耐(nai)(nai)腐(fu)(fu)(fu)(fu)(fu)蝕(shi)性(xing)(xing)能(neng)越差(cha)。從表(biao)1中可以看出,陰陽(yang)極(ji)(ji)(ji)(ji)(ji)面(mian)(mian)(mian)積(ji)(ji)(ji)比(bi)為(wei)(wei)(wei)0.16的(de)(de)(de)(de)銅(tong)鋁(lv)(lv)復(fu)合(he)(he)板(ban)(ban)(ban)的(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)蝕(shi)電(dian)流(liu)(liu)(liu)(liu)密(mi)(mi)度為(wei)(wei)(wei)19.2 μA·cm-2,陰陽(yang)極(ji)(ji)(ji)(ji)(ji)面(mian)(mian)(mian)積(ji)(ji)(ji)比(bi)為(wei)(wei)(wei)0.18的(de)(de)(de)(de)銅(tong)鋁(lv)(lv)復(fu)合(he)(he)板(ban)(ban)(ban)的(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)蝕(shi)電(dian)流(liu)(liu)(liu)(liu)密(mi)(mi)度為(wei)(wei)(wei)36.8 μA·cm-2,而純鋁(lv)(lv)的(de)(de)(de)(de)腐(fu)(fu)(fu)(fu)(fu)蝕(shi)電(dian)流(liu)(liu)(liu)(liu)密(mi)(mi)度為(wei)(wei)(wei)1.852 μA·cm-2,銅(tong)鋁(lv)(lv)復(fu)合(he)(he)板(ban)(ban)(ban)構成的(de)(de)(de)(de)電(dian)偶(ou)對(dui)降低了鋁(lv)(lv)的(de)(de)(de)(de)耐(nai)(nai)蝕(shi)性(xing)(xing)能(neng),隨著陰陽(yang)極(ji)(ji)(ji)(ji)(ji)面(mian)(mian)(mian)積(ji)(ji)(ji)比(bi)的(de)(de)(de)(de)增(zeng)大(da)(da),自腐(fu)(fu)(fu)(fu)(fu)蝕(shi)電(dian)流(liu)(liu)(liu)(liu)密(mi)(mi)度增(zeng)大(da)(da),說明銅(tong)鋁(lv)(lv)陰陽(yang)極(ji)(ji)(ji)(ji)(ji)面(mian)(mian)(mian)積(ji)(ji)(ji)比(bi)越大(da)(da),耐(nai)(nai)腐(fu)(fu)(fu)(fu)(fu)蝕(shi)性(xing)(xing)能(neng)變差(cha)。

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F002.png

圖2   不同陰陽極面積(ji)比的銅(tong)鋁復合板(ban)極化曲線

表1   極(ji)化曲線擬(ni)合數據

微信截圖_202.jpg

圖(tu)(tu)3為(wei)不同陰(yin)陽(yang)極(ji)(ji)面積(ji)比(bi)(bi)的(de)(de)(de)銅(tong)鋁(lv)復(fu)(fu)合(he)板測得(de)的(de)(de)(de)電(dian)(dian)(dian)化(hua)學(xue)阻(zu)(zu)(zu)抗(kang)(kang)(kang)譜,Nyquist圖(tu)(tu)均(jun)由一個容(rong)抗(kang)(kang)(kang)弧組(zu)成(cheng),bode圖(tu)(tu)中(zhong)(zhong)的(de)(de)(de)相(xiang)位角(jiao)圖(tu)(tu)顯示(shi)銅(tong)鋁(lv)復(fu)(fu)合(he)板為(wei)一個時(shi)間(jian)(jian)常(chang)數,而(er)純(chun)鋁(lv)為(wei)兩個時(shi)間(jian)(jian)常(chang)數,將電(dian)(dian)(dian)化(hua)學(xue)阻(zu)(zu)(zu)抗(kang)(kang)(kang)譜用(yong)ZSIMPWIN軟件(jian)擬(ni)合(he)成(cheng)如圖(tu)(tu)4a和b所示(shi)的(de)(de)(de)等(deng)效(xiao)電(dian)(dian)(dian)路圖(tu)(tu),擬(ni)合(he)數據如表(biao)(biao)2所示(shi),其(qi)中(zhong)(zhong)Rs為(wei)溶液電(dian)(dian)(dian)阻(zu)(zu)(zu),電(dian)(dian)(dian)容(rong)用(yong)常(chang)相(xiang)角(jiao)元件(jian)代替,CPEdl代表(biao)(biao)工(gong)作(zuo)(zuo)電(dian)(dian)(dian)極(ji)(ji)表(biao)(biao)面的(de)(de)(de)雙電(dian)(dian)(dian)層電(dian)(dian)(dian)容(rong),Rb代表(biao)(biao)腐蝕產(chan)物層電(dian)(dian)(dian)阻(zu)(zu)(zu),Rct代表(biao)(biao)工(gong)作(zuo)(zuo)電(dian)(dian)(dian)極(ji)(ji)表(biao)(biao)面反應的(de)(de)(de)電(dian)(dian)(dian)荷(he)(he)轉(zhuan)移電(dian)(dian)(dian)阻(zu)(zu)(zu),電(dian)(dian)(dian)荷(he)(he)轉(zhuan)移電(dian)(dian)(dian)阻(zu)(zu)(zu)越小,說明(ming)材料的(de)(de)(de)耐腐蝕性能(neng)越差。從(cong)表(biao)(biao)2中(zhong)(zhong)擬(ni)合(he)的(de)(de)(de)數據可以(yi)看出,陰(yin)陽(yang)極(ji)(ji)面積(ji)比(bi)(bi)為(wei)0.16的(de)(de)(de)銅(tong)鋁(lv)復(fu)(fu)合(he)板的(de)(de)(de)Rct為(wei)1421 Ω·cm2,陰(yin)陽(yang)極(ji)(ji)面積(ji)比(bi)(bi)為(wei)0.18的(de)(de)(de)銅(tong)鋁(lv)復(fu)(fu)合(he)板Rct為(wei)219 Ω·cm2,說明(ming)隨著陰(yin)陽(yang)極(ji)(ji)面積(ji)比(bi)(bi)的(de)(de)(de)增(zeng)大(da),工(gong)作(zuo)(zuo)電(dian)(dian)(dian)極(ji)(ji)表(biao)(biao)面的(de)(de)(de)電(dian)(dian)(dian)荷(he)(he)轉(zhuan)移電(dian)(dian)(dian)阻(zu)(zu)(zu)減小,材料的(de)(de)(de)耐腐蝕性能(neng)降低,純(chun)鋁(lv)電(dian)(dian)(dian)荷(he)(he)轉(zhuan)移電(dian)(dian)(dian)阻(zu)(zu)(zu)最(zui)大(da),該結果與極(ji)(ji)化(hua)曲(qu)線(xian)的(de)(de)(de)結果相(xiang)吻合(he)。從(cong)bode圖(tu)(tu)中(zhong)(zhong)的(de)(de)(de)阻(zu)(zu)(zu)抗(kang)(kang)(kang)曲(qu)線(xian)可以(yi)看出,純(chun)鋁(lv)的(de)(de)(de)阻(zu)(zu)(zu)抗(kang)(kang)(kang)值最(zui)大(da),且增(zeng)大(da)陰(yin)陽(yang)極(ji)(ji)面積(ji)比(bi)(bi)時(shi)阻(zu)(zu)(zu)抗(kang)(kang)(kang)值降低,也(ye)表(biao)(biao)明(ming)銅(tong)鋁(lv)復(fu)(fu)合(he)板的(de)(de)(de)耐腐蝕性能(neng)降低。

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F003.jpg

圖3   不(bu)同陰陽極面積比的(de)銅鋁復合板電化(hua)學阻(zu)抗譜

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F004.png

圖4   電化學阻抗等效電路(lu)圖

表2   電(dian)化學阻抗(kang)等效電(dian)路(lu)擬合(he)數據(ju)

微信截圖_202.jpg

圖5為經過不同時(shi)間鹽霧腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)后的(de)(de)(de)銅(tong)鋁復合板極化曲線(xian),相應(ying)的(de)(de)(de)擬合數據如表(biao)3所示(shi),從表(biao)中可以看出(chu),隨著腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)時(shi)間的(de)(de)(de)延長,腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)電流密度呈(cheng)現先增加后降低最后增加的(de)(de)(de)趨勢,這(zhe)是因為在腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)開(kai)始之前,材(cai)料(liao)表(biao)面(mian)會覆蓋一層鈍化膜(mo),保護基(ji)體(ti)免(mian)受腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)溶液(ye)的(de)(de)(de)侵蝕(shi)(shi)(shi)(shi)(shi)(shi),此時(shi)材(cai)料(liao)的(de)(de)(de)耐(nai)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)性能(neng)較好。當(dang)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)發展到24 h時(shi),材(cai)料(liao)表(biao)面(mian)的(de)(de)(de)氧化膜(mo)被腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)破壞,裸露出(chu)來的(de)(de)(de)基(ji)體(ti)與(yu)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)液(ye)接觸(chu)面(mian)積增大,使(shi)得材(cai)料(liao)的(de)(de)(de)耐(nai)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)性能(neng)變差(cha)。隨著腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)進行到144 h的(de)(de)(de)時(shi)候,材(cai)料(liao)表(biao)面(mian)生(sheng)成(cheng)新的(de)(de)(de)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)產物覆蓋在基(ji)體(ti)表(biao)面(mian),阻礙腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)溶液(ye)對基(ji)體(ti)的(de)(de)(de)進一步侵蝕(shi)(shi)(shi)(shi)(shi)(shi),材(cai)料(liao)的(de)(de)(de)耐(nai)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)性能(neng)提高。當(dang)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)到達240 h時(shi),由于后生(sheng)成(cheng)的(de)(de)(de)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)產物疏松多孔(kong)容易(yi)脫落,使(shi)得基(ji)體(ti)與(yu)溶液(ye)再(zai)一次接觸(chu),試樣的(de)(de)(de)耐(nai)腐(fu)(fu)蝕(shi)(shi)(shi)(shi)(shi)(shi)性能(neng)再(zai)次降低。

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F005.png

圖5   鹽霧腐蝕不同時間后的銅鋁復(fu)合(he)板極(ji)化曲線(xian)

表3   極化曲線擬(ni)合數(shu)據(ju)

微信截圖_202.jpg

圖(tu)(tu)(tu)6為(wei)經過(guo)(guo)不同鹽(yan)霧(wu)腐(fu)(fu)蝕(shi)時(shi)(shi)間后(hou)(hou)的(de)(de)銅鋁復合(he)板(ban)電(dian)化(hua)學阻(zu)抗譜,從(cong)(cong)圖(tu)(tu)(tu)6a中可以看(kan)出,阻(zu)抗譜均由(you)一個容抗弧(hu)組(zu)成,且(qie)容抗弧(hu)半徑隨(sui)著腐(fu)(fu)蝕(shi)時(shi)(shi)間的(de)(de)延(yan)長(chang)(chang),呈(cheng)現(xian)先(xian)減(jian)小(xiao)(xiao)(xiao)(xiao)再增(zeng)加(jia)最后(hou)(hou)減(jian)小(xiao)(xiao)(xiao)(xiao)的(de)(de)趨(qu)勢(shi),說明材料的(de)(de)耐腐(fu)(fu)蝕(shi)性(xing)能隨(sui)著鹽(yan)霧(wu)腐(fu)(fu)蝕(shi)時(shi)(shi)間的(de)(de)增(zeng)加(jia)呈(cheng)現(xian)先(xian)提(ti)高(gao)后(hou)(hou)降(jiang)低(di)(di)再提(ti)高(gao)的(de)(de)趨(qu)勢(shi)。圖(tu)(tu)(tu)6b圖(tu)(tu)(tu)中相位(wei)角圖(tu)(tu)(tu)顯示(shi)為(wei)一個時(shi)(shi)間常數(shu)。通過(guo)(guo)ZSIMPWIN軟件擬合(he)出的(de)(de)等效(xiao)電(dian)路圖(tu)(tu)(tu) (圖(tu)(tu)(tu)4) 數(shu)據如表4所示(shi)。從(cong)(cong)表4中可以看(kan)出,沒經過(guo)(guo)鹽(yan)霧(wu)腐(fu)(fu)蝕(shi)的(de)(de)銅鋁復合(he)板(ban)Rct為(wei)1.0×104 Ω·cm2,鹽(yan)霧(wu)腐(fu)(fu)蝕(shi)24 h后(hou)(hou)Rct降(jiang)低(di)(di)到1.9×103 Ω·cm2,到144 h時(shi)(shi)Rct升(sheng)高(gao)到7.6×103 Ω·cm2,當腐(fu)(fu)蝕(shi)發(fa)展(zhan)到240 h時(shi)(shi),Rct再次降(jiang)低(di)(di)到3.0×103 Ω·cm2。由(you)此(ci)可以看(kan)出,隨(sui)著腐(fu)(fu)蝕(shi)時(shi)(shi)間的(de)(de)延(yan)長(chang)(chang),電(dian)荷轉移電(dian)阻(zu)均呈(cheng)現(xian)先(xian)減(jian)小(xiao)(xiao)(xiao)(xiao)再增(zeng)加(jia)最后(hou)(hou)減(jian)小(xiao)(xiao)(xiao)(xiao)的(de)(de)趨(qu)勢(shi),波特圖(tu)(tu)(tu)中的(de)(de)阻(zu)抗值也是(shi)呈(cheng)現(xian)先(xian)減(jian)小(xiao)(xiao)(xiao)(xiao)再增(zeng)加(jia)最后(hou)(hou)減(jian)小(xiao)(xiao)(xiao)(xiao)的(de)(de)趨(qu)勢(shi),該(gai)結果(guo)與(yu)極化(hua)曲(qu)線的(de)(de)結果(guo)相吻合(he)。

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F006.jpg

圖6   鹽霧腐蝕不(bu)同時(shi)間后的銅鋁復(fu)合板電化學阻抗譜

表4   電化學阻抗等效電路(lu)擬(ni)合(he)數據

b4.jpg

2.2 腐蝕(shi)(shi)微觀形貌及腐蝕(shi)(shi)產物(wu)成(cheng)分(fen)分(fen)析


經過不同時(shi)間鹽(yan)霧腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)后的(de)(de)銅鋁(lv)(lv)界(jie)面腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)微(wei)觀形貌如圖(tu)7所示,從(cong)圖(tu)中(zhong)可(ke)以看出,腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)集(ji)中(zhong)在Al一側(ce),Cu一側(ce)幾乎(hu)無變(bian)(bian)化,且在界(jie)面處的(de)(de)腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)最(zui)為(wei)(wei)嚴重。腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)24 h時(shi) (圖(tu)7b),在鋁(lv)(lv)一側(ce)出現寬度均勻、接(jie)近500 μm的(de)(de)狹長腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)坑(keng)(keng),腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)坑(keng)(keng)處被腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)的(de)(de)基(ji)體(ti)(ti)呈現蜂(feng)窩狀,在鋁(lv)(lv)一側(ce)沿著(zhu)銅鋁(lv)(lv)界(jie)面處分布著(zhu)較為(wei)(wei)致密的(de)(de)白色塊(kuai)狀腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)產(chan)(chan)物(wu);腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)144 h時(shi)腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)坑(keng)(keng)面積(ji)(ji)變(bian)(bian)大(da),從(cong)圖(tu)中(zhong)可(ke)以看到腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)坑(keng)(keng)內開(kai)始生成新的(de)(de)龜裂狀腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)產(chan)(chan)物(wu);腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)到達240 h時(shi),鋁(lv)(lv)基(ji)體(ti)(ti)剝蝕(shi)(shi)(shi)現象(xiang)顯(xian)著(zhu),腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)產(chan)(chan)物(wu)脫(tuo)落現象(xiang)明(ming)顯(xian),裸露出的(de)(de)鋁(lv)(lv)基(ji)體(ti)(ti)面積(ji)(ji)更大(da)。圖(tu)8為(wei)(wei)腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)產(chan)(chan)物(wu)的(de)(de)成分分析(xi),其中(zhong)圖(tu)8a是(shi)腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)產(chan)(chan)物(wu)XRD檢測結果,結果顯(xian)示腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)產(chan)(chan)物(wu)的(de)(de)成分為(wei)(wei)Al2O3,AlO(OH) 和Al(OH)3。從(cong)圖(tu)8b的(de)(de)能譜(pu)分析(xi)上可(ke)以看出,腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)坑(keng)(keng)內腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)產(chan)(chan)物(wu)的(de)(de)元素除了有Al和O之外,還有一定含量的(de)(de)Cl,說明(ming)Cl-是(shi)致使銅鋁(lv)(lv)復合(he)板發生腐(fu)(fu)(fu)(fu)(fu)(fu)(fu)蝕(shi)(shi)(shi)的(de)(de)主要因素。

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F007.png

圖(tu)(tu)7 ;  不(bu)同(tong)鹽霧(wu)腐蝕時(shi)間銅鋁復合板界面形(xing)貌(mao)圖(tu)(tu)

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F008.jpg

圖(tu)8   腐蝕產物的XRD譜及EDS分析


2.3 腐蝕動力學(xue)


圖9為銅(tong)鋁復(fu)合(he)板在(zai)5%NaCl鹽霧環境下進(jin)行不同時間連續腐(fu)(fu)蝕(shi)(shi)的(de)動(dong)力學(xue)曲(qu)(qu)線(xian),通過origin軟件擬合(he)得到的(de)曲(qu)(qu)線(xian)方程(cheng)(cheng)如圖中(zhong)所示(shi),其中(zhong)R2=0.9962,說明(ming)擬合(he)效果(guo)良(liang)好。擬合(he)的(de)方程(cheng)(cheng)呈現(xian)冪指數形式:W=abn,其中(zhong)n的(de)大小代表腐(fu)(fu)蝕(shi)(shi)產(chan)物對(dui)(dui)腐(fu)(fu)蝕(shi)(shi)的(de)影(ying)響,當(dang)n<1時,說明(ming)腐(fu)(fu)蝕(shi)(shi)產(chan)物對(dui)(dui)腐(fu)(fu)蝕(shi)(shi)過程(cheng)(cheng)具有(you)抑(yi)制(zhi)作用;當(dang)n>1時,說明(ming)腐(fu)(fu)蝕(shi)(shi)產(chan)物對(dui)(dui)腐(fu)(fu)蝕(shi)(shi)過程(cheng)(cheng)具有(you)促進(jin)作用。銅(tong)鋁復(fu)合(he)板鹽霧腐(fu)(fu)蝕(shi)(shi)得到的(de)腐(fu)(fu)蝕(shi)(shi)動(dong)力學(xue)方程(cheng)(cheng)中(zhong)n值為1.55359,大于1,說明(ming)腐(fu)(fu)蝕(shi)(shi)產(chan)物對(dui)(dui)銅(tong)鋁復(fu)合(he)板的(de)腐(fu)(fu)蝕(shi)(shi)具有(you)促進(jin)作用。

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F009.png

圖9   鹽霧環境下的腐蝕動力學曲線


2.4 銅鋁復合板鹽霧腐蝕機理(li)


圖10是銅鋁(lv)復合板鹽霧腐蝕示意圖,當Cu和Al復合在一起時,兩種金屬的(de)(de)電(dian)(dian)(dian)(dian)位差構成電(dian)(dian)(dian)(dian)偶對,Cu的(de)(de)電(dian)(dian)(dian)(dian)位高于Al的(de)(de)電(dian)(dian)(dian)(dian)位,所以腐蝕的(de)(de)過(guo)程中(zhong)(zhong)鋁(lv)為陽極,Cu為陰極,因此Al的(de)(de)腐蝕較(jiao)為嚴重(zhong),而Cu側幾乎不腐蝕,這是對陰極Cu的(de)(de)一種保護作用。腐蝕過(guo)程中(zhong)(zhong)涉及的(de)(de)電(dian)(dian)(dian)(dian)化學(xue)反應方程式有:

AF633C07-0EE1-4537-B36B-5832C3FCC4CE-F010.png

圖10   銅鋁復合板鹽(yan)霧腐(fu)蝕示意圖


陽極:

微信截圖_202.jpg

陰極:

微信截圖_202.jpg

在腐(fu)蝕(shi)(shi)剛開始階段,由于(yu)金(jin)屬表面覆蓋(gai)一層致密的(de)(de)(de)鈍化膜,保護基(ji)體(ti)免受腐(fu)蝕(shi)(shi)性(xing)溶液(ye)的(de)(de)(de)侵蝕(shi)(shi),腐(fu)蝕(shi)(shi)速率較慢(man);隨(sui)著(zhu)腐(fu)蝕(shi)(shi)時間(jian)逐(zhu)(zhu)漸(jian)(jian)延(yan)長,由于(yu)侵蝕(shi)(shi)性(xing)離子Cl-的(de)(de)(de)存在,使(shi)得鈍化膜破壞(huai),基(ji)體(ti)與溶液(ye)相接觸(chu),腐(fu)蝕(shi)(shi)速率加快,鋁基(ji)體(ti)上(shang)出現點蝕(shi)(shi)坑并產生新的(de)(de)(de)腐(fu)蝕(shi)(shi)產物,且靠近(jin)銅鋁界面處的(de)(de)(de)Al腐(fu)蝕(shi)(shi)較為(wei)嚴(yan)重;腐(fu)蝕(shi)(shi)逐(zhu)(zhu)步進行的(de)(de)(de)過程中,鋁基(ji)體(ti)上(shang)小的(de)(de)(de)點蝕(shi)(shi)坑逐(zhu)(zhu)漸(jian)(jian)擴(kuo)展,銅鋁界面附近(jin)多個蝕(shi)(shi)坑連通形成更大更深的(de)(de)(de)腐(fu)蝕(shi)(shi)坑,腐(fu)蝕(shi)(shi)產物增多,除了塊狀之外(wai)還有龜裂狀的(de)(de)(de)腐(fu)蝕(shi)(shi)產物,阻礙(ai)基(ji)體(ti)與Cl-的(de)(de)(de)接觸(chu),腐(fu)蝕(shi)(shi)速率變慢(man),此(ci)時涉及的(de)(de)(de)反應(ying)方程式(shi)有:

微信截圖_202.jpg

其中AlOOH對基體具(ju)有(you)很強的保護作用;腐蝕(shi)后期由于(yu)后來逐漸形成疏松多孔(kong)易于(yu)脫落的腐蝕(shi)產(chan)物,與Cl-反應(ying)溶解,使(shi)得(de)基體再(zai)次裸(luo)露在外面,與溶液接(jie)觸(chu)面積增大,腐蝕(shi)速率提高(gao),此時涉及(ji)的反應(ying)方程式有(you):

微信截圖_202.jpg

因此腐蝕(shi)過(guo)(guo)程(cheng)是(shi)一個(ge)循(xun)環(huan)往復的過(guo)(guo)程(cheng),直到鋁(lv)基體被逐漸剝蝕(shi)掉。


3 結論


(1) 銅鋁復合(he)板在腐蝕(shi)(shi)過程中構(gou)成電(dian)偶(ou)對加速了Al的(de)腐蝕(shi)(shi),銅鋁復合(he)板經過鹽(yan)霧腐蝕(shi)(shi)后,腐蝕(shi)(shi)主要(yao)發生在Al一側,Cu側幾乎(hu)無變(bian)化(hua);且隨著(zhu)銅鋁陰陽極面積(ji)比的(de)增大,材(cai)料(liao)的(de)耐腐蝕(shi)(shi)性(xing)能變(bian)差。


(2) 由于銅鋁復(fu)合(he)(he)板的腐(fu)蝕(shi)(shi)是(shi)一個循環往(wang)復(fu)的過(guo)程,包括(kuo)基體(ti)的溶解、腐(fu)蝕(shi)(shi)產物的形成與(yu)脫落過(guo)程;隨著鹽霧腐(fu)蝕(shi)(shi)時間(jian)逐漸延長(chang),電化學檢(jian)測(ce)結果表明銅鋁復(fu)合(he)(he)板的耐腐(fu)蝕(shi)(shi)性能呈現(xian)先提高(gao)后(hou)降低再提高(gao)的趨勢。


(3) 銅鋁復合板(ban)失重曲線(xian)符合冪指數方程W=1.948×10-5t3.17156,腐(fu)(fu)(fu)蝕產(chan)物(wu)(wu)對腐(fu)(fu)(fu)蝕過(guo)程具有促進作用。腐(fu)(fu)(fu)蝕產(chan)物(wu)(wu)成分(fen)為Al2O3、AlO(OH) 和Al(OH)3,Cl-使得材料(liao)發(fa)生點蝕,在靠近界面處,鋁基體(ti)發(fa)生腐(fu)(fu)(fu)蝕最為嚴(yan)重;隨(sui)后(hou)腐(fu)(fu)(fu)蝕坑進一步(bu)向(xiang)橫向(xiang)和縱向(xiang)擴展,腐(fu)(fu)(fu)蝕產(chan)物(wu)(wu)逐(zhu)漸增多,再與Cl-反應而(er)脫落反復循(xun)環進行(xing)。