The Journal of
the Korean Journal of Metals and Materials

The Journal of
the Korean Journal of Metals and Materials

Monthly
  • pISSN : 1738-8228
  • eISSN : 2288-8241

Editorial Office


  1. ์ˆœ์ฒœ๋Œ€ํ•™๊ต ์‹ ์†Œ์žฌ๊ณตํ•™๊ณผ (Department of Advanced Materials Engineering, Sunchon National University, Suncheon 57922, Republic of Korea)
  2. ํฌ์Šค์ฝ” ๊ธฐ์ˆ ์—ฐ๊ตฌ์› (POSCO Technical Research Laboratories, Gwangyang 57807, Republic of Korea)



A516 steel, heat affected zone, hydrogen embrittlement, hydrogen permeation, corrosion, sulfide stress cracking

1. ์„œ ๋ก 

์ตœ๊ทผ ์ž๋™์ฐจ, ํ•ด์–‘ํ”Œ๋žœํŠธ ๋ฐ ์—๋„ˆ์ง€ ์‚ฐ์—…์˜์—ญ์—์„œ๋Š” ์‚ฐ์—…์ด ๊ณ ๋„ํ™”๋จ์— ๋”ฐ๋ผ ์ฃผ ์—๋„ˆ์ง€์›์ธ ํ™”์„์—ฐ๋ฃŒ์˜ ์ˆ˜์š”๊ฐ€ ์ฆ๊ฐ€ํ•˜๊ณ  ์žˆ์ง€๋งŒ, ์š”๊ตฌ๋˜๋Š” ์ˆ˜์š”๋Ÿ‰ ๋Œ€๋น„ ํ™”์„์—ฐ๋ฃŒ์˜ ๊ณต๊ธ‰๋Ÿ‰์€ ์„ธ๊ณ„์ ์ธ ์›์œ  ๊ณ ๊ฐˆ์— ๋”ฐ๋ผ ๊ฐ์†Œํ•˜๊ณ  ์žˆ๋Š” ์ถ”์„ธ์ด๋‹ค. ์ด์— ๋”ฐ๋ผ, ์„์œ  ํ™”ํ•™ ๋ฐ ํ”Œ๋žœํŠธ ๋“ฑ์˜ ๊ฐ ์‚ฐ์—…๊ตฐ์—์„œ๋Š” ์ถ”๊ฐ€์ ์ธ ์›์œ  ๊ณต๊ธ‰์„ ์œ„ํ•ด ์ƒ๋Œ€์  ํ’ˆ์งˆ์ด ๋‚ฎ์€ ์ €๊ธ‰ ์›์œ ๋ฅผ ์ƒ๋Œ€์  ๊ณ ๊ธ‰ ์›์œ ๋กœ ์ •์ œํ•˜๋ ค๋Š” ๋…ธ๋ ฅ์„ ๊ธฐ์šธ์ด๊ณ  ์žˆ๋‹ค [1-4]. ์ €๊ธ‰ ์›์œ ์˜ ์ •์ œ ํ™˜๊ฒฝ์€ ๊ณ ๊ธ‰ ์›์œ  ์ •์ œ ํ™˜๊ฒฝ ๋Œ€๋น„ H2S์™€ ๊ฐ™์€ ๋ถˆ์ˆœ๋ฌผ์ด ๋‹ค๋Ÿ‰ ํฌํ•จ๋˜๋Š” ๋“ฑ ๊ฐ€ํ˜นํ•œ ์กฐ๊ฑด์œผ๋กœ ์›์œ  ์ •์ œ๋ฅผ ์œ„ํ•œ ๊ธˆ์†์šฉ๊ธฐ์˜ ์†์ƒ์ด ํฌ๊ฒŒ ์šฐ๋ ค๋˜๊ณ  ์žˆ๋‹ค. ํŠนํžˆ ๊ธˆ์†์šฉ๊ธฐ์˜ ์†Œ์žฌ๋กœ ํญ๋„“์€ ์ ์šฉ์ด ์ด๋ฃจ์–ด์ง€๊ณ  ์žˆ๋Š” ์••๋ ฅ์šฉ๊ธฐ์šฉ ๊ฐ•์žฌ์˜ ๊ฒฝ์šฐ, ๊ณ ๋‚ด์‹ ํŠน์„ฑ ๋ฐ ์šฐ์ˆ˜ํ•œ ์ˆ˜์†Œ์ทจํ™”์ €ํ•ญ์„ฑ์ด ์š”๊ตฌ๋˜๊ณ  ์žˆ๋‹ค. ์ผ๋ฐ˜์ ์œผ๋กœ ์ €๊ธ‰ ์›์œ  ๋‚ด ํ•จ์œ ๋˜์–ด ์žˆ๋Š” H2S์˜ ๊ฒฝ์šฐ, ๊ฐ•์žฌ์˜ ๋ถ€์‹์†๋„๋ฅผ ๋†’์ด๊ณ  ๋ถ€์‹๋ฐ˜์‘์— ๊ธฐ์ธํ•˜์—ฌ ํ˜•์„ฑ๋œ ์ˆ˜์†Œ์›์ž๊ฐ€ ๊ฐ• ํ‘œ๋ฉด์— ํก์ฐฉ ๋ฐ ๋‚ด๋ถ€๋กœ ์นจํˆฌ๋  ์ˆ˜ ์žˆ๋„๋ก ์œ ๋„ํ•˜์—ฌ ๊ฒฐ๊ตญ ๊ฐ•์žฌ์˜ ์ทจ์„ฑํŒŒ๊ดด ํ˜„์ƒ์„ ์•ผ๊ธฐํ•˜๋Š” ๋ฐ์— ์ง์ ‘์ ์ธ ์—ญํ• ์„ ํ•˜๋Š” ๊ฒƒ์œผ๋กœ ์•Œ๋ ค์ ธ ์žˆ๋‹ค. ๋‹ค์Œ์€ ์ฒ ๊ฐ•์žฌ๋ฃŒ์˜ ์–‘๊ทน์šฉํ•ด ๋ฐ˜์‘๊ณผ H2S๊ฐ€ ํฌํ•จ๋œ ์‚ฐ์„ฑ์˜ ์ˆ˜์šฉ์•ก ๋ถ„์œ„๊ธฐ ๋‚ด์— ๋…ธ์ถœ๋œ ๊ฐ•์žฌ ํ‘œ๋ฉด์—์„œ ๋ฐœ์ƒํ•˜๋Š” ๋Œ€ํ‘œ์  ์Œ๊ทนํ™˜์›๋ฐ˜์‘์„ ๋‚˜ํƒ€๋‚ธ๋‹ค [5-9].

(1)
์–‘๊ทน์šฉํ•ด๋ฐ˜์‘ :   Fe   โ†’   Fe 2 +   +   2 e -  
(2)
์Œ๊ทนํ™˜์›๋ฐ˜์‘   ( ํƒˆ๊ธฐ์กฐ๊ฑด ) :   H +     +   e -   โ†’   H
(3)
์Œ๊ทนํ™˜์›๋ฐ˜์‘   ( ํ†ต๊ธฐ์กฐ๊ฑด ) :   O 2   +   4 H +     +   4 e -   โ†’   2 H 2 O

์ผ๋ฐ˜์ ์œผ๋กœ, H2S์— ์˜ํ•œ poisoning ํšจ๊ณผ [10]์— ์˜ํ•ด ๊ฐ•์žฌ ๋‚ด๋ถ€๋กœ ์‰ฝ๊ฒŒ ์œ ์ž…๋œ ์ˆ˜์†Œ์›์ž๋Š” ๊ฒฉ์žํ™•์‚ฐ ๋ฐ ๊ฒฐํ•จ ์ง€์—ญ์—์„œ์˜ ํŠธ๋žฉ ํ˜„์ƒ์„ ๊ฑฐ์น˜๋ฉฐ ํ™•์‚ฐํ•˜๊ณ  ์ดํ›„, ํŠธ๋žฉ๋œ ์ˆ˜์†Œ์›์ž๋Š” ์ง€์†์ ์ธ ์ˆ˜์†Œ ์ง‘์ ๊ณผ ๋ถ„์žํ˜•์„ฑ์— ๋”ฐ๋ฅธ ๋ถ€ํ”ผํŒฝ์ฐฝ์— ์˜ํ•ด ์ˆ˜์†Œ์œ ๊ธฐ๊ท ์—ด์„ ์•ผ๊ธฐํ•œ๋‹ค๊ณ  ์•Œ๋ ค์ ธ ์žˆ๋‹ค [5, 7-9]. ๋˜ํ•œ, H2S ํ™˜๊ฒฝ ๋‚ด ๋…ธ์ถœ๋œ ๊ฐ•์žฌ์— ๋‹ค์–‘ํ•œ ํ˜•ํƒœ์˜ ์™ธ๋ถ€์‘๋ ฅ์ด ์ถ”๊ฐ€์ ์œผ๋กœ ์ธ๊ฐ€๋˜๋Š” ์กฐ๊ฑด์—์„œ๋Š” ํ™ฉํ™”๋ฌผ์‘๋ ฅ๊ท ์—ด(sulfide stress cracking, SSC)์ด ์ฃผ๋œ ์ทจ์„ฑํŒŒ๊ดด ๋ฉ”์ปค๋‹ˆ์ฆ˜์œผ๋กœ ๊ฑฐ๋ก ๋˜๊ณ  ์žˆ๋‹ค [11,12].

ํ•œํŽธ, ๊ธˆ์†ํ•™์  ๊ด€์ ์—์„œ, ๊ฐ€์—ด ๋ฐ ๊ธ‰๋ƒ‰์˜ ์—ด์ด๋ ฅ์„ ๊ฑฐ์น˜๋ฉด์„œ ์ƒ์ดํ•œ ๋ฏธ์„ธ์กฐ์ง์„ ํ˜•์„ฑํ•˜๊ฒŒ ๋˜๋Š” ์šฉ์ ‘ ๊ณต์ •์€ ๋ชจ์žฌ์™€๋Š” ๊ธฐ๊ณ„์  ๋ฐ ์ „๊ธฐํ™”ํ•™์  ํŠน์„ฑ์ด ์ƒ์ดํ•˜๊ฒŒ ๋‚˜ํƒ€๋‚œ๋‹ค. ํŠนํžˆ, ์šฉ์ ‘๋ถ€ ์ธ๊ทผ์—์„œ ์šฉ์ ‘ ์‹œ ์ธ๊ฐ€๋˜๋Š” ์ž…์—ด์— ์˜ํ•ด CGHAZ (coarse-grain HAZ), FGHAZ (fine-grain HAZ), ICHAZ (intercritical HAZ), SCHAZ (subcritical HAZ) ๋“ฑ๊ณผ ๊ฐ™์€ ๋‹ค์–‘ํ•œ ๋ฏธ์„ธ์กฐ์ง์  ๋ณ€ํ™”๋ฅผ ์ˆ˜๋ฐ˜ํ•˜๋Š” ์šฉ์ ‘ ์—ด์˜ํ–ฅ๋ถ€๋Š” ์ถ”๊ฐ€์ ์ธ ํ•ฉ๊ธˆ์„ค๊ณ„๋ฅผ ํ†ตํ•ด ํŠน์„ฑ์„ ํ–ฅ์ƒ์‹œํ‚ฌ ์ˆ˜ ์žˆ๋Š” ์šฉ์ ‘๊ธˆ์†๋ถ€์™€ ๋‹ฌ๋ฆฌ ๋ชจ์žฌ์˜ ์„ฑ๋ถ„์„ ํ† ๋Œ€๋กœ ๋ฏธ์„ธ์กฐ์ง์  ๋ณ€ํƒœ๋งŒ์ด ๋ฐœ์ƒ๋˜์–ด, ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ๋ฟ ์•„๋‹ˆ๋ผ ์ˆ˜์†Œ์ทจํ™”ํŠน์„ฑ์ด ์—ด์œ„ํ•œ ์ง€์—ญ์œผ๋กœ ํ‰๊ฐ€๋˜๊ณ  ์žˆ๋‹ค. ์—ด์˜ํ–ฅ๋ถ€ ๋‚ด์˜ ์ˆ˜์†Œ์ทจํ™” ์ธก๋ฉด์—์„œ, ์šฉ์ ‘ ์‹œ ๊ฐ•์žฌ์˜ ์ทจํ™”ํ˜„์ƒ์„ ์•ผ๊ธฐํ•˜๋Š” ๋ฐ์— ์ง์ ‘์ ์ธ ์˜ํ–ฅ์„ ๋ฏธ์น˜๋Š” ์š”์ธ์œผ๋กœ, ์ธ๊ฐ€๋œ ์—ด์ด๋ ฅ์— ๋”ฐ๋ผ ํ˜•์„ฑ๋˜๋Š” ์ €์˜จ๋ณ€ํƒœ์กฐ์ง์ด ์กด์žฌํ•œ๋‹ค. ๋‹ค์ˆ˜์˜ ์„ ํ–‰ ์—ฐ๊ตฌ์—์„œ๋Š” ์ˆ˜์†Œ์ทจํ™”๋ฏผ๊ฐ๋„ ์ฆ๊ฐ€์— ์ง€๋ฐฐ์ ์ธ ์˜ํ–ฅ์„ ๋ฏธ์น˜๋Š” ์š”์ธ์œผ๋กœ ์ €์˜จ๋ณ€ํƒœ์กฐ์ง์˜ ๋ถ„์œจ์„ ์ฃผ๋กœ ์–ธ๊ธ‰ํ•˜๊ณ  ์žˆ๋‹ค. ํ•˜์ง€๋งŒ ๋†’์€ ๋ถ„์œจ์˜ ์ €์˜จ๋ณ€ํƒœ์กฐ์ง์„ ํ˜•์„ฑํ•œ๋‹ค ํ• ์ง€๋ผ๋„ ์ €์˜จ๋ณ€ํƒœ์กฐ์ง์˜ ํŽธ์ค‘๋„ ๋ฐ ๋ถ„ํฌ๋„๊ฐ€ ์‹ค์ œ ์šฉ์ ‘๋œ ๊ฐ•์žฌ์˜ ๋ถ€์‹๋ฐ˜์‘์— ๊ธฐ์ธํ•œ ์ˆ˜์†Œ์ทจํ™” ํ˜„์ƒ์— ๋ฏธ์น˜๋Š” ์˜ํ–ฅ์€ ์ƒ์ดํ•  ๊ฒƒ์œผ๋กœ ์˜ˆ์ƒ๋˜๋ฉฐ, ์ตœ๊ทผ์—๋Š” API X65๊ธ‰ ๊ฐ•์žฌ๋ฅผ ๋Œ€์ƒ์œผ๋กœ ์ƒ์ดํ•œ ์šฉ์ ‘๊ณต์ • ์ ์šฉ ํ›„ ๊ฐ ์šฉ์ ‘๋ถ€ ๋‚ด ์กด์žฌํ•˜๋Š” ์ €์˜จ๋ณ€ํƒœ์กฐ์ง์˜ ๊ฒฝ๋„ ๋ฐ coincidence site lattice (CSL) ์ž…๊ณ„ ๋ถ„์œจ ๋“ฑ์„ ํ† ๋Œ€๋กœ ์ˆ˜์†Œ์œ ๊ธฐ๊ท ์—ด (hydrogen induced cracking, HIC) ๊ฑฐ๋™์„ ๋ถ„์„ํ•œ ์—ฐ๊ตฌ [13]๊ฐ€ ๋ณด๊ณ ๋˜๊ธฐ๋„ ํ•˜์˜€๋‹ค. ํ•˜์ง€๋งŒ ์ €์˜จ๋ณ€ํƒœ์ƒ์˜ ํŽธ์ค‘๋„ ๋ฐ ๋ถ„ํฌ๋„์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๋Š” ์—ฌ์ „ํžˆ ๋ถ€์กฑํ•œ ์‹ค์ •์ด๋ฉฐ, ๋Œ€๋‹ค์ˆ˜์˜ ์—ฐ๊ตฌ๊ฐ€ ์ˆ˜์†Œ์ทจํ™”ํ˜„์ƒ ๊ทœ๋ช…๋ฐฉ๋ฒ•์— ์žˆ์–ด, ์ „ํ†ต์ ์ธ ์•ผ๊ธˆํ•™์  ์ ‘๊ทผ๋ฒ•์— ๊ธฐ๋ฐ˜์„ ๋‘๊ณ , ์ธ์œ„์ ์ธ ์ˆ˜์†Œ์ฃผ์ž…์„ ํ†ตํ•œ ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ ์—ด์œ„์ •๋„ ํ‰๊ฐ€์— ์ดˆ์ ์„ ๋‘๊ณ  ์žˆ๋‹ค. ์ฃผ๋กœ ์ „๊ธฐํ™”ํ•™์  ์Œ๊ทน์ฐจ์ง•๋ฒ•์„ ํ†ตํ•ด ํ‘œ๋ฉด ๋ถ€์‹๋ฐ˜์‘์„ ์ „์ ์œผ๋กœ ๋ฐฐ์ œ์‹œํ‚ค๋ฉฐ ๋‹ค๋Ÿ‰์˜ ์ˆ˜์†Œ๋ฅผ ์ฃผ์ž…ํ•˜์—ฌ ๊ฐ• ๋‚ด๋ถ€์—์„œ์˜ ํ™•์‚ฐ๊ฑฐ๋™์„ ํ‰๊ฐ€ํ•˜๋ฉฐ ์ผ๋ จ์˜ ํ™•์‚ฐ๋ณ€์ˆ˜ ๊ฐ’๋“ค์„ ๋„์ถœํ•˜๋Š” ๊ฒƒ์ด๋‹ค. ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ๊ณ„์ˆ˜ ๋ฐ ํˆฌ๊ณผ๋„ ๋“ฑ์˜ ํ™•์‚ฐ๋ณ€์ˆ˜ ๊ฐ’๋“ค์„ ํ† ๋Œ€๋กœ ์ทจ์„ฑํŒŒ๊ดด ์ €ํ•ญ์„ฑ์˜ ์ง€ํ‘œ๋กœ ๊ฐ„์ฃผํ•˜๋Š” ๊ฒƒ์ด ์ผ๋ฐ˜์ ์ด๋‹ค. ํ•˜์ง€๋งŒ ์ธ์œ„์  ์กฐ๊ฑด ํ•˜์— ๋„์ถœ๋œ ํ™•์‚ฐ๋ณ€์ˆ˜ ๊ฐ’๋“ค์˜ ์˜๋ฏธ์™€ ํŠน์ • ๊ฐ•์žฌ๊ฐ€ ์ ์šฉ๋˜๋Š” ์‹ค์ œ ํ™˜๊ฒฝ ๋‚ด์—์„œ ๋ฐœ์ƒํ•˜๋Š” ์ทจ์„ฑํŒŒ๊ดด๊ฑฐ๋™๊ณผ ๋ถˆ์ผ์น˜ํ•˜๋Š” ํ˜„์ƒ๋“ค์ด ๋‚˜ํƒ€๋‚˜๊ณ  ์žˆ์œผ๋ฉฐ [14], ๋ณธ ์—ฐ๊ตฌ๋Š” ๊ทธ ๋ถˆ์ผ์น˜ ํ˜„์ƒ์˜ ์˜ˆ๋ฅผ ๋‹จ์ ์œผ๋กœ ๋ณด์—ฌ์ฃผ๋ฉฐ ๊ทธ ๋ฉ”์ปค๋‹ˆ์ฆ˜์  ๋ถ„์„๊ณผ ๋…ผ์˜๋ฅผ ์ฃผ ๋ชฉ์ ์œผ๋กœ ํ•œ๋‹ค.

์šฐ์„ , ์••๋ ฅ์šฉ๊ธฐ์šฉ A516-65 ๊ฐ•์žฌ๋ฅผ ๋Œ€์ƒ์œผ๋กœ ์ƒ์ดํ•œ ์šฉ์ ‘ ์ž…์—ด๋Ÿ‰์œผ๋กœ ๋ชจ์‚ฌ๋œ ์šฉ์ ‘ ์—ด์˜ํ–ฅ๋ถ€ (CGHAZ์™€ ICHAZ)์˜ ๋ฏธ์„ธ์กฐ์ง์  ๊ฑฐ๋™๊ณผ ์ˆ˜์†Œํ™•์‚ฐ๊ฑฐ๋™์˜ ๊ด€๊ณ„๋ฅผ ์ œ์‹œํ•œ ํ›„, ์‹ค์ œ sour ํ™˜๊ฒฝ ๋‚ด ๋ฐœ์ƒํ•˜๋Š” SSC ํ˜„์ƒ์— ์˜ํ–ฅ์„ ๋ฏธ์น˜๋Š” ์ฃผ๋œ ๊ธˆ์†ํ•™์  ์ธ์ž๋“ค์— ๋Œ€ํ•ด ๋…ผ์˜ํ•˜๊ณ ์ž ํ•œ๋‹ค.

2. ์‹คํ—˜๋ฐฉ๋ฒ•

2.1 ์‹œํŽธ ์ค€๋น„ ๋ฐ ๋ฏธ์„ธ์กฐ์ง ๋ถ„์„

๋ณธ ์—ฐ๊ตฌ์— ์‚ฌ์šฉ๋œ ์‹œํŽธ์€ ์••๋ ฅ์šฉ๊ธฐ์šฉ ASTM 516-65 ๊ฐ•์žฌ๋กœ, ๊ทธ ํ™”ํ•™์  ์กฐ์„ฑ์„ ํ‘œ 1์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ์šฉ์ ‘ ์—ด์˜ํ–ฅ๋ถ€ (CGHAZ ๋ฐ ICHAZ) ๋ชจ์‚ฌ๋ฅผ ์œ„ํ•ด MTCS (metal thermal cycle simulator)๋ฅผ ํ™œ์šฉํ•˜์˜€๋‹ค. ๊ทธ๋ฆผ 1์€ ๊ฐ๊ฐ์˜ ์šฉ์ ‘ ์—ด์˜ํ–ฅ๋ถ€์˜ ์—ด์ด๋ ฅ์„ ๋ชจ์‚ฌํ•˜๊ธฐ ์œ„ํ•ด, Rosenthal์˜ ์—ด์œ ๋™๋ฐฉ์ •์‹ (thermal field equation) [15]์„ ์ด์šฉํ•˜์—ฌ ๋„์ถœํ•œ ์šฉ์ ‘ ์šฉ์œต์„ ์œผ๋กœ๋ถ€ํ„ฐ ๋ชจ์žฌ๊นŒ์ง€์˜ ๊ฑฐ๋ฆฌ ๋ณ„๋กœ ์‹œ๊ฐ„์— ๋”ฐ๋ฅธ ์˜จ๋„ ๊ตฌ๋ฐฐ๋ฅผ ๋‚˜ํƒ€๋‚ธ ๊ฒƒ์ด๋‹ค. MTCS๋ฅผ ํ†ตํ•ด ์—ด์˜ํ–ฅ๋ถ€๋ฅผ ์žฌํ˜„ํ•œ ์‹œํŽธ์— ์ ์šฉ๋œ ์ž…์—ด๋Ÿ‰์€ 20, 35, 50 kJ/cm์˜ 3๊ฐ€์ง€๋กœ ์ฑ„ํƒํ•˜์˜€์œผ๋ฉฐ ๊ฐ๊ฐ์˜ ์˜จ๋„๊ตฌ๋ฐฐ๋Š” ์‹ (4) [15]๋ฅผ ํ†ตํ•ด ๋„์ถœ๋˜์—ˆ๋‹ค.

(4)
T - T 0   =   q ฮฝ 2 ฯ€ฮป e x p ( - r 2 4 a t )

์ด๋•Œ T์™€ t๋Š” ์—ด ์‚ฌ์ดํด์˜ ์˜จ๋„ ๋ฐ ์‹œ๊ฐ„์ด๋ฉฐ, T0๋Š” ์šฉ์ ‘ ์ „ ์˜ˆ์—ด์˜จ๋„, q/v๋Š” ์ž…์—ด๋Ÿ‰, ฮป๋Š” ์žฌ๋ฃŒ์˜ ์—ด์ „๋„๋„(thermal conductivity), a๋Š” ์žฌ๋ฃŒ์˜ ์—ด ํ™•์‚ฐ๋„ (thermal diffusivity), r์€ ์šฉ์ ‘ ์—ด์›์œผ๋กœ๋ถ€ํ„ฐ์˜ ๊ฑฐ๋ฆฌ๋ฅผ ๋‚˜ํƒ€๋‚ธ๋‹ค.

์ดํ›„, ๋ฏธ์„ธ์กฐ์ง ๊ด€์ฐฐ์„ ์œ„ํ•ด, ๊ฐ๊ฐ์˜ ์‹œํŽธ์€ SiC paper๋ฅผ ํ†ตํ•ด #4000๊นŒ์ง€ ๋‹จ๊ณ„์ ์œผ๋กœ grinding ํ›„ 1 ยตm๊นŒ์ง€ micro-polishingํ•˜์˜€๋‹ค. ์—ฐ๋งˆ๋œ ์‹œํŽธ์€ 3% nital์„ ํ†ตํ•ด etching ํ›„, ์ดˆ์ŒํŒŒ ์„ธ์ฒ™์„ ์‹ค์‹œํ•˜์˜€๋‹ค. ์ถ”๊ฐ€์ ์œผ๋กœ, M-A (martensite-austenite)๋งŒ์„ ๋‹จ๋…์ ์œผ๋กœ ๊ด€์ฐฐํ•˜๊ธฐ ์œ„ํ•ด LePera ์šฉ์•ก์œผ๋กœ M-A๋ฅผ ์„ ํƒ์ ์œผ๋กœ etching ํ•˜์˜€๋‹ค. ์ ์šฉ๋œ etching๋ฒ• [16]์€, ์šฐ์„ ์ ์œผ๋กœ ํŽ˜๋ผ์ดํŠธ๋ฅผ etchingํ•œ ํ›„ ๋‘๋ฒˆ์งธ ๋‹จ๊ณ„์—์„œ ๋‚จ์€ ํƒ„ํ™”๋ฌผ (carbide)๋ฅผ etchingํ•˜์—ฌ M-A๋งŒ ๋‚จ๋Š” ๋ฐฉ์‹์œผ๋กœ ์ง„ํ–‰๋˜์—ˆ๋‹ค. ์ดํ›„, ๊ด‘ํ•™ ํ˜„๋ฏธ๊ฒฝ (optical microscopy, OM) ๋ฐ ์ „๊ณ„๋ฐฉ์‚ฌํ˜• ์ฃผ์‚ฌ์ „์žํ˜„๋ฏธ๊ฒฝ (field emission-scanning electron microscopy, FE-SEM)์„ ํ†ตํ•ด ๋ฏธ์„ธ์กฐ์ง ๋ฐ M-A๋ฅผ ๊ด€์ฐฐํ•˜์˜€๊ณ  OM์˜ image analyzer๋ฅผ ํ™œ์šฉํ•˜์—ฌ ์‹œํŽธ ๋ณ„ M-A๋ถ„์œจ์„ ์ •๋Ÿ‰์ ์œผ๋กœ ๋„์ถœํ•˜์˜€๋‹ค. ์ถ”๊ฐ€์ ์œผ๋กœ, ์ž…์—ด๋Ÿ‰์— ๋”ฐ๋ฅธ ๋ฏธ์„ธ์กฐ์ง ๋ณ„ ๊ฒฝ๋„ ์ธก์ •์„ ์œ„ํ•ด 0.5 kgf์˜ ํ•˜์ค‘์œผ๋กœ ๋น„์ปค์Šค ๊ฒฝ๋„๋ฅผ ์ธก์ •ํ•˜์˜€๋‹ค.

2.2 ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰ ์ธก์ •

๊ฐ•์žฌ ๋‚ด๋ถ€์˜ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์„ ์ธก์ •ํ•˜๊ธฐ ์œ„ํ•ด JIS Z3113 [17]์— ์ž…๊ฐํ•˜์—ฌ ๊ธ€๋ฆฌ์„ธ๋ฆฐ ์‹œํ—˜๋ฒ•์„ ํ™œ์šฉํ•˜์˜€๋‹ค. ๊ฐ•์žฌ ๋‚ด๋ถ€์— ์ „๊ธฐํ™”ํ•™์ ์œผ๋กœ ์ˆ˜์†Œ๋ฅผ ์ฃผ์ž…ํ•˜๊ธฐ ์œ„ํ•ด potentiostat์žฅ๋น„ (gamry reference 600)๋ฅผ ์‚ฌ์šฉํ•˜์˜€๋‹ค. 20 ร— 30 ร— 2 mm3 ํฌ๊ธฐ์˜ ์‹œํŽธ์„ SiC #2000๊นŒ์ง€ polishing ํ›„ ์ธ์œ„์ ์ธ ์ˆ˜์†Œ charging์„ ์œ„ํ•ด NACE ๊ทœ๊ฒฉ์šฉ์•ก (5% NaCl + 0.5% CH3COOH)์— 0.05 M Na2S๊ฐ€ ์ฒจ๊ฐ€๋œ ์šฉ์•ก์—์„œ 5 mA์˜ ์Œ๊ทน์ „๋ฅ˜๋ฅผ 20 h ๋™์•ˆ ์ธ๊ฐ€ํ•˜์˜€๋‹ค. Charging ํ›„ ๊ธ€๋ฆฌ์„ธ๋ฆฐ ์šฉ์•ก์— ์นจ์ง€ํ•˜์—ฌ 48 h ๋™์•ˆ ๋ฐฉ์ถœ๋˜๋Š” ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์„ ์ธก์ •ํ•˜์˜€๋‹ค. ์ธก์ •๋œ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์€ ์‹ (5)์— ์˜ํ•ด ์ •๋Ÿ‰์ ์œผ๋กœ ๋„์ถœ๋˜์—ˆ์œผ๋ฉฐ wt%๋กœ ํ™˜์‚ฐํ•˜์—ฌ ๋น„๊ต ๋ฐ ํ‰๊ฐ€ํ•˜์˜€๋‹ค.

(5)
V ( m l )   =   ( h G 1 - h G ) V 1 ยท 273 . 15 8 . 2 ยท ( 273 . 15   +   T 1 ( โ„ƒ ) )

์—ฌ๊ธฐ์„œ V1์€ ์œก์•ˆ์œผ๋กœ ํ™•์ธ๋œ ์ˆ˜์†Œ์˜ ์–‘, hG1์€ 1๊ธฐ์•• 0ยฐC์—์„œ ์ธก์ •๋œ ๊ธ€๋ฆฌ์„ธ๋ฆฐ์˜ ๋†’์ด, hG๋Š” 1๊ธฐ์•• T1์—์„œ ์ธก์ •๋œ ๊ธ€๋ฆฌ์„ธ๋ฆฐ์˜ ๋†’์ด, T1์€ ์ธก์ •๋œ ์˜จ๋„๋ฅผ ์˜๋ฏธํ•œ๋‹ค.

2.3 ์ „๊ธฐํ™”ํ•™์  ์ˆ˜์†Œํˆฌ๊ณผ์‹คํ—˜

์‹œํŽธ ๋ณ„ ๋‚ด๋ถ€ ์ˆ˜์†Œํ™•์‚ฐ๊ฑฐ๋™์„ ๋ถ„์„ํ•˜๊ธฐ ์œ„ํ•ด, ISO 17081 ํ‘œ์ค€ ์‹œํ—˜๋ฒ• [18]์— ์ž…๊ฐํ•œ ์ „๊ธฐํ™”ํ•™์  ์ˆ˜์†Œํˆฌ๊ณผ์‹คํ—˜ (electrochemical hydrogen permeation test)์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. ๊ทธ๋ฆผ 2๋Š” ์ „๊ธฐํ™”ํ•™์  ์ˆ˜์†Œํˆฌ๊ณผ์‹คํ—˜์— ํ™œ์šฉ๋œ cell์˜ ๊ฐ„๋žตํ•œ ๋ชจ์‹๋„๋ฅผ ๋‚˜ํƒ€๋‚ธ ๊ฒƒ์œผ๋กœ, ์ค‘์•™๋ถ€์˜ ์‹œํŽธ์„ ๊ธฐ์ค€์œผ๋กœ ์šฐ์ธก์˜ ์ˆ˜์†Œ์ฃผ์ž…๋ถ€ (charging side)์™€ ์ขŒ์ธก์˜ ์ˆ˜์†Œ๊ฒ€์ถœ๋ถ€ (detection side)๋กœ ๊ตฌ๋ถ„๋œ ํ˜•ํƒœ๋ฅผ ๋‚˜ํƒ€๋‚ธ๋‹ค. ์ˆ˜์†Œํˆฌ๊ณผ์‹คํ—˜์€ ์ „๊ธฐํ™”ํ•™์  ์ˆ˜์†Œ ์ฃผ์ž…์„ ํ†ตํ•ด ์‹œํŽธ์„ ํˆฌ๊ณผํ•˜๋Š” ์ˆ˜์†Œ์›์ž๋ฅผ ์ขŒ์ธก์˜ ๊ฒ€์ถœ๋ถ€์—์„œ ์‚ฐํ™”์‹œ์ผœ ๊ฒ€์ถœํ•˜๋Š” ์›๋ฆฌ๋ฅผ ๊ฐ€์ง„๋‹ค. ๋ณธ ์‹คํ—˜์— ์ ์šฉ๋œ ์‹œํŽธ์˜ ๋‘๊ป˜๋Š” 1 mm ์ด์ƒ์œผ๋กœ, ๋™์ผ ASTM A516 ๊ฐ•์žฌ๋ฅผ ๋Œ€์ƒ์œผ๋กœ ์ˆ˜ํ–‰ํ•œ ์„ ํ–‰์—ฐ๊ตฌ [19] ๊ฒฐ๊ณผ๋ฅผ ํ† ๋Œ€๋กœ, ์ˆ˜์†Œ์›์ž์˜ volume diffusion ์กฐ๊ฑด์„ ๋งŒ์กฑํ•˜๋Š” ๊ฒƒ์œผ๋กœ ๊ฐ„์ฃผํ•˜์˜€๋‹ค. ์‹คํ—˜ ์ „ detection side์˜ ์‹œํŽธ ํ‘œ๋ฉด์— ์ˆ˜์†Œ ์›์ž์˜ ์‚ฐํ™” ํšจ์œจ์„ ๋†’์ด๊ณ  ํˆฌ๊ณผ์ „๋ฅ˜์˜ ์‹ ๋ขฐ์„ฑ ํ™•๋ณด๋ฅผ ์œ„ํ•ด, SiC paper๋กœ #2000๊นŒ์ง€ ์—ฐ๋งˆํ•˜๊ณ  HCl ์šฉ์•ก ๋‚ด ์‚ฐ์„ธ ํ›„, Pd ๋„๊ธˆ ์šฉ์•ก (PdCl2 2.54 g + 500 ml NH3) ๋‚ด์—์„œ -2.8 mA/cm2์˜ ์ „๋ฅ˜๋ฐ€๋„๋ฅผ 180 s ๋™์•ˆ ์ธ๊ฐ€ํ•˜์—ฌ 100~150 nm ๋‘๊ป˜์˜ Pd ๋„๊ธˆ์ธต์„ ํ˜•์„ฑ์‹œ์ผฐ๋‹ค. ์ดํ›„, ์ขŒ์ธก์˜ ์ˆ˜์†Œ ๊ฒ€์ถœ๋ถ€์— Ar์„ ์ด์šฉํ•˜์—ฌ ํƒˆ๊ธฐ๋œ 0.1 M NaOH ์šฉ์•ก์„ ์ฃผ์ž…ํ•˜๊ณ  270 mVSCE์˜ ์–‘๊ทน ์ „์œ„๋ฅผ ์ •์ „์œ„ ๋ถ„๊ทน (potentiostatic polarization) ๋ฐฉ์‹์œผ๋กœ ์ธ๊ฐ€ํ•˜์—ฌ 0.1 ยตA/cm2 ์ดํ•˜์˜ ๋ฐฐ๊ฒฝ ์ „๋ฅ˜๋ฅผ ํš๋“ํ•˜์˜€๋‹ค. ์ˆ˜์†Œ charging์„ ์œ„ํ•ด ์ˆ˜์†Œ ์ฃผ์ž…๋ถ€์—๋Š” 0.5% NaCl + 0.5% CH3COOH + 0.05 M Na2S + 0.3% NH4SCN ์šฉ์•ก์„ ์ฃผ์ž…ํ•˜๊ณ  1 mA/cm2์˜ ์Œ๊ทน์ „๋ฅ˜๋ฅผ ์ •์ „๋ฅ˜ ๋ฐฉ์‹์œผ๋กœ ์ธ๊ฐ€ํ•˜์˜€๋‹ค. ์ดํ›„, ์ธก์ •๋˜๋Š” ์ˆ˜์†Œ์›์ž์˜ ์‚ฐํ™”์ „๋ฅ˜ ๊ฐ’์ด ์ •์ƒ์ƒํƒœ (steady-state condition)์— ๋„๋‹ฌํ•œ ํ›„ desorption์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. ์ „๊ธฐํ™”ํ•™์  ์ˆ˜์†Œํˆฌ๊ณผ์‹คํ—˜ ํ›„ ํš๋“ํ•œ ์‹คํ—˜๊ฒฐ๊ณผ๋ฅผ ๋ฐ”ํƒ•์œผ๋กœ ์ˆ˜์†Œํ™•์‚ฐ ๋ณ€์ˆ˜๋ฅผ ๋„์ถœํ•˜๊ธฐ ์œ„ํ•ด, decay ๊ทธ๋ž˜ํ”„๋ฅผ ๋Œ€์ƒ์œผ๋กœ ์ •์ƒ์ƒํƒœ ์ „๋ฅ˜๋ฐ€๋„๋ฅผ normalizingํ•˜๊ณ  ์‹ (6) [20]๋ฅผ ํ†ตํ•œ curve-fitting์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค.

(6)
H   current   decay   phase   =   1   -   2 L ฯ€ D t โˆ‘ n = 0 โˆž   e x p ( - ( 2 n + 1 ) 2 L 2 4 D t )

์—ฌ๊ธฐ์„œ, D๋Š” ์ˆ˜์†Œํ™•์‚ฐ๊ณ„์ˆ˜, n์€ ์ •ํ™•ํ•œ curve fitting์„ ์œ„ํ•œ 0, 1, 2, 3, 4์˜ ์ƒ์ˆ˜, L์€ ์‹œํŽธ ๋‘๊ป˜, t๋Š” ์‹œ๊ฐ„ (s)๋ฅผ ์˜๋ฏธํ•œ๋‹ค.

์‹œํŽธ ๋ณ„ ๋‚ด๋ถ€ ๋‹จ์œ„๋ถ€ํ”ผ๋‹น ํŠธ๋žฉ ๋ฐ€๋„๋Š” ์•„๋ž˜ ์‹ (7) [21]๋ฅผ ํ†ตํ•ด ๋„์ถœ๋˜์—ˆ๋‹ค.

(7)
D L D ฯ„   - 1   =   3 N T < C >

์—ฌ๊ธฐ์„œ DL์€ ์ˆœ์ˆ˜ํ•œ lattice ํ™•์‚ฐ๊ณ„์ˆ˜, Dฯ„์€ ํŠธ๋žฉ์ด ๊ณ ๋ ค๋œ ํ™•์‚ฐ๊ณ„์ˆ˜, NT๋Š” ๋‹จ์œ„๋ถ€ํ”ผ๋‹น ํŠธ๋žฉ ๋ฐ€๋„, <C>๋Š” ๊ฐ•์žฌ ๋‚ด๋ถ€ ํ‰๊ท  ์ˆ˜์†Œ๋†๋„ (ํŠธ๋žฉ์ด ๊ณ ๋ ค๋œ ๋‚ด๋ถ€ ์ˆ˜์†Œ์šฉํ•ด๋„, Capp)๋ฅผ ์˜๋ฏธํ•œ๋‹ค. ์ด๋•Œ, DL์˜ ๊ฒฝ์šฐ, ์„ ํ–‰์—ฐ๊ตฌ๊ฒฐ๊ณผ์— ๋”ฐ๋ฅด๋ฉด pure iron์„ ๋Œ€์ƒ์œผ๋กœ ์ธก์ •ํ•œ DL ๊ฐ’์€ 7.5 ร— 10-9m2/s [21]๋กœ ์ธก์ •๋˜๋‚˜, ๋ฌธํ—Œ๋“ค๋งˆ๋‹ค ์ƒ์ดํ•œ ๊ฒฐ๊ณผ์น˜๊ฐ€ ๋ณด๊ณ ๋˜๊ณ  ์žˆ๋‹ค. ์„์œ ํ™”ํ•™์‚ฐ์—…์šฉ API (american petroleum institute) ๊ฐ•๊ด€์šฉ X52 ์†Œ์žฌ์—์„œ๋Š” DL ๊ฐ’์ด 3.25 ร— 10-9m2/s [22]๋กœ ๋‹ค์†Œ ๋‚ฎ๊ฒŒ ๋ณด๊ณ ๋œ ๊ฒƒ์„ ํ† ๋Œ€๋กœ, pure iron๊ณผ ๋น„๊ตํ•˜์—ฌ ์นจ์ž…ํ˜• C ์›์ž ๋ฐ ์น˜ํ™˜ํ˜• ํ•ฉ๊ธˆ์„ฑ๋ถ„ ์ฒจ๊ฐ€๋Š” ๊ฒฉ์ž๋‚ด๋ถ€์— strain field๋ฅผ ํ˜•์„ฑํ•˜๊ณ  ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ์†๋„๋ฅผ ๋‹ค์†Œ ๋Šฆ์ถ”๋Š” ํšจ๊ณผ๊ฐ€ ์žˆ๋Š” ๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋˜์—ˆ๋‹ค. ์ด์— ๋ณธ ์—ฐ๊ตฌ์—์„œ ์‚ฌ์šฉ๋œ ์†Œ์žฌ๊ฐ€ pure iron์ด ์•„๋‹Œ, C, Mn, Cu, Ni ๋“ฑ์˜ ํ•ฉ๊ธˆ์„ฑ๋ถ„์ด ๋ฏธ๋Ÿ‰ ํฌํ•จ๋œ ์„์œ ํ™”ํ•™์‚ฐ์—…์šฉ ์ €ํƒ„์†Œ ๊ธฐ๋ฐ˜ ๊ฐ•์žฌ์ž„์„ ๊ณ ๋ คํ•˜์—ฌ, DL๊ฐ’์„ 3.25 ร— 10-9m2/s๋กœ ๊ฐ„์ฃผํ•˜์—ฌ ์ ์šฉํ•˜์˜€๋‹ค. ๋˜ํ•œ <C>๋Š” ์ˆ˜์†Œํˆฌ๊ณผ ์ƒ์Šน๊ณก์„ ์„ ํ†ตํ•ด ํš๋“ํ•œ ๊ทธ๋ž˜ํ”„๋ฅผ ๋ฐ”ํƒ•์œผ๋กœ ํš๋“ํ•œ ์ˆ˜์†Œ์›์ž์˜ ํˆฌ๊ณผ์œ ๋Ÿ‰ (permeability, JssL)์„ ํ™•์‚ฐ๊ณ„์ˆ˜ (diffusivity, Dapp)๋กœ ๋‚˜๋ˆ„์–ด ๋„์ถœ๋˜์—ˆ๋‹ค [18].

2.4 ๋ฌด๊ฒŒ๊ฐ๋Ÿ‰ ์ธก์ • ๋ฐ SSRT ์‹คํ—˜

์ž…์—ด๋Ÿ‰์— ๋”ฐ๋ฅธ ์šฉ์ ‘ ์—ด์˜ํ–ฅ๋ถ€ (CGHAZ, ICHAZ) ๋ณ„ ๋ถ€์‹ํ™˜๊ฒฝ ๋‚ด ๋ฌด๊ฒŒ๊ฐ๋Ÿ‰ ํŠน์„ฑ์„ ๋น„๊ตํ•˜๊ธฐ ์œ„ํ•ด ๊ฐ ์‹œํŽธ์˜ ์ดˆ๊ธฐ ๋ฌด๊ฒŒ ์ธก์ • ํ›„, ํ†ต๊ธฐ๋œ 5% NaCl + 0.5% CH3COOH + 0.05 M Na2S ์šฉ์•ก์— 10์ผ๊ฐ„ ์นจ์ง€๋ฅผ ์ง„ํ–‰ํ•˜์˜€๋‹ค. ์นจ์ง€ ํ›„ ์‹œํŽธ์„ ์ดˆ์ŒํŒŒ ์„ธ์ฒ™ํ•˜์—ฌ ๋ถ€์‹์ƒ์„ฑ๋ฌผ์„ ์ œ๊ฑฐํ•œ ๋’ค ๋ฌด๊ฒŒ๋ฅผ ์ธก์ •ํ•˜์—ฌ ์‹ (8)์„ ์ด์šฉํ•˜์—ฌ ๋ฌด๊ฒŒ๊ฐ๋Ÿ‰์„ ๊ณ„์‚ฐํ•˜์˜€๋‹ค.

(8)
Weight   reduction ( g / cm 2 )     =   W ( b ) - W ( a ) A

์—ฌ๊ธฐ์„œ, W(b)๋Š” ์นจ์ง€ ์ „ ๋ฌด๊ฒŒ, W(a)๋Š” ์นจ์ง€ ํ›„ ๋ฌด๊ฒŒ์ด๋ฉฐ, A๋Š” ๋‹จ๋ฉด์ ์„ ์˜๋ฏธํ•œ๋‹ค.

์‹ค์ œ flux-cored arc welding (FCAW)์„ ์‹ค์‹œํ•œ ์ธ์žฅ์‹œํ—˜ํŽธ์„ ๋Œ€์ƒ์œผ๋กœ ๊ฐ•์žฌ์˜ ์ˆ˜์†Œ์ทจํ™”๋ฏผ๊ฐ๋„ ํ‰๊ฐ€๋ฅผ ์œ„ํ•ด ASTM G129 [23]์— ๋ช…์‹œ๋˜์–ด ์žˆ๋Š” SSRT (slow strain rate tensile) ์‹คํ—˜์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. ์šฐ์„  FCAW๋Š” Xํ˜• ๊ทธ๋ฃจ๋ธŒ๋กœ ์ œ์ž‘๋œ 15 t ๋‘๊ป˜์˜ ํŒ์žฌ๋ฅผ ๋Œ€์ƒ์œผ๋กœ ํ‰๊ท  20 kJ/cm์˜ ์ž…์—ด๋Ÿ‰์œผ๋กœ 4 pass ์šฉ์ ‘์„ ์ง„ํ–‰ํ•˜์˜€๊ณ  0.08 wt% C, 1.1 wt% Mn, 0.6 wt% Si์„ ์ฃผ์„ฑ๋ถ„์œผ๋กœ ํ•˜๋Š” ์šฉ์ ‘์žฌ๋ฃŒ๊ฐ€ ์ ์šฉ๋˜์—ˆ๋‹ค. ๊ทธ๋ฆผ 3์— FCAW ํ›„ ์šฉ์ ‘ ์‹œํŽธ ์ฑ„์ทจ์œ„์น˜, ํ˜•์ƒ ๋ฐ ์ ˆ์ฐจ์— ๋Œ€ํ•œ ๊ฐ„๋žตํ•œ ๋ชจ์‹๋„์™€ SSRT ํ‰๊ฐ€๋ฅผ ์œ„ํ•ด ์ธ์žฅ์‹œํŽธ์œผ๋กœ ์ œ์ž‘๋œ ์‹œํŽธ์˜ ํ˜•์ƒ์„ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

SSRT ์‹คํ—˜์€ ์‹œํŽธ์— ๋งค์šฐ ๋А๋ฆฐ ์†๋„๋ฅผ ์ธ๊ฐ€ํ•˜์—ฌ ์‹œํŽธ์˜ ์ˆ˜์†Œ ์ทจํ™” ๋ฏผ๊ฐ๋„๋ฅผ ํ‰๊ฐ€ํ•˜๋Š” ๋ฐฉ๋ฒ•์œผ๋กœ ๋ณธ ์‹คํ—˜์—์„œ๋Š” 5% NaCl + 0.5% CH3COOH + 0.05 M Na2S + 0.5% NH4SCN ์šฉ์•ก ์นจ์ง€ ์ƒํƒœ์—์„œ 2 ร— 10-6/s์˜ ์ผ์ •์†๋„๋กœ ์ธ์žฅ์‹คํ—˜์„ ์ง„ํ–‰ํ•จ์œผ๋กœ์จ SSC ๊ฑฐ๋™ ๋ฐ ์ €ํ•ญ์„ฑ์„ ํ‰๊ฐ€ํ•ด๋ณด๊ณ ์ž ํ•˜์˜€๋‹ค. ๋ณธ ์‹คํ—˜์šฉ์•ก ๋‚ด ์ฒจ๊ฐ€๋œ Na2S๋Š” CH3COOH์™€ ๋ฐ˜์‘ํ•˜์—ฌ ๋‹ค์Œ๊ณผ ๊ฐ™์ด H2S๋ฅผ ํ˜•์„ฑ์‹œํ‚ด์œผ๋กœ์จ [24] sour ํ™˜๊ฒฝ์กฐ๊ฑด์„ ์ œ๊ณตํ•œ๋‹ค.

(9)
2 CH 3 COOH   +   Na 2 S   โ†’   H 2 S   +   2 CH 3 COONa

๋น„๊ต์žฌ๋กœ ๊ณต๊ธฐ ์ค‘์—์„œ SSRT ์‹คํ—˜์„ ์ˆ˜ํ–‰ํ•˜์—ฌ ํŒŒ๋‹จํ˜•์ƒ์„ ๊ด€์ฐฐํ•˜์˜€๊ณ , ์ถ”๊ฐ€์ ์œผ๋กœ, ์ธ์žฅ์‹œํ—˜๊ณผ ๋””์ง€ํ„ธ ์ด๋ฏธ์ง€์ƒ๊ด€๋ฒ• (digital image correlation, DIC)์„ ํ™œ์šฉํ•˜์—ฌ ๋™์ ์‘๋ ฅ ํ•˜์—์„œ ๋ณ€ํ˜•๋ฅ ์˜ ๋ถ„ํฌ ๋ณ€ํ™”๋ฅผ ํ† ๋Œ€๋กœ ์‘๋ ฅ์ง‘์ค‘๋ถ€๋ฅผ ๊ด€์ฐฐํ•˜์˜€๋‹ค. DIC๋Š” mercury RT๋ฅผ ํ™œ์šฉํ•˜์—ฌ 10-3/s์˜ ์ธ์žฅ์†๋„ ํ•˜์—์„œ ์‹œํŽธ์˜ ๋ณ€ํ˜•๋ฅ ์„ ์ „ ์˜์—ญ์— ๊ฑธ์ณ ๊ด€์ฐฐํ•˜๊ณ  ๊ตญ๋ถ€์˜์—ญ์—์„œ ์ง‘์ค‘๋˜๋Š” ๋ณ€ํ˜•๋ฅ  ์ •๋„๋ฅผ ์ƒ‰์ƒ์ฐจ๋กœ ๊ตฌ๋ถ„ํ•˜์—ฌ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

3. ๊ฒฐ๊ณผ๋ฐ๊ณ ์ฐฐ

3.1 ์ž…์—ด๋Ÿ‰ ๋ณ„ ๋ฏธ์„ธ์กฐ์ง ๊ด€์ฐฐ ๋ฐ M-A ๋ถ„์œจ์ธก์ •

๊ทธ๋ฆผ 4๋Š” 20, 35, 50 kJ/cm์˜ ์ž…์—ด๋Ÿ‰์œผ๋กœ ์—ด๋ชจ์‚ฌ๋œ CGHAZ ๋ฐ ICHAZ ์‹œํŽธ์˜ ๋ฏธ์„ธ์กฐ์ง ๊ด€์ฐฐ ๊ฒฐ๊ณผ๋ฅผ ๋‚˜ํƒ€๋‚ธ๋‹ค. ์ „์ฒด์ ์œผ๋กœ ๋ฒ ์ด๋‚˜์ดํŠธ ์กฐ์ง์ด ํ˜•์„ฑ๋œ CGHAZ์˜ ๊ฒฝ์šฐ ์ž…์—ด๋Ÿ‰์ด ์ฆ๊ฐ€ํ•จ์— ๋”ฐ๋ผ ๋ฒ ์ด๋‚˜์ดํŠธ ์กฐ์ง ๋‚ด lath ๋‘๊ป˜๊ฐ€ ์ฆ๊ฐ€ํ•˜์˜€์œผ๋ฉฐ ๋น„์ปค์Šค ๊ฒฝ๋„๋Š” ๊ฐ์†Œํ•˜์˜€๋‹ค. ์ด๋Š”, ์ž…์—ด๋Ÿ‰ ์ฆ๊ฐ€์— ๋”ฐ๋ฅธ ๋ƒ‰๊ฐ์†๋„ ๊ฐ์†Œ์— ๊ธฐ์ธํ•œ ๊ฒฐ๊ณผ๋กœ ์ž…์—ด๋Ÿ‰์ด ๋†’์„์‹œ ์ƒ๋Œ€์ ์œผ๋กœ ๊ณ ์˜จ ๋…ธ์ถœ ์‹œ๊ฐ„์ด ๊ธธ์–ด ์˜ค์Šคํ…Œ๋‚˜์ดํŠธ ๊ฒฐ์ •๋ฆฝ ์„ฑ์žฅ์— ์˜ํ•œ ์ €์˜จ์—์„œ ๋ณ€ํƒœ๋˜๋Š” ๋ฒ ์ด๋‚˜์ดํŠธ lath ๋‘๊ป˜ ์ฆ๊ฐ€์— ๊ธฐ์—ฌํ•œ ๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค. ํ•œํŽธ, ICHAZ์—์„œ๋Š” 20 kJ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ ํŽ˜๋ผ์ดํŠธ/ํŽ„๋ผ์ดํŠธ ๋ฐ ๋ฒ ์ด๋‚˜์ดํŠธ๊ฐ€ ๋ณตํ•ฉ์ ์œผ๋กœ ์กด์žฌํ•˜๋˜ ๋ฒ ์ด๋‚˜์ดํŠธ ์กด์žฌ์˜์—ญ์˜ ๊ตญ๋ถ€์  ํŽธ์ค‘๋„๊ฐ€ ๋†’์€ ๊ฒƒ์œผ๋กœ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ๋ฐ˜๋ฉด 35 kJ ์ด์ƒ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ๋Š” ๋Œ€๋ถ€๋ถ„ ๋ฏธ์„ธํ•œ ํฌ๊ธฐ์˜ ํŽ˜๋ผ์ดํŠธ/ํŽ„๋ผ์ดํŠธ ์กฐ์ง์ด ํ˜•์„ฑ๋˜์—ˆ๋‹ค. Intercritical ์˜์—ญ์—์„œ์˜ ์ƒ๋ณ€ํƒœ๊ฑฐ๋™์„ ๊ณ ๋ คํ•ด๋ณด๋ฉด, ๋ชจ์žฌ๋ฅผ ๊ตฌ์„ฑํ•˜๊ณ  ์žˆ๋˜ ํŽ˜๋ผ์ดํŠธ/๋ฐด๋“œ ํŽ„๋ผ์ดํŠธ ์กฐ์ง ์ค‘ ๋ฐด๋“œ ํŽ„๋ผ์ดํŠธ์™€ ์ธ์ ‘ํ•œ ํŽ˜๋ผ์ดํŠธ ๊ฒฐ์ •๋ฆฝ์—์„œ ์˜ค์Šคํ…Œ๋‚˜์ดํŠธ๋กœ์˜ ์šฐ์„  ๋ณ€ํƒœ๊ฐ€ ๊ตญ๋ถ€์ ์œผ๋กœ ์ผ์–ด๋‚˜๊ธฐ ์‹œ์ž‘ํ•˜๋ฉฐ, 20 kJ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ์˜ ๋น ๋ฅธ ๋ƒ‰๊ฐ์†๋„๋กœ ์ธํ•ด ์˜ค์Šคํ…Œ๋‚˜์ดํŠธ๋Š” ๋ฒ ์ด๋‚˜์ดํŠธ๋กœ ์žฌ๋ณ€ํƒœํ•˜๋Š” ๊ฒƒ์œผ๋กœ ์ดํ•ด๋  ์ˆ˜ ์žˆ๋‹ค. ์ฆ‰, ๋‚ฎ์€ ์ž…์—ด์กฐ๊ฑด์—์„œ์˜ ๋น ๋ฅธ ๋ƒ‰๊ฐ์†๋„์—์„œ๋Š” ์กฐ์ง ๋‚ด ๋ณ€ํƒœ์˜ ๋ฒ”์œ„๊ฐ€ ๊ตญ๋ถ€์  ์šฐ์„ ๋ณ€ํƒœ ์˜์—ญ์œผ๋กœ ํ•œ์ •๋˜์–ด ๊ฒฐ๊ณผ์ ์œผ๋กœ ๋ฒ ์ด๋‚˜์ดํŠธ๊ฐ€ ์กด์žฌํ•˜๋˜, ์กด์žฌ์˜์—ญ์˜ ๊ตญ๋ถ€์  ํŽธ์ค‘๋„๊ฐ€ ๋†’์€ ๊ฒƒ์œผ๋กœ ์‚ฌ๋ฃŒ๋œ๋‹ค. ๋ฐ˜๋ฉด, ์ƒ๋Œ€์ ์œผ๋กœ ๋†’์€ ์ž…์—ด์กฐ๊ฑด์—์„œ๋Š” ์˜ค์Šคํ…Œ๋‚˜์ดํŠธ ๋ณ€ํƒœ๊ฐ€ ๋‹ค์ˆ˜์˜ ํŽ˜๋ผ์ดํŠธ ๊ฒฐ์ •๋ฆฝ ์ „๋ฐ˜์œผ๋กœ ๋ณด๋‹ค ํ™•์žฅ๋˜์–ด ๊ฒฐ๊ตญ ๋ฏธ์„ธํ•œ ํฌ๊ธฐ์˜ ํŽ˜๋ผ์ดํŠธ/๋ถ„์‚ฐ๋œ ํŽ„๋ผ์ดํŠธ ํ˜•ํƒœ์˜ ์กฐ์ง์ด ํ˜•์„ฑ๋˜๋Š” ๊ฒƒ์œผ๋กœ ํŒŒ์•…๋œ๋‹ค.

๊ทธ๋ฆผ 5๋Š” M-A์˜ ์„ ํƒ์  etching ํ›„ OM์„ ํ†ตํ•ด ๊ด€์ฐฐํ•œ ๋ฏธ์„ธ์กฐ์ง ํ˜•์ƒ์„ ๋‚˜ํƒ€๋‚ด๋ฉฐ ๊ทธ๋ฆผ 6์€ image analyzer๋ฅผ ํ™œ์šฉํ•˜์—ฌ ์ •๋Ÿ‰์ ์œผ๋กœ ๋„์ถœํ•œ M-A๋ถ„์œจ์„ ๋‚˜ํƒ€๋‚ธ๋‹ค. ์ธก์ • ๊ฒฐ๊ณผ, ์ „์ฒด์ ์ธ M-A๋Š” CGHAZ ๋Œ€๋น„ ICHAZ์—์„œ ๊ทธ ๋ถ„์œจ์ด ์ƒ๋Œ€์ ์œผ๋กœ ๋†’์€ ๊ฒƒ์œผ๋กœ ๋‚˜ํƒ€๋‚ฌ๋Š”๋ฐ, ๋Œ€๋ถ€๋ถ„ 20 kJ์˜ ์ž…์—ด์กฐ๊ฑด์ด M-Aํ˜•์„ฑ ๋ฐ ๋ถ„์œจ์ฐจ์ด๋ฅผ ์ง€๋ฐฐํ•˜๋Š” ์กฐ๊ฑด์ž„์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค. ์ด๋Š” ์•ž์„œ ์–ธ๊ธ‰ํ•œ intercritical ์˜์—ญ ๋‚ด ์ƒ๋ณ€ํƒœ์‹œ ๋‚ฎ์€ ์ž…์—ด์กฐ๊ฑด์—์„œ์˜ ๋น ๋ฅธ ๋ƒ‰๊ฐ์†๋„์— ๊ธฐ์ธํ•œ ๊ตญ๋ถ€์  ์šฐ์„ ๋ณ€ํƒœ ์˜์—ญ์œผ๋กœ์˜ ํƒ„์†Œ ํŽธ์ค‘ ํ˜„์ƒ๊ณผ ๋ฐ€์ ‘ํ•œ ๊ด€๋ จ์ด ์žˆ๋‹ค. ๊ฒฐ๊ตญ, ๋ฒ ์ด๋‚˜์ดํŠธ ์กฐ์ง์˜ lath ๊ณ„๋ฉด์— ๊ฑธ์ณ ๊ณ ๋ฅด๊ฒŒ ๋ถ„์‚ฐ๋œ ํ˜•ํƒœ๋ฅผ ๋ณด์ด๋Š” CGHAZ ๋‚ด M-A์™€ ๋‹ฌ๋ฆฌ ICHAZ์—์„œ๋Š” ์ฃผ๋กœ ๋ฒ ์ด๋‚˜์ดํŠธ๊ฐ€ ๊ตญ๋ถ€์ ์œผ๋กœ ๋ฐ€์ง‘๋˜์–ด ์กด์žฌํ•˜๋Š” ์˜์—ญ์— ํŽธ์ค‘๋œ ํ˜•ํƒœ๋กœ ์กด์žฌํ•˜๋Š” ๊ฒฐ๊ณผ๋ฅผ ๊ฐ€์ ธ์˜จ ๊ฒƒ์ด๋‹ค. ๋ฌผ๋ก  35 kJ ์ด์ƒ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ๋Š” ํƒ€ ์„ ํ–‰์—ฐ๊ตฌ [25]์—์„œ ์ œ์‹œํ•œ M-A ๋ถ„์œจ (๋Œ€๋žต 2% ๋‚ด์™ธ)๊ณผ ์œ ์‚ฌํ•˜๊ฒŒ ๋‚ฎ์€ ์ˆ˜์ค€์˜ M-A ๋ถ„์œจ์ด ๋„์ถœ๋œ ๊ฒƒ์„ ํ† ๋Œ€๋กœ, ๋ณธ ๊ฐ•์žฌ์˜ ๊ฒฝ์šฐ 20 kJ์˜ ์ €์ž…์—ด ์กฐ๊ฑด์— ๊ตญํ•œํ•˜์—ฌ ์ƒ๋‹นํžˆ ๋†’์€ ์ˆ˜์ค€์˜ M-A ๋ถ„์œจ์ด ํŠนํžˆ ICHAZ ๋‚ด์— ๋„์ถœ๋˜๋Š”๋ฐ, ๋”ฐ๋ผ์„œ ํŠน์ • ๊ฐ’ ์ดํ•˜์˜ ์ž…์—ด์ˆ˜์ค€์—์„œ๋Š” ์ž…์—ด๋Ÿ‰ ์กฐ๊ฑด์— ๋”ฐ๋ฅธ M-A ๋ถ„์œจ ๋ณ€ํ™”๊ฐ€ํด ๊ฒƒ์œผ๋กœ ์˜ˆ์ƒํ•ด ๋ณผ ์ˆ˜ ์žˆ๋‹ค.

3.2 ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰ ์ธก์ •

๊ทธ๋ฆผ 7์€ ์ธ์œ„์ ์ธ ์ˆ˜์†Œ charging์„ ํ†ตํ•ด, ๊ฐ•์žฌ ํ‘œ๋ฉด์˜ ๋ถ€์‹๋ฐ˜์‘์„ ๋ฐฐ์ œํ•œ ์ƒํƒœ์—์„œ ๊ฐ• ๋‚ด๋ถ€๋กœ ์œ ์ž…๋œ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์„ ์ธก์ •ํ•œ ๊ฒฐ๊ณผ๋ฅผ ๋‚˜ํƒ€๋‚ธ๋‹ค. ์ธ๊ฐ€๋œ ์ž…์—ด๋Ÿ‰์ด ๋‚ฎ์„์ˆ˜๋ก ์ „์ฒด์ ์ธ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์€ ๋†’๊ฒŒ ์ธก์ •๋˜์—ˆ๊ณ , ํŠนํžˆ 35 ๋ฐ 50 kJ์˜ ์ž…์—ด๋Œ€๋น„, 20 kJ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ์˜ ์ˆ˜์†Œ๋Ÿ‰์ด ํ˜„์ €ํžˆ ๋†’์€ ์ˆ˜์ค€์œผ๋กœ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ์ด๋Š”, ๋ƒ‰๊ฐ์†๋„๊ฐ€ ๋น ๋ฅธ ์กฐ๊ฑด์ผ์ˆ˜๋ก ์ €์˜จ๋ณ€ํƒœ์กฐ์ง (๋ฒ ์ด๋‚˜์ดํŠธ)์˜ ๋ถ„์œจ์ด ๋†’๊ฒŒ ํ˜•์„ฑ๋˜์–ด ๋‚ด๋ถ€ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ์˜ ํŠธ๋žฉ์‚ฌ์ดํŠธ๊ฐ€ ์ฆ๊ฐ€ํ•œ ๋ฐ์— ๋”ฐ๋ฅธ ๊ฒƒ์œผ๋กœ ์ผ๋ฐ˜์ ์ธ ์„ ํ–‰์—ฐ๊ตฌ ๊ฒฐ๊ณผ [26] ๋“ค๊ณผ ์ผ์น˜ํ•œ๋‹ค. ํ•œํŽธ, ์—ด์˜ํ–ฅ๋ถ€ ๋ณ„ ์กฐ๊ฑด์˜ ๊ฒฝ์šฐ, CGHAZ๊ฐ€ ICHAZ ๋Œ€๋น„ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์ด ๋†’๊ฒŒ ์ธก์ •๋˜์—ˆ๋‹ค. ์„ ํ–‰๋ฌธํ—Œ์— ๋”ฐ๋ฅด๋ฉด, ์šฉ์ ‘ ํ›„ ๋ƒ‰๊ฐ ์‹œ ์ƒ์„ฑ๋œ ์ €์˜จ์กฐ์ง์ธ ๋ฒ ์ด๋‚˜์ดํŠธ ๋‚ด ํŽ˜๋ผ์ดํŠธ/์‹œ๋ฉ˜ํƒ€์ดํŠธ ๊ณ„๋ฉด๊ณผ M-A์˜ ๊ณ„๋ฉด์€ ์ˆ˜์†Œ์›์ž์˜ ๊ฐ€์—ญํŠธ๋žฉ์œผ๋กœ ์ž‘์šฉํ•˜์—ฌ ๋‚ด๋ถ€ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋ฅผ ์ฆ๊ฐ€์‹œํ‚ค๋Š” ๊ฒƒ์œผ๋กœ ์•Œ๋ ค์ ธ ์žˆ๋‹ค [27,28]. ๋ณธ ๊ฒฐ๊ณผ๋ฅผ ๋ฐ”ํƒ•์œผ๋กœ, ๋ณธ ์‹œํŽธ ๋‚ด์—์„œ ๋†’์€ ์ˆ˜์ค€์˜ M-A๋ถ„์œจ ๋Œ€๋น„ ๋†’์€ ์ˆ˜์ค€์˜ ๋ฒ ์ด๋‚˜์ดํŠธ ์กฐ์ง ๋ถ„์œจ์ด ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰ ์ฆ๊ฐ€์— ๋ณด๋‹ค ํšจ๊ณผ์ ์ž„์„ ์ง์ž‘ํ•  ์ˆ˜ ์žˆ๋‹ค. ์•ž์„œ ์–ธ๊ธ‰ํ•œ ๋ฐ”์™€ ๊ฐ™์ด, ๋ณธ ์‹คํ—˜๊ฒฐ๊ณผ๋Š” ํ‘œ๋ฉด ๋ถ€์‹๋ฐ˜์‘์ด ๋ฐฐ์ œ๋œ ์กฐ๊ฑด์—์„œ ๋‹ค๋Ÿ‰์˜ ์ˆ˜์†Œ๋ฅผ ์ธ์œ„์ ์œผ๋กœ ์ผ์ •์‹œ๊ฐ„ ์ธ๊ฐ€์‹œํ‚ค๋ฉฐ ์ „์ฒด ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์„ ๋„์ถœํ•  ๋ฟ, ๊ฐ• ๋‚ด๋ถ€ ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ ๋ฐ ํŠธ๋žฉ ๊ฑฐ๋™์— ๋Œ€ํ•œ ์„ธ๋ถ€ ์ •๋ณด๋ฅผ ์ œ๊ณตํ•˜๊ธฐ ํž˜๋“ค๋‹ค. ์ด์— ๋Œ€ํ•œ ์ถ”๊ฐ€์ ์ธ ๋ถ„์„์€ ๋‹ค์Œ 3.3์ ˆ์—์„œ ์ƒ์„ธํžˆ ๋…ผ์˜๋  ๊ฒƒ์ด๋‹ค.

3.3 ์ „๊ธฐํ™”ํ•™์  ์ˆ˜์†Œํˆฌ๊ณผ ๊ฑฐ๋™ ๋ถ„์„

๊ทธ๋ฆผ 8์€ ์šฉ์ ‘ ์กฐ๊ฑด ๋ณ„ ์‹œํŽธ์˜ ์ˆ˜์†Œํ™•์‚ฐ๊ฑฐ๋™์„ ํ‰๊ฐ€ํ•˜๊ธฐ ์œ„ํ•ด ์ˆ˜ํ–‰๋œ ์ „๊ธฐํ™”ํ•™์  ํˆฌ๊ณผ์‹คํ—˜์—์„œ์˜ decay ๊ทธ๋ž˜ํ”„๋ฅผ ๋‚˜ํƒ€๋‚ธ๋‹ค. ๋˜ํ•œ, ๊ทธ๋ฆผ 9๋Š” ์‹คํ—˜์ ์œผ๋กœ ์–ป์–ด์ง„ decay ๊ทธ๋ž˜ํ”„๋ฅผ curve fitting ํ•œ ํ›„ ๋„์ถœํ•œ ์ˆ˜์†Œํ™•์‚ฐ๊ณ„์ˆ˜ (Dapp_decay(fitting))๋ฅผ ๋‚˜ํƒ€๋‚ธ๋‹ค. ์‹ค์ œ๋กœ, ์ˆ˜์†Œํˆฌ๊ณผ ์ƒ์Šน๊ณก์„ ์„ ์šฐ์„  ํ™•๋ณดํ•˜์˜€์œผ๋‚˜ ๊ทธ ๊ฒฝ์šฐ ํˆฌ๊ณผ์œ ๋Ÿ‰ ๊ฐ’์˜ ์žฌํ˜„์„ฑ์ด ์ถฉ๋ถ„ํžˆ ํ™•๋ณด๋˜์ง€ ์•Š์•˜๋‹ค. ๋ณธ ์‹œํ—˜ํŽธ์€ ASTM A516 ์ƒ์šฉ๊ฐ•์žฌ๋กœ, ๊ฐœ์žฌ๋ฌผ ์ˆ˜์ค€์ œ์–ด๊ฐ€ ๋˜์ง€ ์•Š์•„ ๋‚ด๋ถ€ ๊ฐœ์žฌ๋ฌผ์˜ ํฌ๊ธฐ ๋ฐ ๋ถ„์œจ์ด ๋†’์€ ์ผ๋ฐ˜์žฌ์— ํ•ด๋‹น๋˜๋ฉฐ, ์ด ๊ฒฝ์šฐ ์ˆ˜์†Œํˆฌ๊ณผ ์ดˆ๊ธฐ data์˜ ์žฌํ˜„/์‹ ๋ขฐ์„ฑ์ด ๋‚ฎ์•„ ์ˆ˜์†Œํ™•์‚ฐ๊ฑฐ๋™ ํ•ด์„์— ์žˆ์–ด ์˜ค๋ฅ˜์˜ ๊ฐ€๋Šฅ์„ฑ์ด ๋†’์€ ๊ฒƒ์œผ๋กœ ํŒ๋‹จํ•˜์˜€๋‹ค. ๋”ฐ๋ผ์„œ, ์ˆ˜์†Œํˆฌ๊ณผ ์ดˆ๊ธฐ์— ์‹œํŽธ ํ‘œ๋ฉด ๋ฐ ๋‚ด๋ถ€์— ์กด์žฌํ•˜๋Š” ๊ฐœ์žฌ๋ฌผ์— ์˜ํ•œ ์ˆ˜์†Œํ™•์‚ฐ์˜ ์˜ํ–ฅ์„ ๋ฐฐ์ œํ•˜๊ณ , ๊ฒฉ์ž ๋ฐ ๊ฐ€์—ญํŠธ๋žฉ๋งŒ์ด ๊ฐœ์ž…๋˜์–ด ํ™•์‚ฐ๊ฑฐ๋™์„ ๋ถ„์„ํ•˜๋Š” desorption ํ›„ decay ๊ณก์„  ๋ถ„์„์„ ํ†ตํ•œ ํ™•์‚ฐ๋ณ€์ˆ˜ ๊ฐ’ ๋„์ถœ์ด ๋ณด๋‹ค ์‹ ๋ขฐ๋„๊ฐ€ ๋†’์€ ๊ฒƒ์œผ๋กœ ํ™•์ธ๋˜์–ด ๋ถ„์„์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค.

๊ทธ๋ฆผ 8์—์„œ ๋ณด์ด๋Š” ๋ฐ”์™€ ๊ฐ™์ด, ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ ์†๋„๋Š” ์ž…์—ด๋Ÿ‰์ด ๋‚ฎ์€ 20 kJ ์‹œํŽธ์—์„œ ๊ฐ€์žฅ ๋А๋ฆฌ๊ฒŒ ์ธก์ •๋˜์—ˆ์œผ๋ฉฐ ์ž…์—ด๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ์†๋„๋Š” ์ฆ๊ฐ€ํ•˜๋Š” ๊ฒฝํ–ฅ์„ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ์ฐธ๊ณ ๋กœ ํ‘œ 2์— decay ๊ณก์„ ์—์„œ ๋„์ถœ๋œ ํ™•์‚ฐ๊ณ„์ˆ˜ (Dapp_decay(fitting))์™€ ์ˆ˜์†Œํˆฌ๊ณผ์ดˆ๊ธฐ ์ „๋ฅ˜ ๊ฐ’์ด ์„ ํ˜•์ ์œผ๋กœ ์ƒ์Šนํ•˜๊ธฐ ์‹œ์ž‘ํ•˜๋Š” ๊ตฌ๊ฐ„์— ์™ธ์‚ฝํ•˜์˜€์„ ๋•Œ์˜ ์‹œ๊ฐ„ (tbt)์„ ํ†ตํ•ด ๋„์ถœ๋œ ํ™•์‚ฐ๊ณ„์ˆ˜ (Dapp_rising(tbt))๊ฐ๊ฐ์„ ๋น„๊ตํ•˜์—ฌ ๋‚˜ํƒ€๋‚ด์—ˆ๋Š”๋ฐ, ์ „๋ฐ˜์ ์œผ๋กœ (Dapp_decay(fitting)) ๋Œ€๋น„ (Dapp_rising(tbt))๊ฐ’์ด ๋†’๊ฒŒ ๋„์ถœ๋˜์—ˆ๊ณ , ํŠนํžˆ ์กฐ์ง ๋‚ด ์ €์˜จ๋ณ€ํƒœ์ƒ์˜ ๋ถˆ๊ท ์ผํ•œ ํŽธ์ค‘๋„๊ฐ€ ๋†’๊ฒŒ ๋‚˜ํƒ€๋‚œ 20 kJ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ ๊ทธ ์ฐจ์ด๊ฐ€ ์ƒ๋Œ€์ ์œผ๋กœ ํฌ๊ฒŒ ๋‚˜ํƒ€๋‚ฌ์œผ๋‚˜, ์‹œํŽธ ๋ณ„ ์šฉ์ ‘์ž…์—ด ์กฐ๊ฑด์— ๋”ฐ๋ฅธ ๊ฒฝํ–ฅ์„ฑ์€ ๋™์ผํ•˜๊ฒŒ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ๋˜ํ•œ, ์œ ์‚ฌ๊ฐ•์ข…์„ ๋Œ€์ƒ์œผ๋กœ ์ˆ˜ํ–‰ํ•œ ์„ ํ–‰์—ฐ๊ตฌ [29]์—์„œ ์ œ์‹œ๋œ ํ™•์‚ฐ๊ณ„์ˆ˜ ๊ฐ’๋“ค (๋ชจ์žฌ๊ธฐ์ค€ 1โ€“2 ร— 10-9m2/s) ๊ณผ์˜ ๋น„๊ต ์ธก๋ฉด์—์„œ๋„ ์ ์ ˆ ๋ฒ”์œ„ ๋‚ด์— ์žˆ๋Š” ๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค.

์„ ํ–‰๋ฌธํ—Œ์— ๋”ฐ๋ฅด๋ฉด M-A์ƒ ๋‚ด ๋งˆ๋ฅดํ…์‚ฌ์ดํŠธ/์˜ค์Šคํ…Œ๋‚˜์ดํŠธ ๊ณ„๋ฉด์˜ binding ์—๋„ˆ์ง€๋Š” ๋Œ€๋žต 52 kJ/mol [30] ์ •๋„์ด๋ฉฐ ๋ฒ ์ด๋‚˜์ดํŠธ ์กฐ์ง ๋‚ด ํŽ˜๋ผ์ดํŠธ/์‹œ๋ฉ˜ํƒ€์ดํŠธ ๊ณ„๋ฉด์˜ binding ์—๋„ˆ์ง€ (11-18 kJ/mol) [5,31] ๋Œ€๋น„ ๋†’์€ ์ˆ˜์ค€์œผ๋กœ ์ˆ˜์†Œ์›์ž ํ™•์‚ฐ์†๋„๋ฅผ ๊ฐ์†Œ์‹œํ‚ค๋Š”๋ฐ ํฌ๊ฒŒ ๊ธฐ์—ฌํ•  ๊ฒƒ์ด๋ผ๊ณ  ํŒ๋‹จ๋˜์—ˆ์œผ๋‚˜ ์‹ค์ œ ์‹คํ—˜์ ์œผ๋กœ ํš๋“ํ•œ ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ์†๋„๋Š” CGHAZ๊ฐ€ ๋‚ฎ๊ฒŒ ์ธก์ •๋˜์—ˆ๋‹ค. ์ด๋Š”, ๋†’์€ ๋ถ„์œจ์˜ ๋ฒ ์ด๋‚˜์ดํŠธ๊ฐ€ ์ƒ๋Œ€์ ์œผ๋กœ ํŽธ์ค‘๋˜์–ด ์žˆ๋Š” M-A ๋Œ€๋น„ ์ˆ˜์†Œ์›์ž์˜ ํšจ๊ณผ์ ์ธ ํŠธ๋žฉ์‚ฌ์ดํŠธ๋กœ ์ž‘์šฉํ•˜์—ฌ ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ์†๋„๋ฅผ ํฌ๊ฒŒ ๊ฐ์†Œ์‹œํ‚จ ๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋˜์—ˆ๋‹ค. ํŠนํžˆ, ICHAZ์˜ ๊ฒฝ์šฐ ๋ฏธ์„ธ์กฐ์ง ๊ด€์ฐฐ ๊ฒฐ๊ณผ์—์„œ ์–ธ๊ธ‰ํ•œ ๋ฐ”์™€ ๊ฐ™์ด, ๊ตญ๋ถ€์ ์œผ๋กœ ํŽธ์ค‘๋œ M-A์™€ ํŽ˜๋ผ์ดํŠธ์˜ ๋ฏธ์„ธ์กฐ์ง์€ M-A์— ์„ ํƒ์ ์œผ๋กœ ์ˆ˜์†Œ์›์ž๊ฐ€ ์ผ๋ถ€ ํŠธ๋žฉ ๋œ๋‹ค ํ• ์ง€๋ผ๋„ ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ์†๋„๊ฐ€ ๋น ๋ฅธ ํŽ˜๋ผ์ดํŠธ ๊ธฐ์ง€๋ฅผ ํ†ตํ•ด ์ˆ˜์†Œ์›์ž๋Š” ์šฉ์ดํ•˜๊ฒŒ ํ™•์‚ฐํ•˜์—ฌ ์ˆ˜์†Œ์›์ž์˜ ํ™•์‚ฐ์†๋„๊ฐ€ ์ƒ๋Œ€์ ์œผ๋กœ ๋†’์€ ๊ฒƒ์œผ๋กœ ์ถ”์ธก๋˜์—ˆ๋‹ค. ์ถ”๊ฐ€์ ์œผ๋กœ, ๊ฐ•์žฌ ๋‚ด ์ˆ˜์†Œ์›์ž์˜ ํŠธ๋žฉ๋ฐ€๋„๋ฅผ ์ธก์ • ๋ฐ ๋น„๊ตํ•˜๊ธฐ ์œ„ํ•ด, ์‹ (7)๋ฅผ ํ†ตํ•ด ํŠธ๋žฉ๋ฐ€๋„๋ฅผ ๋„์ถœํ•˜์˜€์œผ๋ฉฐ, ๊ทธ ๊ฒฐ๊ณผ๋ฅผ ๊ทธ๋ฆผ 10์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ๊ฐ•์žฌ ๋‚ด๋ถ€ ์ˆ˜์†Œ์›์ž์˜ ํŠธ๋žฉ๋ฐ€๋„๋Š” ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์ด ๋†’๊ณ  ๋ฐ ์ˆ˜์†Œํ™•์‚ฐ๊ณ„์ˆ˜๊ฐ€ ๋‚ฎ์€ ๊ฒฝํ–ฅ๊ณผ ์ž˜ ์ƒ์‘ํ•˜์˜€์œผ๋ฉฐ ์ž…์—ด๋Ÿ‰์ด ๋‚ฎ์„์ˆ˜๋ก, ๋ฒ ์ด๋‚˜์ดํŠธ ๋ถ„์œจ์ด ๋†’์„์ˆ˜๋ก ๋‚ด๋ถ€ ํŠธ๋žฉ๋ฐ€๋„๋Š” ๋†’๊ฒŒ ์ธก์ •๋˜์—ˆ๋‹ค. ์•ž์„  ์ผ๋ จ์˜ ๊ฒฐ๊ณผ๋ฅผ ๋ฐ”ํƒ•์œผ๋กœ, ์ˆ˜์†Œ์›์ž์˜ ๋‚ฎ์€ ํ™•์‚ฐ๊ณ„์ˆ˜์™€ ๋†’์€ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์„ ๋ฐ”ํƒ•์œผ๋กœ ํŒ๋‹จํ•˜๊ฑด๋ฐ, ์ˆ˜์†Œ์ทจํ™”ํŠน์„ฑ์ด ๊ฐ€์žฅ ์—ด์œ„ํ•œ ์ง€์—ญ์€ CGHAZ์ผ ๊ฒƒ์œผ๋กœ ์‰ฝ๊ฒŒ ์˜ˆ์ƒํ•  ์ˆ˜ ์žˆ๋‹ค. ํ•˜์ง€๋งŒ, ์‹ค์ œ ์šฉ์ ‘ ์‹œํŽธ์„ ๋Œ€์ƒ์œผ๋กœ, H2S๊ฐ€ ํฌํ•จ๋œ ๋ถ€์‹ ํ™˜๊ฒฝ ๋‚ด์—์„œ ์ธ์žฅ์‹คํ—˜์„ ์ˆ˜ํ–‰ํ•œ ๊ฒฐ๊ณผ, ์•ž์„  ์˜ˆ์ƒ๊ณผ ๋‹ค๋ฅธ ๊ฒฐ๊ณผ๊ฐ€ ๋„์ถœ๋˜์—ˆ๊ณ  ์ž์„ธํ•œ ๊ฒฐ๊ณผ๋Š” ๋‹ค์Œ 3.4์ ˆ์—์„œ ์ƒ์„ธํžˆ ๋…ผ์˜๋  ๊ฒƒ์ด๋‹ค.

3.4 SSRT ์‹คํ—˜ ๋ฐ ๋ฌด๊ฒŒ๊ฐ๋Ÿ‰ ์ธก์ •

๊ทธ๋ฆผ 11์€ CGHAZ ๋ฐ ICHAZ ์‹œํŽธ์˜ 10์ผ๊ฐ„ ๋ถ€์‹ํ™˜๊ฒฝ ๋‚ด ์นจ์ง€ ํ›„ ๋ฌด๊ฒŒ๊ฐ๋Ÿ‰ ๋ฐ ๋‹จ๋ฉด ํ˜•์ƒ์„ ๋‚˜ํƒ€๋‚ธ๋‹ค. ๊ทธ๋ฆผ 11 (a)์—์„œ ๋ณด์ด๋Š” ๋ฐ”์™€ ๊ฐ™์ด, CGHAZ์˜ ๋ฌด๊ฒŒ๊ฐ๋Ÿ‰์€ ICHAZ ๋Œ€๋น„ ๋†’๊ฒŒ ์ธก์ •๋˜์—ˆ๋Š”๋ฐ ์ด๋Š” CGHAZ์˜ ๋†’์€ ๋ฒ ์ด๋‚˜์ดํŠธ ๋ถ„์œจ์— ๊ธฐ์ธํ•˜์—ฌ ์ „์ฒด์ ์ธ ๋ถ€์‹์ €ํ•ญ์„ฑ์ด ๋‹ค์†Œ ๋‚ฎ์€ ๊ฒƒ์œผ๋กœ ํŒ๋‹จํ•  ์ˆ˜ ์žˆ๋‹ค. ํ•˜์ง€๋งŒ ๊ฐ ์‹œํŽธ์˜ ๋‹จ๋ฉด๋ถ€ ๊ด€์ฐฐ ๊ฒฐ๊ณผ, ICHAZ ํ‘œ๋ฉด์—์„œ๋Š” pitting๊ณผ ์œ ์‚ฌํ•œ ํ˜•ํƒœ์˜ ๊ตญ๋ถ€์  ๋ถ€์‹ํ”์ ์ด ๊ด€์ฐฐ๋˜์—ˆ๋‹ค (๊ทธ๋ฆผ 11(b)). ์‹œํŽธ ์ „ ์˜์—ญ์— ๊ฑธ์ณ ๋ฒ ์ด๋‚˜์ดํŠธ ์กฐ์ง์ด ํ˜•์„ฑ๋˜์–ด ์žˆ๋Š” CGHAZ ๋Œ€๋น„, ICHAZ์˜ ๊ฒฝ์šฐ M-A์˜ ๊ตญ๋ถ€ํŽธ์ค‘๋„๊ฐ€ ๋†’์€ ๊ฒƒ๊ณผ ๋ฐ€์ ‘ํ•œ ๊ด€๋ จ์ด ์žˆ๋Š” ๊ฒƒ์œผ๋กœ ์ง์ž‘ํ•  ์ˆ˜ ์žˆ๋‹ค.

๊ทธ๋ฆผ 12๋Š” ์‹ค์ œ ์šฉ์ ‘ (FCAW: 20 kJ์˜ ์ž…์—ด์กฐ๊ฑด) ์‹œํŽธ์„ ๋Œ€์ƒ์œผ๋กœ ์šฉ์ ‘ ํ›„ ๊ณต๊ธฐ ์ค‘์—์„œ SSRT ์‹คํ—˜ ํ›„ ๊ด€์ฐฐํ•œ ์‹œํŽธ์˜ ํŒŒ๋‹จํ˜•์ƒ (12 (a)) ๋ฐ DIC๋ฅผ ํ†ตํ•ด ํ™•์ธํ•œ ๋™์ ํ•˜์ค‘ ํ•˜์—์„œ์˜ ์‘๋ ฅ์ง‘์ค‘๋ถ€ (12 (b)), ๊ทธ๋ฆฌ๊ณ  H2S๊ฐ€ ํฌํ•จ๋œ ๋ถ€์‹ํ™˜๊ฒฝ ๋‚ด์—์„œ SSRT ์‹คํ—˜ ํ›„ ๊ด€์ฐฐํ•œ ์‹œํŽธ์˜ ํŒŒ๋‹จํ˜•์ƒ (12 (c))์„ ๋‚˜ํƒ€๋‚ธ๋‹ค. DIC ๊ฒฐ๊ณผ๋ฅผ ํ† ๋Œ€๋กœ, ์ธ์žฅ์‘๋ ฅ์ด ์ง‘์ค‘๋˜๋Š” ์˜์—ญ์€ ๊ฐ€์žฅ ์—ฐํ•œ์กฐ์ง์„ ํ˜•์„ฑํ•˜๊ณ  ์žˆ๋Š” ๋ชจ์žฌ๋ถ€์ž„์„ ํŒ๋‹จํ•  ์ˆ˜ ์žˆ๊ณ  ์ตœ์ข… ํŒŒ๋‹จ์˜์—ญ ๋˜ํ•œ ์ˆœ์ˆ˜ ๋ชจ์žฌ๋ถ€๋กœ ๊ตญํ•œ๋˜๋ฉฐ ๋„คํ‚น ํ˜„์ƒ์„ ์ˆ˜๋ฐ˜ํ•˜์˜€์Œ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค. ํ•˜์ง€๋งŒ H2S๊ฐ€ ํฌํ•จ๋œ ๋ถ€์‹ํ™˜๊ฒฝ ๋‚ด์— ๋…ธ์ถœ๋  ๊ฒฝ์šฐ, ๊ท ์—ด๊ฐœ์‹œ ๋ฐ ์ „ํŒŒ์˜์—ญ ๊ด€์ฐฐ์„ ํ†ตํ•œ ํŒŒ๋‹จ์–‘์ƒ์„ ๊ณ ๋ คํ•ด๋ณผ ๋•Œ, ๋ชจ์žฌ๋ถ€๊ฐ€ ์•„๋‹Œ ICHAZ์—์„œ ๊ท ์—ด๊ฐœ์‹œ๊ฐ€ ์ด๋ฃจ์–ด์ง€๊ณ , SCHAZ ๋ฐ ๋ชจ์žฌ๋ถ€ ์ชฝ์œผ๋กœ ๊ท ์—ด์ „ํŒŒ๊ฐ€ ์ผ์–ด๋‚˜๋ฉฐ ๋„คํ‚น์ด ๊ฑฐ์˜ ๊ด€์ฐฐ๋˜์ง€ ์•Š์Œ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค. ์ฆ‰, ์ธ์žฅ์‘๋ ฅ์ด ๊ฐ€์žฅ ์ง‘์ค‘๋˜๋Š” ๋ชจ์žฌ๋ถ€๊ฐ€ ์•„๋‹Œ ICHAZ๋กœ ๊ท ์—ด๊ฐœ์‹œ์˜์—ญ์ด ์˜ฎ๊ฒจ๊ฐ€๋ฉฐ ์ทจํ™”ํ˜„์ƒ์ด ๊ฐœ์ž…๋œ ๊ฒƒ์œผ๋กœ ํŒŒ์•…๋œ๋‹ค. ๊ทธ๋ฆผ 12 (c)์˜ SSRT ํ›„ ๊ด€์ฐฐ๋œ ํŒŒ๋‹จ์‹œํŽธ ํ•˜๋‹จ๋ถ€์—์„œ ์‚ฌ๊ฐํ˜• ๋ฐ•์Šค๋กœ ํ‘œ์‹œ๋œ ํ™”์‚ดํ‘œ ์˜์—ญ์„ ํฌํ•จํ•œ ํŒŒ๋‹จ๋ฉด์„ ๊ด€์ฐฐํ•˜์—ฌ ๊ทธ๋ฆผ 12 (d)์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ์ฃผ๋กœ ์—ฐ์„ฑ ํŒŒ๋ฉด์ธ micro dimple (M.D) ํ˜•ํƒœ์ด๋‚˜ ์ผ๋ถ€ ์˜์—ญ์€ ์ค€๋ฒฝ๊ฐœ ํŒŒ๋ฉด์ธ quasi cleavage (Q.C)๊ฐ€ ๊ด€์ฐฐ๋˜์—ˆ๊ณ , ๊ทธ Q.C ํŒจํ„ด์€ ํ‘œ๋ฉด์—์„œ ์‹œ์ž‘๋˜์–ด ์ค‘์‹ฌ๋ถ€์— ์ด๋ฅด๋Š” ์˜์—ญ์— ๊ฑธ์ณ ์—ฐ๊ฒฐ๋œ ํ˜•ํƒœ๋กœ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ์ด๋ก ์ ์œผ๋กœ, H2S๊ฐ€ ํฌํ•จ๋œ ๋ถ€์‹ ํ™˜๊ฒฝ์— ๊ฐ•์žฌ๊ฐ€ ๋…ธ์ถœ๋  ๊ฒฝ์šฐ ๊ฐ•์žฌ์˜ ์–‘๊ทน์šฉํ•ด ๋ฐ ์Œ๊ทนํ™˜์› ๋ฐ˜์‘์— ๊ธฐ์ธํ•œ ์ˆ˜์†Œ์œ ์ž… ๋ฐ ์ทจํ™”ํ˜„์ƒ์ด ๋ฐœ์ƒํ•˜๊ณ , ํ‘œ๋ฉด์€ ์ ์ฐจ ํ™ฉํ™”๋ฌผ/์‚ฐํ™”๋ฌผ ๊ธฐ๋ฐ˜์˜ ๋ถ€์‹์ƒ์„ฑ๋ฌผ๋กœ ๋ฎ์—ฌ๊ฐ€๋Š” ํ˜„์ƒ์ด ๊ฐœ์ž…๋œ๋‹ค. ์•ž ์ ˆ์˜ ๋ถ„์„๊ฒฐ๊ณผ๋ฅผ ํ† ๋Œ€๋กœ ์ˆ˜์†Œ์œ ์ž…์— ๋”ฐ๋ฅธ ์ทจํ™”๋„ ์ธก๋ฉด์—์„œ๋Š” CGHAZ์—์„œ ์ทจ์„ฑ๊ท ์—ด์˜ ๊ฐœ์‹œ์™€ ์ „ํŒŒ๊ฐ€ ๋ฐœ์ƒํ•  ๊ฒƒ์œผ๋กœ ์˜ˆ์ƒํ•  ์ˆ˜ ์žˆ์œผ๋‚˜, ์‹ค์ œ ํŒŒ๋‹จ๊ฒฐ๊ณผ๋Š” ์˜ˆ์ƒ๊ณผ ๋‹ค๋ฅด๊ฒŒ ๋‚˜ํƒ€๋‚ฌ๋‹ค.

๊ทธ๋ฆผ 13 (a)์—์„œ ๋ณด์ด๋Š” ๋ฐ”์™€ ๊ฐ™์ด ํŒŒ๋‹จ๋ฉด ์ธ๊ทผ ๋ฏธ์„ธ์กฐ์ง์€ ํŽ˜๋ผ์ดํŠธ ๋ฐ ์ €์˜จ๋ณ€ํƒœ์กฐ์ง์ด ๊ณต์กดํ•˜์—ฌ ์กด์žฌํ•˜๋Š” ํ˜•์ƒ์ด ๋‚˜ํƒ€๋‚˜๋ฉฐ ๊ท ์—ด๋ถ€ ์ธ๊ทผ์˜์—ญ์˜ ๋น„์ปค์Šค ๊ฒฝ๋„ ๊ฐ’์ด 180 HV ์ด์ƒ์œผ๋กœ ๋†’๊ฒŒ ์ธก์ •๋˜๊ธฐ๋„ ํ•˜์˜€๋‹ค. ๋˜ํ•œ, ๊ทธ ํŒŒ๋‹จ๋ถ€ ICHAZ ์ธ๊ทผ์˜์—ญ ํ‘œ๋ฉด์—๋Š” pitting๊ณผ ์œ ์‚ฌํ•œ ๊ตญ๋ถ€๋ถ€์‹ ํ˜•ํƒœ์˜ ์†์ƒ์ด ๋นˆ๋ฒˆํžˆ ๊ด€์ฐฐ๋˜์—ˆ๋‹ค (๊ทธ๋ฆผ 13 (b)). ์„ ํ–‰์—ฐ๊ตฌ์— ๋”ฐ๋ฅด๋ฉด ๋‚ด๋ถ€ ์ž”๋ฅ˜์‘๋ ฅ์ด ๋†’์€ ์ €์˜จ๋ณ€ํƒœ์กฐ์ง์˜ ๊ฒฝ์šฐ, ์ฒ  ์›์ž์˜ ์–‘๊ทน์šฉํ•ด๋ฐ˜์‘์— ๋Œ€ํ•œ ํ™œ์„ฑํ™”์—๋„ˆ์ง€ ์žฅ๋ฒฝ์ด ๋‚ฎ์•„ ์–‘๊ทน ์šฉํ•ด๋ฐ˜์‘์ด ์ด‰์ง„๋œ๋‹ค๊ณ  ์•Œ๋ ค์ ธ ์žˆ๋‹ค [32]. ๋ณธ ์—ฐ๊ตฌ์—์„œ์™€ ๊ฐ™์ด H2S๋ฅผ ํฌํ•จํ•œ ์‚ฐ์„ฑ๋ถ„์œ„๊ธฐ ๋‚ด์—์„œ, ๋ฒ ์ด๋‚˜์ดํŠธ ๋ฐ M-A ๋“ฑ์˜ ์ €์˜จ๋ณ€ํƒœ์ƒ์ด ๊ตญ๋ถ€์ ์œผ๋กœ ํŽธ์ค‘๋˜์–ด ์žˆ๋Š” ICHAZ๋Š” ๊ตญ๋ถ€์  ์šฉํ•ด๋ฐ˜์‘์ด ์ด‰์ง„๋˜์–ด pitting ํ˜•ํƒœ์˜ ๋ถ€์‹์†์ƒ์ด ๋ฐœ์ƒ๋˜๋ฉฐ ์™ธ๋ถ€์—์„œ ์ธ๊ฐ€๋œ ์ธ์žฅ์‘๋ ฅ์ด ๋ณด๋‹ค ์ง‘์ค‘๋  ์ˆ˜ ์žˆ๋Š” ์กฐ๊ฑด์„ ์ œ๊ณตํ•˜๋Š” ๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค. ๋˜ํ•œ ๊ทธ๋ฆผ 13 (b)์—์„œ ํ‘œ๋ฉด๋ถ€ ๋ถ€์‹ ์ด์™ธ์— ํ•˜๋‹จ๋ถ€ ์กฐ๋Œ€ ๊ท ์—ด์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค. ๊ฐ• ๋‚ด๋ถ€์—์„œ๋Š” ์ฃผ๋กœ ๋น„๊ธˆ์† ๊ฐœ์žฌ๋ฌผ/์„์ถœ๋ฌผ ๋“ฑ์—์„œ ์ทจํ™”๊ท ์—ด์ด ๊ฐœ์‹œ๋˜์–ด SSC ํŒŒ๋‹จ์„ ์ผ์œผํ‚จ๋‹ค๋Š” ์„ ํ–‰์—ฐ๊ตฌ [33] ๊ฒฐ๊ณผ๋ฅผ ๊ณ ๋ คํ•  ๋•Œ, ICHAZ์—์„œ ๊ฐœ์‹œ๋˜์–ด ๋ฐœ์ƒ๋œ ํŒŒ๋‹จ์€ ํ‘œ๋ฉด์—์„œ ํ˜•์„ฑ๋œ pitting ํ˜•ํƒœ์˜ ๊ตญ๋ถ€์  ์†์ƒ์ด ๋‚ด๋ถ€ blister ๊ท ์—ด (hydrogen induced blister cracks, HIBC) [33]๊ณผ ์—ฐ๊ฒฐ๋˜๋ฉฐ ์‘๋ ฅ์ง‘์ค‘์„ ๊ฐ€์†ํ™”์‹œํ‚จ๋ฐ์— ๋”ฐ๋ฅธ ๊ฒƒ์œผ๋กœ ์ถ”์ธก๋œ๋‹ค. ๋ฐ˜๋ฉด, 35 kJ์˜ ๋†’์€ ์ž…์—ด์กฐ๊ฑด ํ•˜์—์„œ ์‹œํŽธ์„ ํš๋“ํ•œ ํ›„ ๋ถ€์‹ํ™˜๊ฒฝ ๋‚ด ๋™์ผ ์‹คํ—˜ ์ˆ˜ํ–‰ ์‹œ์—๋Š”, ๊ฐ€์žฅ ์—ฐํ•œ ์กฐ์ง์„ ํ˜•์„ฑํ•˜๊ณ  ์žˆ๋Š” ๋ชจ์žฌ๋ถ€์—์„œ ํŒŒ๋‹จ์ด ๋ฐœ์ƒํ•œ ์ถ”๊ฐ€์‹คํ—˜๊ฒฐ๊ณผ๋ฅผ ๊ณ ๋ คํ•  ๋•Œ, ๋ณธ ๊ฐ•์žฌ์˜ ์ทจ์„ฑํŒŒ๊ดด๊ฑฐ๋™ ๋ฐ ํŒŒ๋‹จ์œ„์น˜๋Š” ์ž…์—ด๋Ÿ‰์— ํฌ๊ฒŒ ์˜์กดํ•˜๋ฉฐ, 20 kJ์˜ ์ €์ž…์—ด ์กฐ๊ฑด์— ๊ตญํ•œํ•˜์—ฌ ICHAZ ์กฐ์ง ๋‚ด ์ €์˜จ๋ณ€ํƒœ์ƒ์˜ ๋†’์€ ๊ตญ๋ถ€์  ํŽธ์ค‘๋„์— ๊ธฐ์ธํ•˜์—ฌ ์ทจ์„ฑํŒŒ๊ดด ์ €ํ•ญ์„ฑ์ด ๊ฐ€์žฅ ์—ด์œ„ํ•˜๊ฒŒ ๋‚˜ํƒ€๋‚œ ๊ฒƒ์œผ๋กœ ์‚ฌ๋ฃŒ๋œ๋‹ค.

์š”์ปจ๋Œ€, ๊ฐ•์žฌ ๋‚ด๋ถ€ ์ˆ˜์†Œํ™•์‚ฐ๊ณ„์ˆ˜๊ฐ€ ๋‚ฎ๊ณ , ํ™•์‚ฐ์„ฑ์ˆ˜์†Œ๋Ÿ‰์ด ๋†’์€ CGHAZ์˜ ๊ฒฝ์šฐ ์ˆ˜์†Œ์ทจํ™”๋„๊ฐ€ ๊ฐ€์žฅ ๋†’๊ฒŒ ํ‰๊ฐ€๋  ์ˆ˜ ์žˆ์œผ๋‚˜, H2S๋ฅผ ํฌํ•จํ•œ ์‚ฐ์„ฑํ™˜๊ฒฝ์— ๋…ธ์ถœํ•˜์—ฌ ์‘๋ ฅ์ธ๊ฐ€ ์‹œ, ํŒŒ๋‹จ์ €ํ•ญ์„ฑ์ด ๊ฐ€์žฅ ๋‚ฎ์€ ์˜์—ญ์€ ์ €์˜จ๋ณ€ํƒœ์ƒ์˜ ๋ถ„์œจ์€ ์ƒ๋Œ€์ ์œผ๋กœ ๋‚ฎ์œผ๋‚˜ ๊ตญ๋ถ€ํŽธ์ค‘๋„๊ฐ€ ๊ฐ€์žฅ ๋†’์€ ICHAZ์ž„์„ ํ™•์ธํ•˜์˜€๋‹ค. ์ด์™€ ๊ฐ™์ด 20 kJ์˜ ์ €์ž…์—ด ์กฐ๊ฑด ํ•˜์—์„œ ICHAZ ์กฐ์ง ๋‚ด ํ˜•์„ฑ๋œ ์ €์˜จ๋ณ€ํƒœ์ƒ์˜ ๋†’์€ ๊ตญ๋ถ€ํŽธ์ค‘๋„๋Š” ๋ถ€์‹๊ณผ ์‘๋ ฅ์˜ ๋ณตํ•ฉ์กฐ๊ฑด ํ•˜์—์„œ ๊ตญ๋ถ€์  ๋ถ€์‹์†์ƒ์„ ์œ ๋ฐœํ•˜๋ฉฐ ์‘๋ ฅ ์ง‘์ค‘์— ๋”ฐ๋ฅธ ํŒŒ๋‹จ์ €ํ•ญ์„ฑ์„ ๊ฐ์†Œ์‹œํ‚ค๋Š” ๊ฒƒ์œผ๋กœ ์‚ฌ๋ฃŒ๋œ๋‹ค. ๋‹ค๋งŒ ๋ณธ ์—ฐ๊ตฌ๋Š” ์ „๊ธฐํ™”ํ•™์  ์ˆ˜์†Œ์ธ๊ฐ€์กฐ๊ฑด๊ณผ H2S๋ฅผ ํฌํ•จํ•œ ์‚ฐ์„ฑํ™˜๊ฒฝ์— ๋…ธ์ถœํ•˜์—ฌ ์‘๋ ฅ์ธ๊ฐ€ ์กฐ๊ฑด์—์„œ์˜ ๊ฐ•์žฌ ๋‚ด๋ถ€ ์ˆ˜์†Œ๋Ÿ‰ ๋“ฑ์˜ ์ฐจ์ด ์œ ๋ฌด์— ๋Œ€ํ•œ ์ถ”๊ฐ€์—ฐ๊ตฌ๊ฐ€ ํ•„์š”ํ•˜๋‹ค๋Š” ํ•œ๊ณ„๋ฅผ ๋‚ด์ œํ•˜๊ณ  ์žˆ์œผ๋ฉฐ, ๋‹ค์ธต์šฉ์ ‘๊ณต์ • ํ•˜์—์„œ ์ค‘๋ณต ์—ด์ด๋ ฅ ์กฐ๊ฑด์œผ๋กœ ๋ฏธ์„ธ์กฐ์ง์ด ํ˜•์„ฑ๋˜๋Š” ์˜์—ญ (e.g. ICCGHAZ, CGICHAZ, ICICHAZ ๋“ฑ)์„ ๋Œ€์ƒ์œผ๋กœ ๋ณด๋‹ค ์„ธ๋ถ„ํ™”ํ•˜์—ฌ ํ–ฅํ›„ ์ถ”๊ฐ€ ์—ฐ๊ตฌ๋ฅผ ์ง„ํ–‰ํ•ด ๋ณผ ํ•„์š”๊ฐ€ ์žˆ๋‹ค.

4. ๊ฒฐ ๋ก 

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์••๋ ฅ์šฉ๊ธฐ์šฉ A516-65 ๊ฐ•์žฌ๋ฅผ ๋Œ€์ƒ์œผ๋กœ ์ƒ์ดํ•œ ์šฉ์ ‘ ์ž…์—ด๋Ÿ‰ (20, 35, 50 kJ/cm)์œผ๋กœ ์—ด ๋ชจ์‚ฌ๋œ ์—ด์˜ํ–ฅ๋ถ€์˜ ์ˆ˜์†Œํ™•์‚ฐ๊ฑฐ๋™ ๋ฐ ์ทจ์„ฑํŒŒ๊ดด ํŠน์„ฑ์— ๋Œ€ํ•œ ๋ถ„์„์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. ์ฃผ์š” ์‹คํ—˜๊ฒฐ๊ณผ๋Š” ์•„๋ž˜์™€ ๊ฐ™์ด ๊ฐ„๋žตํžˆ ์š”์•ฝ๋œ๋‹ค.

1) ์„ธ ์ž…์—ด์กฐ๊ฑด ๋ชจ๋‘์—์„œ CGHAZ ๋‚ด ๋ฒ ์ด๋‚˜์ดํŠธ๊ฐ€ ๊ด€์ฐฐ๋˜์—ˆ๊ณ  ICHAZ์—์„œ๋Š” 20 kJ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ ํŽ˜๋ผ์ดํŠธ์™€ ๋ฒ ์ด๋‚˜์ดํŠธ๊ฐ€ ๋ณตํ•ฉ์ ์œผ๋กœ ์กด์žฌํ•˜๋˜ ๋ฒ ์ด๋‚˜์ดํŠธ ์กด์žฌ์˜์—ญ์˜ ๋ถˆ๊ท ์ผํ•œ ํŽธ์ค‘๋„๊ฐ€ ๋†’์€ ๊ฒƒ์œผ๋กœ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ๋ฐ˜๋ฉด 35 kJ ์ด์ƒ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ๋Š” ๋Œ€๋ถ€๋ถ„ ๋ฏธ์„ธํ•œ ํฌ๊ธฐ์˜ ํŽ˜๋ผ์ดํŠธ/ํŽ„๋ผ์ดํŠธ ์กฐ์ง์ด ํ˜•์„ฑ๋˜์—ˆ๋‹ค. M-A ๋ถ„์œจ ์ธก์ • ๊ฒฐ๊ณผ 20 kJ์˜ ์ž…์—ด์กฐ๊ฑด์—์„œ CGHAZ์™€ ICHAZ ๋ชจ๋‘์—์„œ ๋†’์€ M-A ๋ถ„์œจ์ด ์ธก์ •๋˜์—ˆ๋Š”๋ฐ, CGHAZ ๋Œ€๋น„ ICHAZ์—์„œ M-A ๋ถ„์œจ๊ณผ ํ•จ๊ป˜ ์กด์žฌ์˜์—ญ์˜ ๊ตญ๋ถ€์  ํŽธ์ค‘๋„ ๋˜ํ•œ ๋†’์€ ๊ฒƒ์œผ๋กœ ๋‚˜ํƒ€๋‚ฌ๋‹ค.

2) ์ธ์œ„์  ์ˆ˜์†Œ charging ๋ฐ ํˆฌ๊ณผ์‹คํ—˜๊ฒฐ๊ณผ, ๋ฒ ์ด๋‚˜์ดํŠธ์™€ M-A ๋ชจ๋‘ ์ˆ˜์†Œ์›์ž์˜ ๊ฐ€์—ญํŠธ๋žฉ์œผ๋กœ ์ž‘์šฉํ•˜์—ฌ, ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰ ์ฆ๊ฐ€์— ๊ธฐ์—ฌํ•  ์ˆ˜ ์žˆ์œผ๋ฉฐ, ๋ฒ ์ด๋‚˜์ดํŠธ ๋ถ„์œจ์ด ๋ณด๋‹ค ๋†’์€ CGHAZ์˜ ํ™•์‚ฐ์„ฑ ์ˆ˜์†Œ๋Ÿ‰์ด ๋ณด๋‹ค ๋†’๊ฒŒ ์ธก์ •๋จ์„ ํ† ๋Œ€๋กœ, ๋ณธ HAZ ๋ชจ์‚ฌ ์‹œํŽธ์—์„œ M-A ๋Œ€๋น„ ๋ฒ ์ด๋‚˜์ดํŠธ์˜ ์ˆ˜์†ŒํŠธ๋žฉ ํšจ์œจ์ด ๋ณด๋‹ค ๋†’์€ ๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋˜์—ˆ๋‹ค.

3) FCAW (20 kJ/cm์˜ ์ž…์—ด์กฐ๊ฑด) ์‹œํ—˜ํŽธ์—์„œ, ๊ณต๊ธฐ ์ค‘์—์„œ ์ˆ˜ํ–‰๋œ SSRT ์‹คํ—˜๊ฒฐ๊ณผ์™€ ๋‹ฌ๋ฆฌ sour ํ™˜๊ฒฝ ๋‚ด์—์„œ๋Š” ICHAZ์—์„œ ํŒŒ๋‹จ์ด ๋ฐœ์ƒํ•˜์˜€๋‹ค. CGHAZ์˜ ๊ฒฝ์šฐ ์ˆ˜์†ŒํŠธ๋žฉ ๋ฐ€๋„ ๋ฐ ํ™•์‚ฐ์„ฑ์ˆ˜์†Œ๋Ÿ‰์ด ๊ฐ€์žฅ ๋†’๊ฒŒ ์ธก์ •๋˜์–ด ์ทจ์„ฑํŒŒ๋‹จ์˜ ๊ฐœ์‹œ ๋ฐ ์ „ํŒŒ์˜์—ญ์ด ๋  ๊ฒƒ์œผ๋กœ ์˜ˆ์ƒํ•  ์ˆ˜ ์žˆ์œผ๋‚˜ ์‹ค์ œ SSC ํŒŒ๋‹จ์ €ํ•ญ์„ฑ์ด ๊ฐ€์žฅ ๋‚ฎ์€ ์˜์—ญ์€ ICHAZ๋กœ ๋‹ค๋ฅด๊ฒŒ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ICHAZ์˜ ๊ฒฝ์šฐ, ์ €์˜จ๋ณ€ํƒœ์ƒ์˜ ๋ถ„์œจ์€ ์ƒ๋Œ€์ ์œผ๋กœ ๋‚ฎ์œผ๋‚˜ ๊ตญ๋ถ€ํŽธ์ค‘๋„๊ฐ€ ๋†’์•„ ๋ถ€์‹๊ณผ ์‘๋ ฅ์˜ ๋ณตํ•ฉ์กฐ๊ฑด ํ•˜์—์„œ ๊ตญ๋ถ€์  ๋ถ€์‹์†์ƒ์„ ์œ ๋ฐœํ•˜๋ฉฐ, ๊ทธ๋กœ์ธํ•œ ์‘๋ ฅ์ง‘์ค‘์ด ํŒŒ๋‹จ์ €ํ•ญ์„ฑ์„ ๊ฐ์†Œ์‹œํ‚ค๋Š” ์ฃผ ์š”์ธ์œผ๋กœ ์‚ฌ๋ฃŒ๋œ๋‹ค.

Acknowledgements

This research was partly funded and conducted under the Competency Development Program for Industry Specialists of the Korean Ministry of Trade, Industry and Energy (MOTIE), operated by the Korea Institute for Advancement of Technology (KIAT) (No. P0002019, HRD Program for High Value-Added Metallic Materials Expert). In addition, this work was supported in part by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2019R1C1C1005007).

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Figures and Tables

Fig. 1.

Thermal cycles used in the HAZ simulation: (a) CGHAZ and (b) ICHAZ.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f1.jpg
Fig. 2.

Schematic diagram of an electrochemical hydrogen permeation apparatus.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f2.jpg
Fig. 3.

Schematic diagram of (a) welded joint and welding sequence, and (b) SSRT tested specimen.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f3.jpg
Fig. 4.

Microstructures of specimens obtained by thermal cycles simulation with the heat input of 20, 35, and 50 kJ/cm: CGHAZ (a, c, e) and ICHAZ (b, d, f).

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f4.jpg
Fig. 5.

Microstructures showing M-A constituents (white phase), revealed by LePera etchant: CGHAZ (a, c, e) and ICHAZ (b, d, f).

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f5.jpg
Fig. 6.

Fractions of MA constituents in CGHAZ and ICHAZ obtained by thermal cycles simulation with a heat input of 20, 35, and 50 kJ/cm, which were determined using an image analyzer.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f6.jpg
Fig. 7.

Diffusible hydrogen contents in CGHAZ and ICHAZ obtained by thermal cycles simulation with heat input of 20, 35, and 50 kJ/cm, which were measured using the glycerin volumetric method.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f7.jpg
Fig. 8.

Normalized hydrogen permeation decay curves of base metal and HAZ: (a) CGHAZ and (b) ICHAZ obtained by thermal cycles simulation with a heat input of 20, 35, and 50 kJ/cm.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f8.jpg
Fig. 9.

Hydrogen diffusivities (Dapp_decay (fitting)) of CGHAZ and ICHAZ obtained by a thermal cycling simulation with a heat input of 20, 35, and 50 kJ/cm.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f9.jpg
Fig. 10.

Hydrogen trap density of CGHAZ and ICHAZ obtained by thermal cycles simulation with a heat input of 20, 35, and 50 kJ/cm.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f10.jpg
Fig. 11.

(a) Weight loss per unit area of simulated CGHAZ and ICHAZ, measured after an immersion test in a 5% NaCl + 0.5% CH3COOH + 0.05M Na2S solution, (b) cross-sectional observation of ICHAZ obtained by a thermal cycling simulation after an immersion test.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f11.jpg
Fig. 12.

(a) Specimens fractured by SSRT evaluated in air, (b) DIC image obtained under applied tensile loading in air, (c) specimen fracture by SSRT in a 5% NaCl + 0.5% CH3COOH + 0.05M Na2S solution, and (d) fracture surface of tested specimen after SSRT evaluated in a 5% NaCl + 0.5% CH3COOH + 0.05M Na2S solution.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f12.jpg
Fig. 13.

Cross-sectional views of flux-cored arc welded specimen with heat input of 20 kJ/cm after SSRT evaluated in a 5% NaCl + 0.5% CH3COOH + 0.05M Na2S solution.

../../Resources/kim/KJMM.2020.58/kjmm-2020-58-9-599f13.jpg
Table 1.

Chemical compositions (wt%) of tested specimen.

C Si Mn P S Cr Ni Cu
A516 0.15~0.17 0.37 1.13 0.005 <0.003 <0.02 <0.12 <0.15
Table 2.

Comparison of apparent H-diffusivity values obtained by break through time (tbt) and curve-fitting to H-decay phase equation.

Specimen Thickness (mm) Heat input (kJ/cm) Dapp_decay(fitting) (m2/s) Dapp_rising(tbt) (m2/s)
BM 1.62 - 1.31 ร— 10-9 1.38 ร— 10-9
CGHAZ 1.57 20 3.32 ร— 10-10 5.06 ร— 10-10
1.59 35 6.64 ร— 10-10 7.06 ร— 10-10
1.57 50 6.99 ร— 10-10 8.85 ร— 10-10
ICHAZ 1.58 20 4.06 ร— 10-10 7.53 ร— 10-10
1.57 35 8.49 ร— 10-10 8.71 ร— 10-10
1.58 50 9.58 ร— 10-10 1.08 ร— 10-9