phase morphology and mechanical properties of ethylene

7
754 Polymer(Korea), Vol. 39, No. 5, pp. 754-760 (2015) http://dx.doi.org/10.7317/pk.2015.39.5.754 ISSN 0379-153X(Print) ISSN 2234-8077(Online) ์—ํ‹ธ๋ Œ- ํ”„๋กœํ•„๋ Œ- ๋””์—”- ๋ชจ๋…ธ๋จธ/ ๋ถˆ์†Œ๊ณ ๋ฌด ๋ธ”๋ Œ๋“œ์˜ ์ƒ ๋ชจํด๋กœ์ง€์™€ ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ ์ด๊ธฐ์จยท๊น€์Šน๊ฒธยท์œ ์šฉํ™˜ยท๊ฐ•์„์ธยท์˜ค์ข…๊ฐ‘*ยทํ—ˆ์–‘์ผ**ยท์ •๋ณ‘ํ—Œ***ยท๋‚˜์ฐฝ์šด โ€  ์ „๋ถ๋Œ€ํ•™๊ต ๊ณ ๋ถ„์ž๋‚˜๋…ธ๊ณตํ•™๊ณผ, BK21 ํ”Œ๋Ÿฌ์Šค ๊ฐ์„ฑํ„ฐ์น˜ ๊ณ ๋ถ„์ž๋ณตํ•ฉ์†Œ์žฌ ์—ฐ๊ตฌํŒ€, * ์ „๋ถ๋Œ€ํ•™๊ต ๋Œ€ํ•™์› ๋””์ž์ธ์ œ์กฐ๊ณตํ•™๊ณผ ** ์ „๋‚จ๋Œ€ํ•™๊ต ๊ณ ๋ถ„์ž์œตํ•ฉ์†Œ์žฌ๊ณตํ•™๋ถ€, *** ํ˜„๋Œ€์ž๋™์ฐจ ์—ฐ๊ตฌ์†Œ ์—ฐ๋ฃŒ์ „์ง€์ž๋™์ฐจ 1 ํŒ€ (2015 ๋…„ 2 ์›” 15 ์ผ ์ ‘์ˆ˜, 2015 ๋…„ 3 ์›” 11 ์ผ ์ˆ˜์ •, 2015 ๋…„ 3 ์›” 11 ์ผ ์ฑ„ํƒ) Phase Morphology and Mechanical Properties of Ethylene-Propylene-Diene-Monomer/Fluoroelastomer Blends Gi-Bbeum Lee, Seung Gyeom Kim, Yong Hwan Yoo, Seok In Kang, Jong Gab Oh*, Yang Il Huh**, Byeong-Heon Jeong***, and Changwoon Nah โ€  BK21 Plus Heptic Polymer Composites Research Team, Department of Polymer-Nano Science and Technology, Chonbuk National University, Jeonju 561-756, Korea *Department of Design and Manufacturing, Graduate School, Chonbuk National University, Jeonju 561-756, Korea **Department Polymer and Fiber System Engineering, Chonnam National University, Gwangju 500-757, Korea ***Fuel Cell Vehicle Team 1, R&D Division, Hyundai Motor Group, Yong-in 446-912, Korea (Received February 15, 2015; Revised March 11, 2015; Accepted March 11, 2015) ์ดˆ๋ก: ์—ํ‹ธ๋ Œ- ํ”„๋กœํ•„๋ Œ- ๋””์—”- ๋ชจ๋…ธ๋จธ(EPDM) ๊ณ ๋ฌด์™€ ๋ถˆ์†Œ๊ณ ๋ฌด(FKM) ๋ฅผ ๋‹ค์–‘ํ•œ ์กฐ์„ฑ์œผ๋กœ ๋ธ”๋ Œ๋“œ๋ฅผ ์ œ์กฐํ•˜์—ฌ ์กฐ์„ฑ์— ๋”ฐ๋ฅธ ์ƒ ๋ชจํด๋กœ์ง€์™€ ๊ฐ€๊ตํŠน์„ฑ, ๊ฒฝ๋„ํŠน์„ฑ, ์ธ์žฅํŠน์„ฑ ๊ทธ๋ฆฌ๊ณ  ๋™์  ์ ํƒ„์„ฑ ํŠน์„ฑ์„ ์กฐ์‚ฌํ•˜์˜€๋‹ค. FKM ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜ ๋ก ๊ฐ€๊ต์†๋„๋Š” ์ฆ๊ฐ€ํ•œ ๋ฐ˜๋ฉด ๊ฐ€๊ต๋ฐ€๋„๋Š” ๊ฐ์†Œํ•˜์˜€์œผ๋ฉฐ, ์ „๋ฐ˜์ ์œผ๋กœ ๊ฒฝ๋„, ์ธ์žฅ๊ฐ•๋„, ํŒŒ๋‹จ์‹ ์žฅ๋ฅ  ๋ฐ ์ €์žฅ ๋ชจ๋“ˆ๋Ÿฌ์Šค(E') ๋Š” ์ฆ๊ฐ€ํ•˜์˜€๋‹ค. ๋ชจ๋“  ๋ธ”๋ Œ๋“œ ์ปดํŒŒ์šด๋“œ์—์„œ EPDM๊ณผ FKM ๊ณ ์œ ์˜ ์œ ๋ฆฌ์ „์ด์˜จ๋„(T g ) ๋ฅผ ๋‚˜ํƒ€๋‚ด๊ณ  ์žˆ์–ด, ์ „ํ˜•์ ์ธ ๋น„ ํ˜ผํ™”์„ฑ ๋ธ”๋ Œ๋“œ ๊ฑฐ๋™์„ ๋ณด์˜€๋‹ค. ์ „์žํ˜„๋ฏธ๊ฒฝ(SEM) ๊ณผ ์›์†Œ๋ถ„์„์žฅ์น˜(EDS) ๋ฅผ ์ด์šฉํ•˜์—ฌ ์ƒ ๊ฑฐ๋™์„ ๊ด€์ฐฐํ•œ ๊ฒฐ๊ณผ EPDM/ FKM ๋ธ”๋ Œ๋“œ๋Š” ๋น„ํ˜ผํ™”์„ฑ ๋ธ”๋ Œ๋“œ์˜ ๋Œ€ํ‘œ์ ์ธ ์ƒ๊ฑฐ๋™์ธ ์—ฐ์†์ƒ- ๋ถ„์‚ฐ์ƒ ๋ชจํด๋กœ์ง€๋ฅผ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. FKM ์กฐ์„ฑ์ด 50 phr ์ดํ•˜์—์„œ๋Š” EPDM์ด ์—ฐ์†์ƒ์„ ๋‚˜ํƒ€๋‚ด์—ˆ๊ณ , FKM์ด 80 phr ๊ทผ๋ฐฉ์—์„œ ๊ณต๋™ ์—ฐ์†์ƒ ๊ตฌ์กฐ๋ฅผ ๊ทธ๋ฆฌ๊ณ  FKM์ด 90 phr ์— ์„œ๋Š” FKM ์ด ์—ฐ์†์ƒ์„ ๋‚˜ํƒ€๋‚ด๋Š” ์ƒ์ „์ด๊ฐ€ ๋‚˜ํƒ€๋‚ฌ๋‹ค. Abstract: Rubber blends based on ethylene-propylene-diene-monomer (EPDM) rubber and fluoroelastomer (FKM) hav- ing various blend ratios were prepared. The phase morphology, cure characteristics, hardness, tensile and dynamic vis- coelastic properties of the blends were investigated. The cure rate of the blends increased, while the crosslink-density decreased as the FKM content increased. The hardness, tensile strength and elongation at break, and storage modulus (E' ) increased with increasing FKM loading. A typical incompatible blend behavior was found by observing two distinct tanฮด peaks corresponding to EPDM and FKM. Based on the morphology investigation by scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) analyses, a typical โ€˜sea-islandโ€™ phase morphology was observed for the EPDM/FKM blends. As the FKM loading was increased to 50 phr, the EPDM was found to remain as the con- tinuous phase. At the 80 phr of FKM, a co-continuous phase was observed and the phase inversion was observed at 90 phr of FKM. Keywords: ethylene-propylene-diene-monomer, fluoroelastomer, blend, phase morphology, energy dispersive X-ray spectroscopy, inversion. ์„œ ๋ก  ์›์œ ๊ฐ€๊ฒฉ ์ธ์ƒ๊ณผ ์—๋„ˆ์ง€์ž์› ๊ณ ๊ฐˆ, ์ง€๊ตฌ์˜จ๋‚œํ™” ๋“ฑ ํ™˜๊ฒฝ์— ๊ด€ํ•œ ๊ด€์‹ฌ์ด ๋†’์•„์ง€๋ฉด์„œ ์›์œ ๋Œ€์ฒด ์—๋„ˆ์ง€์™€ ํ™˜๊ฒฝ ์นœํ™”์  ์—ฐ ๋ฃŒ๊ฐœ๋ฐœ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๊ฐ€ ํ™œ๋ฐœํžˆ ์ด๋ฃจ์–ด์ง€๊ณ  ์žˆ๋‹ค. ์ˆ˜์†Œ์—ฐ๋ฃŒ์ „ ์ง€๋Š” ์ด๋Ÿฌํ•œ ํ™˜๊ฒฝ ์นœํ™”์  ์—ฐ๋ฃŒ์‹œ์Šคํ…œ ์ค‘์˜ ํ•˜๋‚˜๋กœ ์ˆ˜์†Œ์™€ ์‚ฐ ์†Œ์˜ ์ „๊ธฐํ™”ํ•™์  ๋ฐ˜์‘์œผ๋กœ ์ „๊ธฐ์—๋„ˆ์ง€๋ฅผ ์ƒ์‚ฐํ•˜๋Š” ์‹œ์Šคํ…œ์ด ๋‹ค. ์ˆ˜์†Œ์—ฐ๋ฃŒ์ „์ง€๋Š” ์ง์ ‘์ ์ธ ์—ฐ์†Œ๊ณผ์ •์ด ์กด์žฌํ•˜์ง€ ์•Š๊ธฐ ๋•Œ ๋ฌธ์— ๊ธฐ์กด์˜ ๋‚ด์—ฐ๊ธฐ๊ด€์—์„œ ๋ฐœ์ƒํ•˜๋Š” ์งˆ์†Œ์‚ฐํ™”๋ฌผ, ์ผ์‚ฐํ™”ํƒ„์†Œ ๋“ฑ์˜ ๋Œ€๊ธฐ์˜ค์—ผ ๋ฌผ์งˆ์ด ๋ฐœ์ƒํ•˜์ง€ ์•Š์œผ๋ฉฐ, ์†Œ์Œ์ด ์—†๊ณ , ๊ธฐ์กด์˜ ๋‚ด์—ฐ๊ธฐ๊ด€๋ณด๋‹ค 30% ๋†’์€ ์—๋„ˆ์ง€ ํšจ์œจ์„ ๊ฐ–๋Š”๋‹ค. 1 ์ด๋Ÿฌํ•œ ์ˆ˜์†Œ โ€  To whom correspondence should be addressed. E-mail: [email protected] ยฉ2015 The Polymer Society of Korea. All rights reserved.

Upload: others

Post on 30-Nov-2021

5 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: Phase Morphology and Mechanical Properties of Ethylene

754

Polymer(Korea), Vol. 39, No. 5, pp. 754-760 (2015)

http://dx.doi.org/10.7317/pk.2015.39.5.754

ISSN 0379-153X(Print)

ISSN 2234-8077(Online)

์—ํ‹ธ๋ Œ-ํ”„๋กœํ•„๋ Œ-๋””์—”-๋ชจ๋…ธ๋จธ/๋ถˆ์†Œ๊ณ ๋ฌด ๋ธ”๋ Œ๋“œ์˜ ์ƒ ๋ชจํด๋กœ์ง€์™€ ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ

์ด๊ธฐ์จยท๊น€์Šน๊ฒธยท์œ ์šฉํ™˜ยท๊ฐ•์„์ธยท์˜ค์ข…๊ฐ‘*ยทํ—ˆ์–‘์ผ**ยท์ •๋ณ‘ํ—Œ***ยท๋‚˜์ฐฝ์šดโ€ 

์ „๋ถ๋Œ€ํ•™๊ต ๊ณ ๋ถ„์ž๋‚˜๋…ธ๊ณตํ•™๊ณผ, BK21 ํ”Œ๋Ÿฌ์Šค ๊ฐ์„ฑํ„ฐ์น˜ ๊ณ ๋ถ„์ž๋ณตํ•ฉ์†Œ์žฌ ์—ฐ๊ตฌํŒ€, *์ „๋ถ๋Œ€ํ•™๊ต ๋Œ€ํ•™์› ๋””์ž์ธ์ œ์กฐ๊ณตํ•™๊ณผ

**์ „๋‚จ๋Œ€ํ•™๊ต ๊ณ ๋ถ„์ž์œตํ•ฉ์†Œ์žฌ๊ณตํ•™๋ถ€, ***ํ˜„๋Œ€์ž๋™์ฐจ ์—ฐ๊ตฌ์†Œ ์—ฐ๋ฃŒ์ „์ง€์ž๋™์ฐจ 1ํŒ€

(2015๋…„ 2์›” 15์ผ ์ ‘์ˆ˜, 2015๋…„ 3์›” 11์ผ ์ˆ˜์ •, 2015๋…„ 3์›” 11์ผ ์ฑ„ํƒ)

Phase Morphology and Mechanical Properties of

Ethylene-Propylene-Diene-Monomer/Fluoroelastomer Blends

Gi-Bbeum Lee, Seung Gyeom Kim, Yong Hwan Yoo, Seok In Kang, Jong Gab Oh*,

Yang Il Huh**, Byeong-Heon Jeong***, and Changwoon Nahโ€ 

BK21 Plus Heptic Polymer Composites Research Team, Department of Polymer-Nano Science and Technology,

Chonbuk National University, Jeonju 561-756, Korea

*Department of Design and Manufacturing, Graduate School, Chonbuk National University, Jeonju 561-756, Korea

**Department Polymer and Fiber System Engineering, Chonnam National University, Gwangju 500-757, Korea

***Fuel Cell Vehicle Team 1, R&D Division, Hyundai Motor Group, Yong-in 446-912, Korea

(Received February 15, 2015; Revised March 11, 2015; Accepted March 11, 2015)

์ดˆ๋ก: ์—ํ‹ธ๋ Œ-ํ”„๋กœํ•„๋ Œ-๋””์—”-๋ชจ๋…ธ๋จธ(EPDM) ๊ณ ๋ฌด์™€ ๋ถˆ์†Œ๊ณ ๋ฌด(FKM)๋ฅผ ๋‹ค์–‘ํ•œ ์กฐ์„ฑ์œผ๋กœ ๋ธ”๋ Œ๋“œ๋ฅผ ์ œ์กฐํ•˜์—ฌ ์กฐ์„ฑ์—

๋”ฐ๋ฅธ ์ƒ ๋ชจํด๋กœ์ง€์™€ ๊ฐ€๊ตํŠน์„ฑ, ๊ฒฝ๋„ํŠน์„ฑ, ์ธ์žฅํŠน์„ฑ ๊ทธ๋ฆฌ๊ณ  ๋™์  ์ ํƒ„์„ฑ ํŠน์„ฑ์„ ์กฐ์‚ฌํ•˜์˜€๋‹ค. FKM ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜

๋ก ๊ฐ€๊ต์†๋„๋Š” ์ฆ๊ฐ€ํ•œ ๋ฐ˜๋ฉด ๊ฐ€๊ต๋ฐ€๋„๋Š” ๊ฐ์†Œํ•˜์˜€์œผ๋ฉฐ, ์ „๋ฐ˜์ ์œผ๋กœ ๊ฒฝ๋„, ์ธ์žฅ๊ฐ•๋„, ํŒŒ๋‹จ์‹ ์žฅ๋ฅ  ๋ฐ ์ €์žฅ ๋ชจ๋“ˆ๋Ÿฌ์Šค(E')

๋Š” ์ฆ๊ฐ€ํ•˜์˜€๋‹ค. ๋ชจ๋“  ๋ธ”๋ Œ๋“œ ์ปดํŒŒ์šด๋“œ์—์„œ EPDM๊ณผ FKM ๊ณ ์œ ์˜ ์œ ๋ฆฌ์ „์ด์˜จ๋„(Tg)๋ฅผ ๋‚˜ํƒ€๋‚ด๊ณ  ์žˆ์–ด, ์ „ํ˜•์ ์ธ ๋น„

ํ˜ผํ™”์„ฑ ๋ธ”๋ Œ๋“œ ๊ฑฐ๋™์„ ๋ณด์˜€๋‹ค. ์ „์žํ˜„๋ฏธ๊ฒฝ(SEM)๊ณผ ์›์†Œ๋ถ„์„์žฅ์น˜(EDS)๋ฅผ ์ด์šฉํ•˜์—ฌ ์ƒ ๊ฑฐ๋™์„ ๊ด€์ฐฐํ•œ ๊ฒฐ๊ณผ EPDM/

FKM ๋ธ”๋ Œ๋“œ๋Š” ๋น„ํ˜ผํ™”์„ฑ ๋ธ”๋ Œ๋“œ์˜ ๋Œ€ํ‘œ์ ์ธ ์ƒ๊ฑฐ๋™์ธ ์—ฐ์†์ƒ-๋ถ„์‚ฐ์ƒ ๋ชจํด๋กœ์ง€๋ฅผ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. FKM ์กฐ์„ฑ์ด 50 phr

์ดํ•˜์—์„œ๋Š” EPDM์ด ์—ฐ์†์ƒ์„ ๋‚˜ํƒ€๋‚ด์—ˆ๊ณ , FKM์ด 80 phr ๊ทผ๋ฐฉ์—์„œ ๊ณต๋™ ์—ฐ์†์ƒ ๊ตฌ์กฐ๋ฅผ ๊ทธ๋ฆฌ๊ณ  FKM์ด 90 phr์—

์„œ๋Š” FKM์ด ์—ฐ์†์ƒ์„ ๋‚˜ํƒ€๋‚ด๋Š” ์ƒ์ „์ด๊ฐ€ ๋‚˜ํƒ€๋‚ฌ๋‹ค.

Abstract: Rubber blends based on ethylene-propylene-diene-monomer (EPDM) rubber and fluoroelastomer (FKM) hav-

ing various blend ratios were prepared. The phase morphology, cure characteristics, hardness, tensile and dynamic vis-

coelastic properties of the blends were investigated. The cure rate of the blends increased, while the crosslink-density

decreased as the FKM content increased. The hardness, tensile strength and elongation at break, and storage modulus (E')

increased with increasing FKM loading. A typical incompatible blend behavior was found by observing two distinct tanฮด

peaks corresponding to EPDM and FKM. Based on the morphology investigation by scanning electron microscopy

(SEM) and energy dispersive x-ray spectroscopy (EDS) analyses, a typical โ€˜sea-islandโ€™ phase morphology was observed

for the EPDM/FKM blends. As the FKM loading was increased to 50 phr, the EPDM was found to remain as the con-

tinuous phase. At the 80 phr of FKM, a co-continuous phase was observed and the phase inversion was observed at

90 phr of FKM.

Keywords: ethylene-propylene-diene-monomer, fluoroelastomer, blend, phase morphology, energy dispersive X-ray

spectroscopy, inversion.

์„œ ๋ก 

์›์œ ๊ฐ€๊ฒฉ ์ธ์ƒ๊ณผ ์—๋„ˆ์ง€์ž์› ๊ณ ๊ฐˆ, ์ง€๊ตฌ์˜จ๋‚œํ™” ๋“ฑ ํ™˜๊ฒฝ์—

๊ด€ํ•œ ๊ด€์‹ฌ์ด ๋†’์•„์ง€๋ฉด์„œ ์›์œ ๋Œ€์ฒด ์—๋„ˆ์ง€์™€ ํ™˜๊ฒฝ ์นœํ™”์  ์—ฐ

๋ฃŒ๊ฐœ๋ฐœ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๊ฐ€ ํ™œ๋ฐœํžˆ ์ด๋ฃจ์–ด์ง€๊ณ  ์žˆ๋‹ค. ์ˆ˜์†Œ์—ฐ๋ฃŒ์ „

์ง€๋Š” ์ด๋Ÿฌํ•œ ํ™˜๊ฒฝ ์นœํ™”์  ์—ฐ๋ฃŒ์‹œ์Šคํ…œ ์ค‘์˜ ํ•˜๋‚˜๋กœ ์ˆ˜์†Œ์™€ ์‚ฐ

์†Œ์˜ ์ „๊ธฐํ™”ํ•™์  ๋ฐ˜์‘์œผ๋กœ ์ „๊ธฐ์—๋„ˆ์ง€๋ฅผ ์ƒ์‚ฐํ•˜๋Š” ์‹œ์Šคํ…œ์ด

๋‹ค. ์ˆ˜์†Œ์—ฐ๋ฃŒ์ „์ง€๋Š” ์ง์ ‘์ ์ธ ์—ฐ์†Œ๊ณผ์ •์ด ์กด์žฌํ•˜์ง€ ์•Š๊ธฐ ๋•Œ

๋ฌธ์— ๊ธฐ์กด์˜ ๋‚ด์—ฐ๊ธฐ๊ด€์—์„œ ๋ฐœ์ƒํ•˜๋Š” ์งˆ์†Œ์‚ฐํ™”๋ฌผ, ์ผ์‚ฐํ™”ํƒ„์†Œ

๋“ฑ์˜ ๋Œ€๊ธฐ์˜ค์—ผ ๋ฌผ์งˆ์ด ๋ฐœ์ƒํ•˜์ง€ ์•Š์œผ๋ฉฐ, ์†Œ์Œ์ด ์—†๊ณ , ๊ธฐ์กด์˜

๋‚ด์—ฐ๊ธฐ๊ด€๋ณด๋‹ค 30% ๋†’์€ ์—๋„ˆ์ง€ ํšจ์œจ์„ ๊ฐ–๋Š”๋‹ค.1 ์ด๋Ÿฌํ•œ ์ˆ˜์†Œ

โ€ To whom correspondence should be addressed.E-mail: [email protected]

ยฉ2015 The Polymer Society of Korea. All rights reserved.

Page 2: Phase Morphology and Mechanical Properties of Ethylene

์—ํ‹ธ๋ Œ-ํ”„๋กœํ•„๋ Œ-๋””์—”-๋ชจ๋…ธ๋จธ/๋ถˆ์†Œ๊ณ ๋ฌด ๋ธ”๋ Œ๋“œ์˜ ์ƒ ๋ชจํด๋กœ์ง€์™€ ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ 755

Polymer(Korea), Vol. 39, No. 5, 2015

์—ฐ๋ฃŒ์ „์ง€์˜ ์„ฑ๋Šฅ๊ณผ ํ’ˆ์งˆ์„ ํ–ฅ์ƒ์‹œํ‚ค๊ธฐ ์œ„ํ•ด ์ˆ˜์†Œ์—ฐ๋ฃŒ์ „์ง€์˜

ํ•ต์‹ฌ๋ถ€ํ’ˆ์ธ ์—ฐ๋ฃŒ์ „์ง€ ์Šคํƒ์˜ ๊ตฌ์กฐ ๋ฐ ๊ตฌ์„ฑ์žฌ๋ฃŒ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ

๊ฐ€ ํ™œ๋ฐœํžˆ ์ด๋ฃจ์–ด์ ธ ์™”๊ณ , ์„ฑ๋Šฅ๊ตฌํ˜„์— ์žˆ์–ด์„œ ์ƒ์—…ํ™”์˜ ๋‹จ๊ณ„

์— ์ด๋ฅด๊ณ  ์žˆ๋‹ค.2-13 ๊ทธ๋Ÿฌ๋‚˜ ์Šคํƒ์˜ ๊ธฐ๋ฐ€์„ ๋‹ด๋‹นํ•˜๊ณ  ์žˆ๋Š” ๊ฐœ

์Šคํ‚ท์˜ ๊ฒฝ์šฐ ์ €์˜จํŠน์„ฑ, ์˜๊ตฌ์••์ถ•์ค„์Œ๋ฅ , ๊ฐ€๊ณตํŠน์„ฑ, ๋‚ดํ™”ํ•™์„ฑ,

๋‚ด๋…ธํ™”์„ฑ ๋“ฑ ์—ฌ๋Ÿฌ ๊ฐ€์ง€ ์ธก๋ฉด์—์„œ ๊ฐœ์„ ์˜ ์—ฌ์ง€๊ฐ€ ๋งŽ์€ ๊ฒƒ์œผ๋กœ

์•Œ๋ ค์ ธ ์žˆ๋‹ค.14

์ˆ˜์†Œ์—ฐ๋ฃŒ์ „์ง€ ์Šคํƒ์šฉ ๊ฐœ์Šคํ‚ท ์žฌ๋ฃŒ๋Š” ์ผ๋ฐ˜์ ์œผ๋กœ ๋ถˆ์†Œ๊ณ ๋ฌด

(FKM), ์‹ค๋ฆฌ์ฝ˜๊ณ ๋ฌด(PDMS), ์—ํ‹ธ๋ Œ-ํ”„๋กœํ•„๋ Œ ๊ณ ๋ฌด(EPDM)๊ฐ€

๋„๋ฆฌ ๊ฒ€ํ† ๋˜๊ณ  ์žˆ๋‹ค.15,16 FKM์€ ๊ฒฐํ•ฉ ์—๋„ˆ์ง€๊ฐ€ ๊ฐ•ํ•œ C-F ํ™”

ํ•™ ๊ตฌ์กฐ์— ์˜ํ•ด ๋‚ด์—ด์„ฑ, ๋‚ดํ™”ํ•™์„ฑ, ๋‚ด์˜ค์กด์„ฑ ๋ฐ ๋‚ดํ›„์„ฑ์ด ๋›ฐ

์–ด๋‚˜๊ธฐ ๋•Œ๋ฌธ์— ๊ฐ•์‚ฐ์„ฑ ๋ฐ ๊ณ ์˜จ์—์„œ ์žฅ๊ธฐ๊ฐ„ ๊ฒฌ๋ŽŒ์•ผํ•˜๋Š” ์—ฐ๋ฃŒ

์ „์ง€์˜ ๊ฐœ์Šคํ‚ท์— ์‚ฌ์šฉํ•˜๊ธฐ ๋งค์šฐ ์ ์ ˆํ•œ ์กฐ๊ฑด์„ ๊ฐ€์ง€๊ณ  ์žˆ๋‹ค.

๊ทธ๋Ÿฌ๋‚˜ FKM์€ ๊ณ ๊ฐ€์ด๊ณ  ๋‚ดํ•œ์„ฑ ๋ฐ ๊ฐ€๊ณต์„ฑ์ด ์ทจ์•ฝํ•˜์—ฌ ๋Œ€๋Ÿ‰

์ƒ์‚ฐ์— ํ•„์ˆ˜์ ์ธ ์‚ฌ์ถœ๊ฐ€๊ณต์— ์ทจ์•ฝํ•˜๋‹ค.17-20 PDMS๋Š” Si-O ๊ตฌ

์กฐ์ธ ๋ฌด๊ธฐ๋ฌผ๋กœ ์ด๋ฃจ์–ด์ ธ ์žˆ๊ธฐ ๋•Œ๋ฌธ์— ์‚ฐํ™” ์•ˆ์ •์„ฑ, ๋‚ด์—ด์„ฑ,

๊ฐ€๊ณต์„ฑ, ์ „๊ธฐ์  ํŠน์„ฑ์ด ์šฐ์ˆ˜ํ•˜๋‚˜ ์˜๊ตฌ์••์ถ•์ค„์Œ๋ฅ , ๋‚ด์‚ฐ์„ฑ, ๊ธฐ

๊ณ„์  ๋ฌผ์„ฑ์ด ์ข‹์ง€ ์•Š๋‹ค.15,21 EPDM์€ ์—ํ‹ธ๋ Œ๊ณผ ํ”„๋กœํ•„๋ Œ, ๋””

์—”์ด ๋ถˆ๊ทœ์น™์ ์œผ๋กœ ๊ฒฐํ•ฉํ•œ ์‚ผ์›์ค‘ํ•ฉ์ฒด๋กœ ๋‚ดํ•œ์„ฑ, ๋‚ดํ›„์„ฑ, ๋‚ด

์ ˆ์—ฐ์„ฑ, ๋‚ด์˜ค์กด์„ฑ ๋“ฑ์ด ์šฐ์ˆ˜ํ•˜๋‚˜ ๋‚ด์œ ์„ฑ, ๋‚ด์šฉ์ œ์„ฑ, ์ ์ฐฉ์„ฑ์ด

์—ด์„ธ์ธ ๋‹จ์ ์ด ์žˆ๋‹ค.18-23 ์ด๋Ÿฌํ•œ ๊ฐ ๊ณ ๋ฌด์˜ ๋‹จ์ ๋“ค์„ ๋ณด์™„ํ•˜

๊ธฐ ์œ„ํ•œ ๋ฐฉ๋ฒ•์œผ๋กœ ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ ๋ฐ ์‘์šฉ์ด ํ™œ

๋ฐœํžˆ ์ด๋ฃจ์–ด์ง€๊ณ  ์žˆ๋‹ค.18-28

๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ๋Š” ๋‹ค๋ฅธ ์„ฑ์งˆ์˜ ๊ณ ๋ถ„์ž๋“ค์„ ํ˜ผํ•ฉํ•œ ๊ฒƒ์œผ๋กœ

๊ธฐ์กด ๊ณ ๋ถ„์ž๋“ค์˜ ๋ฌธ์ œ์ ์„ ์ƒํ˜ธ ๋ณด์™„ํ•˜์—ฌ ์šฐ์ˆ˜ํ•œ ๊ธฐ๊ณ„์ , ์—ด

์ , ๊ด‘ํ•™์  ๋ฌผ์„ฑ ๋“ฑ์„ ๊ฐ–๋„๋ก ํ•œ๋‹ค. ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ์˜ ๋ฌผ์„ฑ์€

๋ชจํด๋กœ์ง€์˜ ์˜ํ–ฅ์„ ๋งŽ์ด ๋ฐ›์œผ๋ฉฐ, ๋ชจํด๋กœ์ง€๋Š” ๊ณ ๋ถ„์ž๋“ค์˜ ์กฐ

์„ฑ, ํ˜ผํ•ฉ ์กฐ๊ฑด, ๊ณ„๋ฉด ์žฅ๋ ฅ, ์ ํƒ„์„ฑ ๋ฐ ํ™”ํ•™์ , ๋ฌผ๋ฆฌ์  ์„ฑ์งˆ ๋“ฑ

์— ์˜ํ•ด ๊ฒฐ์ •๋œ๋‹ค.29 ์ผ๋ฐ˜์ ์œผ๋กœ ๋‘ ๊ณ ๋ถ„์ž๋ฅผ ํ˜ผํ•ฉํ•˜๋ฉด ๋‘ ๊ณ 

๋ถ„์ž ์‚ฌ์ด์˜ ๊ณ„๋ฉด์žฅ๋ ฅ๊ณผ ์ ๋„ ์ฐจ์ด์— ์˜ํ•ด ์กฐ์„ฑ์ด ๋งŽ์€ ์ชฝ์ด

์—ฐ์†์ƒ์„ ํ˜•์„ฑํ•˜๊ณ , ์ ์€ ์ชฝ์ด ๋ถ„์‚ฐ์ƒ์„ ํ˜•์„ฑํ•˜๊ฒŒ ๋˜๋Š”๋ฐ, ์ด

๋•Œ ๋ธ”๋ Œ๋“œ์˜ ๋ฌผ์„ฑ์€ ์—ฐ์†์ƒ์˜ ํŠน์„ฑ์— ํฌ๊ฒŒ ์˜์กดํ•˜๋ฉฐ, ๋ถ„์‚ฐ์ƒ

์€ ๋ณด์™„ํ•˜๋Š” ์—ญํ• ์„ ํ•œ๋‹ค.30 ๋”ฐ๋ผ์„œ ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ์˜ ์šฐ์ˆ˜ํ•œ

๋ฌผ์„ฑ์„ ์–ป๊ธฐ ์œ„ํ•ด์„œ๋Š” ๋ธ”๋ Œ๋“œ์˜ ๋ชจํด๋กœ์ง€๋ฅผ ์˜ˆ์ธกํ•˜๊ณ  ์กฐ์ ˆํ•˜

๋Š” ๊ธฐ์ˆ ์ด ๋งค์šฐ ์ค‘์š”ํ•˜๋‹ค.

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์—ฐ๋ฃŒ์ „์ง€ ๊ฐœ์Šคํ‚ท์— ์‚ฌ์šฉ๋˜๋Š” FKM๊ณผ EPDM

์˜ ๋‹จ์ ์„ ์ƒํ˜ธ ๋ณด์™„ํ•˜๊ธฐ ์œ„ํ•ด EPDM๊ณผ FKM์„ ํ˜ผํ•ฉํ•˜์—ฌ

EPDM/FKM ๋ธ”๋ Œ๋“œ๋ฅผ ์ œ์กฐํ•˜์˜€๊ณ , ๋ธ”๋ Œ๋“œ ์กฐ์„ฑ์— ๋”ฐ๋ฅธ ์ƒ

๋ชจํด๋กœ์ง€์™€ ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ์˜ ๋ณ€ํ™”๋ฅผ ๋‹ค์–‘ํ•œ ๋ถ„์„๋ฒ•์„ ์ด์šฉํ•˜์—ฌ

์กฐ์‚ฌํ•˜์˜€๋‹ค. ํŠนํžˆ ์ „์žํ˜„๋ฏธ๊ฒฝ ๋ชจํด๋กœ์ง€์™€ ์›์†Œ๋ถ„์„์žฅ์น˜(EDS)

๋ฅผ ํ†ตํ•œ ์›์†Œ๋ถ„ํฌ๋„๋ฅผ ๋น„๊ตํ•จ์œผ๋กœ์จ ๋ณด๋‹ค ์ •๋ฐ€ํ•œ ์ƒ ๊ตฌ์กฐ ๋ถ„

์„์„ ์‹œ๋„ํ•˜์˜€๋‹ค.

์‹ค ํ—˜

์žฌ๋ฃŒ. EPDM์€ ethylene norbornene(ENB)์„ ํ•จ์œ ํ•œ ๊ธˆํ˜ธ

ํด๋ฆฌ์ผ์˜ KEP350(ENB = 7.9 wt%, Mooney ์ ๋„ ML1+4,

125 oC = 56)์„ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ, FKM์€ Dupont Dow Elastomer

์‚ฌ์˜ Viton GBL-200S(๋ถˆ์†Œํ•จ๋Ÿ‰ = 68 wt%, Mooney ์ ๋„

ML1+10, 121 oC = 25)๋ฅผ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ๋ณด๊ฐ•์ œ๋Š” ์นด๋ณธ๋ธ”๋ž™(N110)

์„ ์‚ฌ์šฉํ•˜์˜€๊ณ , ์‚ฐํ™” ๋ฐฉ์ง€์ œ๋Š” CIBA Specialty Chemicals

Inc.์‚ฌ์˜ Inganox 1010์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ๊ฐ€๊ต์ œ๋Š” ํ‰ํ™”์•ฝํ’ˆ์‚ฌ์˜

Peroxan HX-50 PS๋ฅผ ์‚ฌ์šฉํ•˜์˜€๊ณ , ๊ฐ€๊ต์กฐ์ œ๋Š” triallyl

isocyanurate(TAIC, stabilized with BHT)๋กœ Tokyo Chemical

Industry์‚ฌ์˜ ์ œํ’ˆ์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค.

๋ธ”๋ Œ๋“œ ๋ฐฐํ•ฉ ๋ฐ ์ œ์กฐ. ๋ณธ ์‹คํ—˜์— ์‚ฌ์šฉ๋œ EPDM/FKM ๋ธ”

๋ Œ๋“œ์˜ ๋ฐฐํ•ฉ๋น„๋ฅผ Table 1์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ๋ธ”๋ Œ๋“œ์˜ ๋ฐฐํ•ฉ์€

EPDM๊ณผ FKM ๊ณ ๋ฌด๋ฅผ ๋‚ด๋ถ€ ํ˜ผํ•ฉ๊ธฐ๋ฅผ ์ด์šฉํ•˜์—ฌ 140 oC์—์„œ

5๋ถ„๊ฐ„ ํ˜ผ๋ จํ•œ ํ›„ ์นด๋ณธ๋ธ”๋ž™๊ณผ ์‚ฐํ™”๋ฐฉ์ง€์ œ๋ฅผ ์ฒจ๊ฐ€ํ•˜์—ฌ, ๋™์ผํ•œ

์กฐ๊ฑด์—์„œ 5๋ถ„๊ฐ„ ๊ณ ๋ฌด์™€ ํ˜ผํ•ฉํ•˜์˜€๋‹ค. ์•ˆ์ •ํ™” ํ›„, ์ด์ถ• ๋กค(Farrel

8422, USA)์„ ํ†ตํ•ด ๊ฐ€๊ต์ œ ๋ฐ ๊ฐ€๊ต์กฐ์ œ๋ฅผ ๊ณ ๋ฌด์™€ ํ•จ๊ป˜ 20๋ถ„

๊ฐ„ ํ˜ผํ•ฉํ•˜์—ฌ EPDM/FKM ๋ธ”๋ Œ๋“œ๋ฅผ ์ œ์กฐํ•˜์˜€๋‹ค. ์ œ์กฐ๋œ ๋ธ”๋ Œ

๋“œ๋Š” 24์‹œ๊ฐ„ ๋™์•ˆ ์ƒ์˜จ์—์„œ ์•ˆ์ •ํ™” ๊ณผ์ •์„ ๊ฑฐ์นœ ํ›„, ๊ฐ€๊ต ๋ ˆ

์˜ค๋ฏธํ„ฐ๋ฅผ ์ด์šฉํ•˜์—ฌ ์ ์ • ๊ฐ€๊ต์‹œ๊ฐ„์„ ์ธก์ •ํ•œ ๋’ค, ์œ ์••์‹ ํ”„๋ ˆ

์Šค(CHV 50H, Carver)๋ฅผ ์ด์šฉํ•˜์—ฌ 170 oC์—์„œ 25 ton์˜ ์••๋ ฅ

์œผ๋กœ ๊ฐ€์••ํ•˜์—ฌ ๋‘๊ป˜ 2 mm์˜ ์‹œํŠธ ์‹œํŽธ์„ ์ œ์ž‘ํ•˜์˜€๋‹ค.

๊ฐ€๊ต ํŠน์„ฑ. ๋ธ”๋ Œ๋“œ์˜ ๊ฐ€๊ตํŠน์„ฑ์„ ์‚ดํŽด๋ณด๊ธฐ ์œ„ํ•ด oscillating

disk rheometer(ODR, Alpha Technologies)๋ฅผ ์ด์šฉํ•˜์—ฌ

ASTM-D2084 ๊ทœ์ •์— ๋”ฐ๋ผ 170 oC์—์„œ 90๋ถ„ ๋™์•ˆ ์ตœ๋Œ€ํ† ํฌ

(MH), ์ตœ์ €ํ† ํฌ(ML), ์Šค์ฝ”์น˜ ์‹œ๊ฐ„(Ts2), ์ ์ • ๊ฐ€๊ต์‹œ๊ฐ„(T90)์„

์ธก์ •ํ•˜์˜€๋‹ค.

๋ชจํด๋กœ์ง€. ๋ธ”๋ Œ๋“œ์˜ ๋ชจํด๋กœ์ง€๋Š” Hitachi์‚ฌ์˜ field emission

scanning electron microscope(FE-SEM, S-4800)๋ฅผ ์ด์šฉํ•˜์—ฌ

๊ด€์ฐฐํ•˜์˜€๊ณ , energy dispersive X-ray spectroscopy(EDS)๋ฅผ ์ด

์šฉํ•œ ์›์†Œ๋ถ„์„์„ ํ•˜์˜€๊ณ , ์ด๋ฅผ ํŒŒ๋‹จ๋ฉด ์ „์ฒด์— ๋Œ€ํ•ด mapping

ํ•จ์œผ๋กœ์จ ๋ธ”๋ Œ๋“œ์˜ ์ƒ์ „์ด ๊ฑฐ๋™์„ ๋น„๊ต๋ถ„์„ํ•˜์˜€๋‹ค.

๊ธฐ๊ณ„์  ๋ฌผ์„ฑ. ๊ฒฝ๋„๋Š” ASTM-D2240 ๊ทœ์ •์— ๋”ฐ๋ผ ๊ฒฝ๋„๊ณ„

(Asker, Kobunishi keiki Co. Ltd)๋ฅผ ์ด์šฉํ•˜์—ฌ Shore A ๊ฒฝ๋„

๋ฅผ ์ธก์ •ํ•˜์˜€๋‹ค. ์‹œํŽธ๋งˆ๋‹ค ์ด 10ํšŒ๋ฅผ ์ธก์ •ํ•˜์—ฌ ํ‰๊ท ๊ฐ’์„ ์‚ฐ์ถœ

ํ•˜์˜€๋‹ค.

์ธ์žฅ์‹œํ—˜์€ JIS K6251-3 ๊ทœ์ •์— ๋”ฐ๋ผ ๋ค๋ฒจํ˜• ์‹œํŽธ์„ ์ œ์กฐ

Table 1. Formulations of EPDM/FKM Blends

(unit: phr)

Sample E10 E7F3 E5F5 E2F8 E1F9 F10

EPDM 100 70 50 20 10

FKM 30 50 80 90 100

Carbon black 5 5 5 5 5 5

Anti-oxidant 0.1 0.1 0.1 0.1 0.1 0.1

Peroxide 3 3 3 3 3 3

TAIC 1 1 1 1 1 1

Page 3: Phase Morphology and Mechanical Properties of Ethylene

756 ์ด๊ธฐ์จยท๊น€์Šน๊ฒธยท์œ ์šฉํ™˜ยท๊ฐ•์„์ธยท์˜ค์ข…๊ฐ‘ยทํ—ˆ์–‘์ผยท์ •๋ณ‘ํ—Œยท๋‚˜์ฐฝ์šด

ํด๋ฆฌ๋จธ, ์ œ39๊ถŒ ์ œ5ํ˜ธ, 2015๋…„

ํ•œ ํ›„, ์ธ์žฅ์‹œํ—˜๊ธฐ(LRX Plus, Lloyd instrument)๋ฅผ ์ด์šฉํ•˜์—ฌ

500 mm/min์˜ ์ธ์žฅ์†๋„๋กœ ์‹ค์‹œํ•˜์˜€์œผ๋ฉฐ, ์ธ์žฅ๊ฐ•๋„ ๋ฐ ํŒŒ๋‹จ

์‹ ์žฅ๋ฅ ์„ ์ธก์ •ํ•˜์˜€๋‹ค.

๋™์  ์ ํƒ„์„ฑ. ๋ธ”๋ Œ๋“œ์˜ ๋™์  ์ ํƒ„์„ฑ์€ ๋‘๊ป˜ 2 mm, ํญ

10 mm, ํ‘œ์ ๊ฑฐ๋ฆฌ 20 mm์ธ ์‹œํŽธ์— ๋Œ€ํ•ด ๋™์ ์ ํƒ„์„ฑ ์‹œํ—˜๊ธฐ

(Q800, TA instrument)๋ฅผ ์ด์šฉํ•˜์—ฌ ์˜จ๋„ ๋ฒ”์œ„ -60~70 oC, ์Šน

์˜จ ์†๋„ 4 oC/min, ์ฃผํŒŒ์ˆ˜ 11 Hz, ๋™์  ๋ณ€ํ˜• 0.25%์˜ ์งˆ์†Œ๋ถ„

์œ„๊ธฐ ํ•˜์—์„œ ์ €์žฅ ๋ชจ๋“ˆ๋Ÿฌ์Šค(E') ๋ฐ tanฮด๋ฅผ ์ธก์ •ํ•˜์˜€๋‹ค.

๊ฒฐ๊ณผ ๋ฐ ํ† ๋ก 

๊ฐ€๊ตํŠน์„ฑ. EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ์กฐ์„ฑ์— ๋”ฐ๋ฅธ ๊ฐ€๊ตํŠน์„ฑ์„

Figure 1์— ๋‚˜ํƒ€๋‚ด์—ˆ๊ณ , ์ตœ์ €ํ† ํฌ(ML), ์ตœ๋Œ€ํ† ํฌ(MH), ๊ฐ€๊ต๋ฐ€

๋„(MH-ML), ์Šค์ฝ”์น˜(scorch) ์‹œ๊ฐ„(ts2), ์ ์ • ๊ฐ€๊ต์‹œ๊ฐ„(t90), ๊ฐ€๊ต

์†๋„์ง€์ˆ˜(CRI) ๋“ฑ์˜ ์ฃผ์š”ํŠน์„ฑ์„ Table 2์— ์ •๋ฆฌํ•˜์˜€๋‹ค.

EPDM, FKM์˜ ์ ์ • ๊ฐ€๊ต์‹œ๊ฐ„์€ ๊ฐ๊ฐ 25.3๋ถ„, 7.4๋ถ„์œผ๋กœ ๋‚˜

ํƒ€๋‚ฌ์œผ๋ฉฐ, EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ๊ฒฝ์šฐ, EPDM๊ณผ FKM ์‚ฌ์ด

์˜ ๊ฐ’์„ ๋‚˜ํƒ€๋ƒˆ๋‹ค. FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ๋ธ”๋ Œ๋“œ์˜ ์ 

์ • ๊ฐ€๊ต์‹œ๊ฐ„์ด ๊ฐ์†Œํ•˜๊ณ  ๊ฐ€๊ต์†๋„์ง€์ˆ˜๊ฐ€ ์ฆ๊ฐ€ํ•˜์˜€์œผ๋ฏ€๋กœ ๊ฐ€

๊ต๋ฐ˜์‘์ด ๋นจ๋ฆฌ ์ผ์–ด๋‚ฌ์Œ์„ ์•Œ ์ˆ˜ ์žˆ๋Š”๋ฐ, ์ด๋Š” FKM์˜ ๊ฐ€๊ต

๋ฐ˜์‘ ์†๋„๊ฐ€ EPDM๋ณด๋‹ค ๋น ๋ฅด๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค.31-33 ์Šค์ฝ”

์น˜ ์‹œ๊ฐ„์€ FKM์˜ ํ•จ๋Ÿ‰์— ์ƒ๊ด€์—†์ด ๊ฑฐ์˜ ์ผ์ •ํ•˜๊ฒŒ ๋‚˜ํƒ€๋‚ฌ๋‹ค.

๊ฐ€๊ต๋ฐ€๋„๋Š” FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ๊ฐ์†Œํ•˜๋Š” ๊ฒฝํ–ฅ์„

๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ์ด๋Š” ๋ณธ ์‹คํ—˜์—์„œ ์ฃผ์–ด์ง„ ๊ฐ€๊ต์กฐ๊ฑด์—์„œ FKM์˜

๊ฐ€๊ต๊ฐ€ ์ถฉ๋ถ„ํžˆ ์ด๋ฃจ์–ด์ง€์ง€ ์•Š์•˜๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค. ๋ณธ ์‹ค

ํ—˜์—์„œ ์„ ํƒํ•œ FKM์˜ ์ตœ์ ๊ฐ€๊ต ์กฐ๊ฑด์€ 1์ฐจ ๊ฐ€๊ต(150~180 oC,

10~30 MPa์˜ ์••๋ ฅ)์™€ 2์ฐจ ๊ฐ€๊ต(ํฌ์ŠคํŠธ ๊ฐ€๊ต, 200~250 oC)๋กœ

์•Œ๋ ค์ ธ ์žˆ๋‹ค.34 ๊ทธ๋Ÿฌ๋‚˜ ๋ณธ ์‹คํ—˜์— ์‚ฌ์šฉ๋œ EPDM์„ 200 oC ์ด

์ƒ์˜ ์˜จ๋„์—์„œ ๊ฐ€๊ตํ•  ๊ฒฝ์šฐ ์—ด ๋…ธํ™”์™€ ๊ฐ™์€ ๋ฌธ์ œ์ ์ด ์žˆ๊ธฐ

๋•Œ๋ฌธ์— 170 oC, 25 ton ์••๋ ฅ ์กฐ๊ฑด์—์„œ ๋™์ผํ•˜๊ฒŒ ๊ฐ€๊ตํ•˜์˜€๋‹ค.

๋”ฐ๋ผ์„œ ๋ธ”๋ Œ๋“œ ๋‚ด FKM ์ƒ์˜ ๊ฒฝ์šฐ ํฌ์ŠคํŠธ ๊ฐ€๊ต์— ์˜ํ•œ ์ถฉ๋ถ„

ํ•œ ๊ฐ€๊ต๊ฐ€ ์ด๋ฃจ์–ด์ง€์ง€ ์•Š์•˜๊ธฐ ๋•Œ๋ฌธ์— ๊ธฐ์ธ๋œ ๊ฑฐ๋™์œผ๋กœ ์ดํ•ด

ํ•  ์ˆ˜ ์žˆ๋‹ค.

๋ชจํด๋กœ์ง€. ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ๋Š” ๋‘ ๊ณ ๋ถ„์ž ์‚ฌ์ด์˜ ๊ณ„๋ฉด์žฅ๋ ฅ๊ณผ

์ ๋„ ์ฐจ์ด๋กœ ์ธํ•ด ์ผ๋ฐ˜์ ์œผ๋กœ ์กฐ์„ฑ์ด ๋งŽ์€ ์ชฝ์ด ์—ฐ์†์ƒ์„ ํ˜•

์„ฑํ•˜๊ณ  ์ ์€ ์ชฝ์ด ๋ถ„์‚ฐ์ƒ์ด ๋œ๋‹ค. ๋ถ„์‚ฐ์ƒ์„ ์ด๋ฃจ๋Š” ๊ณ ๋ถ„์ž์˜

ํ•จ๋Ÿ‰์„ ์กฐ๊ธˆ์”ฉ ์ฆ๊ฐ€์‹œํ‚ค๋ฉด ์–ด๋Š ์ˆœ๊ฐ„ ๋ถ„์‚ฐ์ƒ๊ณผ ์—ฐ์†์ƒ์ด ๋น„

์Šทํ•ด์ง€๋ฉด์„œ ๋‘ ๊ณ ๋ถ„์ž๊ฐ€ ๋™์ผํ•˜๊ฒŒ ์กด์žฌํ•˜๋Š” ๊ณต๋™ ์—ฐ์†์ƒ(co-

continuous)์ด ์กด์žฌํ•  ์ˆ˜ ์žˆ๊ณ , ๋ถ„์‚ฐ์ƒ์˜ ํ•จ๋Ÿ‰์„ ๋” ์ฆ๊ฐ€์‹œํ‚ค

๋ฉด ๋ถ„์‚ฐ์ƒ์ด ์—ฐ์†์ƒ์œผ๋กœ ๋ฐ”๋€Œ๋Š” ์ƒ์ „์ด๊ฐ€ ๋‚˜ํƒ€๋‚œ๋‹ค.21,30 ๊ณ ๋ถ„

์ž ๋ธ”๋ Œ๋“œ๊ฐ€ ์—ฐ์†์ƒ-๋ถ„์‚ฐ์ƒ(sea-island)์˜ ๋ชจํด๋กœ์ง€๋ฅผ ๊ฐ€์งˆ ๊ฒฝ

์šฐ, ๋ธ”๋ Œ๋“œ์˜ ํŠน์„ฑ์€ ์—ฐ์†์ƒ์˜ ์˜ํ–ฅ์„ ๋งŽ์ด ๋ฐ›๊ฒŒ ๋˜๋ฉฐ, ๋ถ„์‚ฐ

์ƒ์€ ๋ณด์™„ํ•˜๋Š” ์—ญํ• ์„ ํ•œ๋‹ค. ๋”ฐ๋ผ์„œ ๋ธ”๋ Œ๋“œ์˜ ๋ชจํด๋กœ์ง€ ๋ฐ ์ƒ

์ „์ด ๋ถ„์„์„ ํ†ตํ•ด ์—ฐ์†์ƒ๊ณผ ๋ถ„์‚ฐ์ƒ์„ ์กฐ์ ˆํ•˜๋ฉด ์›ํ•˜๋Š” ํŠน์„ฑ

์„ ๊ฐ–๋Š” ๋ธ”๋ Œ๋“œ ์ œ์กฐ๊ฐ€ ๊ฐ€๋Šฅํ•˜๋‹ค.

ํ•œํŽธ, ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ์˜ ๋ชจํด๋กœ์ง€ ๋ฐ ์ƒ์ „์ด์˜ ๋ถ„์„์€ ์‹œํŽธ

์„ ๋งค์šฐ ์–‡์€ ๋ฐ•ํŽธ์œผ๋กœ ์ œ์กฐํ•˜์—ฌ ์—ผ์ƒ‰ํ•˜๊ฑฐ๋‚˜ ์—์นญํ•œ ํ›„ ํˆฌ๊ณผ

์ „์žํ˜„๋ฏธ๊ฒฝ(TEM)์„ ์ด์šฉํ•œ ๋ถ„์„๊ณผ ์ฃผ์‚ฌํƒ์นจํ˜„๋ฏธ๊ฒฝ(AFM)์„

์ด์šฉํ•˜์—ฌ ์กฐ์‚ฌํ•˜๋Š” ๋ฐฉ๋ฒ• ๋“ฑ์ด ๋„๋ฆฌ ์‚ฌ์šฉ๋˜๊ณ  ์žˆ๋‹ค. ์‹œํŽธ์„ ํŒŒ

๋‹จํ•œ ํ›„, ์—ผ๋ฃŒ๋ฅผ ํ†ตํ•ด ํŠน์ • ๊ณ ๋ถ„์ž๋ฅผ ์—ผ์ƒ‰ํ•˜๋ฉด ์—ผ์ƒ‰๋œ ๊ณ ๋ถ„

์ž์™€ ์—ผ์ƒ‰๋˜์ง€ ์•Š์€ ๊ณ ๋ถ„์ž์˜ ๋ฐ๊ธฐ ์ฐจ์ด์— ์˜ํ•ด TEM์„ ํ†ต

ํ•œ ๋ชจํด๋กœ์ง€ ๊ด€์ฐฐ์ด ๊ฐ€๋Šฅํ•˜๋‹ค.34,35 ์—์นญ์€ ์šฉ์•ก์„ ์ด์šฉํ•˜์—ฌ ํŠน

์ • ๊ณ ๋ถ„์ž๋ฅผ ์ œ๊ฑฐํ•˜๋Š” ๊ฒƒ์œผ๋กœ ๋ธ”๋ Œ๋“œ์˜ ํŒŒ๋‹จ๋ฉด์„ ์—์นญํ•œ ํ›„,

AFM์ด๋‚˜ ์ „์žํ˜„๋ฏธ๊ฒฝ(SEM)์„ ํ†ตํ•ด ์ด๋ฅผ ๊ด€์ฐฐํ•˜๋ฉด ์—์นญ๋˜์ง€

์•Š์€ ๊ณ ๋ถ„์ž ๋ถ€๋ถ„๊ณผ ์—์นญ๋˜์–ด ๊ณ ๋ถ„์ž๊ฐ€ ๋น ์ ธ๋‚˜๊ฐ„ ๋นˆ ๊ณต๊ฐ„์ด

๋ถ„์‚ฐ์ƒ๊ณผ ์—ฐ์†์ƒ์œผ๋กœ ๋‚˜ํƒ€๋‚œ๋‹ค.36-38 ๊ทธ๋Ÿฌ๋‚˜ ์—ผ์ƒ‰๊ณผ ์—์นญ์„ ์ด

์šฉํ•  ๊ฒฝ์šฐ, ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ ์ค‘ ํŠน์ • ๊ณ ๋ถ„์ž๋ฅผ ์„ ํƒ์ ์œผ๋กœ ์—ผ

์ƒ‰์‹œํ‚ค๊ฑฐ๋‚˜ ์—์นญ์‹œํ‚ค๋Š” ์šฉ์•ก์„ ์ฐพ์•„์•ผํ•  ๋ฟ๋งŒ ์•„๋‹ˆ๋ผ ์—ผ์ƒ‰๊ณผ

์—์นญ๊ณผ์ •์„ ๊ฑฐ์ณ์•ผ ํ•˜๋Š” ๋ฒˆ๊ฑฐ๋กœ์›€์ด ์žˆ๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์ด

๋Ÿฌํ•œ ๋ฒˆ๊ฑฐ๋กœ์›€์„ ์ค„์ด๊ธฐ ์œ„ํ•ด SEM ํŒŒ๋‹จ๋ฉด๊ณผ EDS ์›์†Œ๋ถ„์„

๊ฒฐ๊ณผ๋ฅผ ์ƒํ˜ธ mappingํ•จ์œผ๋กœ์จ ๊ฐ„๋‹จํ•œ ๋ฐฉ๋ฒ•์œผ๋กœ ์ƒ ๋ชจํด๋กœ์ง€

๋ถ„์„์„ ์‹œ๋„ํ•˜์˜€๋‹ค.

EPDM/FKM ๋ธ”๋ Œ๋“œ๋ฅผ ์•ก์ฒด์งˆ์†Œ์—์„œ ํŒŒ๋‹จํ•œ ํ›„, ํŒŒ๋‹จ๋ฉด์„

FE-SEM์„ ์ด์šฉํ•˜์—ฌ ๋ธ”๋ Œ๋“œ์˜ ๋ชจํด๋กœ์ง€๋ฅผ ๊ด€์ฐฐํ•œ ๊ฒฐ๊ณผ(Figure

2), ์ˆœ์ˆ˜ํ•œ EPDM(a)๊ณผ FKM(f)์—์„œ๋Š” ๊ฐ๊ฐ ๋‹จ์ผ ๋ช…์•”์„ ๋‚˜

ํƒ€๋‚ด๊ณ  ์žˆ์ง€๋งŒ, ๋ธ”๋ Œ๋“œ์˜ ๊ฒฝ์šฐ(b, c, d, e) ๋ช…์•”์˜ ์ฐจ์ด๋ฅผ ๋ณดFigure 1. Rheographs of EPDM/FKM blends.

Table 2. Curing Characteristics of EPDM/FKM Blends

Sample E10 E7F3 E5F5 E2F8 E1F9 F10

MH (dNm) 57.6 55.7 53.7 45.0 39.6 38.4

ML (dNm) 6.1 6.6 6.3 5.1 5.6 4.3

MH-ML (dNm) 51.5 49.1 47.4 39.9 34 34.1

ts2 (min) 2.3 2.1 2 2.1 2.3 2.1

t90 (min) 25.3 19.5 17.1 12.2 11.1 7.4

CRI (min-1) 4.4 5.8 6.6 9.9 11.3 19

*CRI (Cure rate index)=100/(cure time - scorch time).

Page 4: Phase Morphology and Mechanical Properties of Ethylene

์—ํ‹ธ๋ Œ-ํ”„๋กœํ•„๋ Œ-๋””์—”-๋ชจ๋…ธ๋จธ/๋ถˆ์†Œ๊ณ ๋ฌด ๋ธ”๋ Œ๋“œ์˜ ์ƒ ๋ชจํด๋กœ์ง€์™€ ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ 757

Polymer(Korea), Vol. 39, No. 5, 2015

์ด๋Š” ๋ชจํด๋กœ์ง€๋ฅผ ๋‚˜ํƒ€๋‚ด๊ณ  ์žˆ๊ณ , ๋ธ”๋ Œ๋“œ์˜ ์กฐ์„ฑ์„ ๊ฐ์•ˆํ•  ๋•Œ

๋ฐ์€ ์˜์—ญ์ด FKM์„ ๋‚˜ํƒ€๋‚ด๋Š” ๊ฒƒ์œผ๋กœ ์ถ”์ •๋œ๋‹ค. FKM์ด 30

๊ณผ 50 phr์ธ ๊ฒฝ์šฐ(b, c) ๋ฐ์€ ๋ถ€๋ถ„์ด ๋ถ„์‚ฐ์ƒ์„ ์–ด๋‘์šด ๋ถ€๋ถ„์ด

์—ฐ์†์ƒ์„ ๋‚˜ํƒ€๋‚ด๋Š” ์†Œ์œ„ โ€˜sea-islandโ€™ ๊ตฌ์กฐ์ฒ˜๋Ÿผ ๋‚˜ํƒ€๋‚ฌ๋‹ค. FKM

์ด 80 phr์ธ ๊ฒฝ์šฐ(d) ๋ฐ์€ ๋ถ€๋ถ„๊ณผ ์–ด๋‘์šด ๋ถ€๋ถ„์ด ๊ณต์กดํ•˜๋Š” ๊ณต

๋™ ์—ฐ์†์ƒ์„, FKM์ด 90 phr์ธ ๊ฒฝ์šฐ(e) ๋ฐ์€ ๋ถ€๋ถ„์ด ๋ถ„์‚ฐ์ƒ์œผ

๋กœ ์—ญ์ „๋˜๋Š” ์ƒ์ „์ด(phase inversion)๊ฐ€ ๋‚˜ํƒ€๋‚œ ๊ฒƒ์œผ๋กœ ๋ณด์ธ

๋‹ค. ๊ทธ๋Ÿฌ๋‚˜ FE-SEM ๋ชจํด๋กœ์ง€๋งŒ์œผ๋กœ๋Š” ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ์˜ ์ƒ

๊ฑฐ๋™์œผ๋กœ ๋‹จ์ •ํ•  ์ˆ˜๋Š” ์—†๋‹ค.

FE-SEM์—์„œ ์ถ”์ •๋œ ๊ฒฐ๊ณผ๋ฅผ ํ™•์ธํ•˜๊ธฐ ์œ„ํ•ด EDS ๋ถ„์„์„ ํ†ต

ํ•œ ํƒ„์†Œ(๋นจ๊ฐ•)์™€ ๋ถˆ์†Œ(์ดˆ๋ก)์— ๋Œ€ํ•œ ์›์†Œ๋ถ„์„ ์ด๋ฏธ์ง€๋ฅผ ์–ป์—ˆ

๊ณ (Figure 3), ๊ฐ ๋ธ”๋ Œ๋“œ์— ๋Œ€ํ•œ ์ฃผ์š” ์›์†Œ๋ถ„์„ ๊ฒฐ๊ณผ๋ฅผ Table

3์— ์ •๋ฆฌํ•˜์˜€๋‹ค. ์ „์ฒด์ ์œผ๋กœ ํƒ„์†Œ์™€ ๋ถˆ์†Œ ์ด๋ฏธ์ง€๊ฐ€ ์„œ๋กœ ์ž˜

๊ฒน์ณ์ง€๊ณ  ์žˆ๊ณ , ์ „์ˆ ํ•œ FE-SEM ๋ชจํด๋กœ์ง€์™€๋„ ๊ฒน์ณ์ง€๋Š” ๊ฒƒ

์œผ๋กœ ๋ฏธ๋ฃจ์–ด Figure 2์—์„œ ์–ป์—ˆ๋˜ ์ƒ ๋ชจํด๋กœ์ง€์˜ ๊ฒฐ๊ณผ๋ฅผ ๋’ท

๋ฐ›์นจํ•˜๊ณ  ์žˆ๋‹ค. FKM์˜ ํ•จ๋Ÿ‰์— ๋น„๋ก€ํ•˜์—ฌ ๋ถˆ์†Œ์›์ž F์˜ ํ•จ๋Ÿ‰

์ด ์ฆ๊ฐ€ํ•˜์˜€์œผ๋ฉฐ ๋ถ„์‚ฐ์ƒ์ธ FKM์˜ ์ž…์ž ๋ชจ์–‘์ด ํƒ€์›ํ˜•๊ณผ ๊ธด

์„ฌ์œ ์ƒ์œผ๋กœ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ์ด๋Š” ๋ธ”๋ Œ๋“œ ํ˜ผํ•ฉ ์‹œ ์ „๋‹จ ์‘๋ ฅ์ด ์ž‘

์šฉํ•œ ๋ฐฉํ–ฅ์œผ๋กœ ๋ถ„์‚ฐ์ƒ์˜ ๋ณ€ํ˜•์ด ์ผ์–ด๋‚ฌ๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ๋ณด์ธ๋‹ค.30

FKM์˜ ํ•จ๋Ÿ‰์ด ๋” ์ฆ๊ฐ€ํ•˜์—ฌ ์กฐ์„ฑ์ด 80 phr์— ์ด๋ฅด๋ฉด EPDM

๊ณผ FKM์ด ๊ณตํžˆ ์—ฐ์†์ƒ์„ ์ด๋ฃจ๋Š” co-continuous ๋ชจํด๋กœ์ง€๊ฐ€

๋‚˜ํƒ€๋‚ฌ์œผ๋ฉฐ, FKM์ด 90 phr์— ์ด๋ฅด๋ฉด FKM์ด ์—ฐ์†์ƒ์œผ๋กœ ์ „

ํ™˜๋˜๋Š” ์ƒ์ „์ด๊ฐ€ ๊ด€์ฐฐ๋˜์—ˆ๋‹ค. Table 3์— ๋‚˜ํƒ€๋‚ธ ์›์†Œํ•จ๋Ÿ‰์—

์„œ๋„ FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก F ํ•จ๋Ÿ‰์ด ์ ์ฐจ ์ฆ๊ฐ€ํ•˜์˜€์œผ

๋ฉฐ, ๊ณต๋™ ์—ฐ์†์ƒ์„ ๋‚˜ํƒ€๋‚ด๋Š” E2F8 ์กฐ์„ฑ์—์„œ๋Š” C์™€ F์˜ ํ•จ๋Ÿ‰

์ด ๊ฑฐ์˜ ๋™์ผํ•˜๊ฒŒ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ์ƒ์ „์ด๊ฐ€ ๊ด€์ฐฐ๋œ E1F9 ์กฐ์„ฑ์—์„œ

๋Š” F๊ฐ€ C์˜ ํ•จ๋Ÿ‰์„ ๋Šฅ๊ฐ€ํ•˜๋Š” ๊ฒƒ์œผ๋กœ ๋‚˜ํƒ€๋‚ฌ๋‹ค.

Figure 2. FE-SEM images of EPDM/FKM blends: (a) E10; (b)

E7F3; (c) E5F5; (d) E2F8; (e) E1F9; (f) F10.

Figure 3. EDS chemical elements mapping of EPDM/FKM blends

(red dot indicate carbon atom and green dot indicate fluorine atom):

(a) E10; (b) F10; (c),(d) E7F3; (e),(f) E5F5; (g),(h) E2F8; (i),(j)

E1F9.

Page 5: Phase Morphology and Mechanical Properties of Ethylene

758 ์ด๊ธฐ์จยท๊น€์Šน๊ฒธยท์œ ์šฉํ™˜ยท๊ฐ•์„์ธยท์˜ค์ข…๊ฐ‘ยทํ—ˆ์–‘์ผยท์ •๋ณ‘ํ—Œยท๋‚˜์ฐฝ์šด

ํด๋ฆฌ๋จธ, ์ œ39๊ถŒ ์ œ5ํ˜ธ, 2015๋…„

๊ธฐ๊ณ„์  ๋ฌผ์„ฑ. EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ์กฐ์„ฑ์— ๋”ฐ๋ฅธ ๊ฒฝ๋„ํŠน์„ฑ

์„ Table 4์— ๋‚˜ํƒ€๋‚ด์—ˆ์œผ๋ฉฐ, Figure 4์—๋Š” ์ธ์žฅ์‹คํ—˜์˜ ์‘๋ ฅ-

๋ณ€ํ˜• ๊ณก์„ ์œผ๋กœ ๋‚˜ํƒ€๋‚ด์—ˆ๊ณ , ๋ธ”๋ Œ๋“œ ์กฐ์„ฑ๋น„์— ๋‹ค๋ฅธ ์ธ์žฅ๊ฐ•๋„

์™€ ํŒŒ๋‹จ์‹ ์žฅ๋ฅ  ๊ฑฐ๋™์„ ๊ฐ๊ฐ Figure 5๊ณผ Figure 6์— ๋‚˜ํƒ€๋‚ด์—ˆ

๋‹ค. FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ•จ์— ๋”ฐ๋ผ ๊ฒฝ๋„๊ฐ€ ์ฆ๊ฐ€ํ•˜์˜€์œผ๋ฉฐ, ์ธ

์žฅ๊ฐ•๋„, ํŒŒ๋‹จ์‹ ์žฅ๋ฅ  ๋ชจ๋‘ ์ฆ๊ฐ€ํ•˜๋Š” ๊ฒฝํ–ฅ์„ ๋ณด์˜€๋‹ค. ์ผ๋ฐ˜์ ์œผ

๋กœ FKM์˜ ๊ฒฝ๋„, ์ธ์žฅ๊ฐ•๋„, ํŒŒ๋‹จ์‹ ์žฅ๋ฅ ์ด EPDM๋ณด๋‹ค ๋†’๊ธฐ

๋•Œ๋ฌธ์— ์ด๋Ÿฌํ•œ ๊ฒฝํ–ฅ์ด ๋‚˜ํƒ€๋‚˜๋Š” ๊ฒƒ์œผ๋กœ ๋ณด์ธ๋‹ค.39 ํŠนํžˆ ์ธ์žฅ

๊ฐ•๋„์˜ ๊ฒฝ์šฐ, E1F9์˜ ์กฐ์„ฑ์—์„œ ๊ธ‰๊ฒฉํ•œ ์ฆ๊ฐ€ ํ˜„์ƒ์ด ๋‚˜ํƒ€๋‚ฌ๋Š”

๋ฐ, ์ด๋Š” FKM์ด ์—ฐ์†์ƒ์œผ๋กœ ๋‚˜ํƒ€๋‚˜๋Š” ์ƒ์ „์ด๊ฐ€ ์ผ์–ด๋‚˜๋ฉด์„œ

๋ธ”๋ Œ๋“œ์˜ ํŠน์„ฑ์ด FKM์˜ ๋ฌผ์„ฑ์— ํฌ๊ฒŒ ์˜์กดํ•˜๊ฒŒ ๋˜์—ˆ๊ธฐ ๋•Œ๋ฌธ

์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค. ์ด ๊ฒฐ๊ณผ๋Š” FE-SEM๊ณผ EDS ๋ถ„์„์„ ํ†ตํ•ด ๊ด€

์ฐฐํ•œ ์ƒ์ „์ด ๊ฑฐ๋™๊ณผ ์ผ์น˜ํ•˜๋Š” ๊ฒƒ์œผ๋กœ ๋ณธ ์‹คํ—˜์—์„œ ์‹œ๋„๋œ

EDS ์›์†Œ๋ถ„์„ ๋ฐ mapping ๋ฐฉ๋ฒ•์ด ๋งค์šฐ ์œ ์šฉํ•˜๋‹ค๊ณ  ํŒ๋‹จ๋œ๋‹ค.

๋™์  ๊ธฐ๊ณ„ํŠน์„ฑ. EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ๋™์  ์ ํƒ„์„ฑ ๊ฑฐ๋™์€

DMA๋ฅผ ํ†ตํ•ด ์ธก์ •ํ•˜์˜€์œผ๋ฉฐ, ์ €์žฅ ๋ชจ๋“ˆ๋Ÿฌ์Šค(E')์™€ ์†์‹ค๊ณ„์ˆ˜

tanฮด๋ฅผ Figures 7, 8์— ๊ฐ๊ฐ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ์ €์žฅ ๋ชจ๋“ˆ๋Ÿฌ์Šค๋Š”

FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ์ฆ๊ฐ€ํ•˜๋Š” ๊ฒฝํ–ฅ์„ ๋ณด์˜€๋Š”๋ฐ ์ด๋Š”

Table 3. EDS Analysis of the EPDM/FKM Blends

SampleE10 E7F3 E5F5 E2F8 E1F9 F10

Wt% At% Wt% At% Wt% At% Wt% At% Wt% At% Wt% At%

C 96.6 97.7 93.2 95.8 79 85.7 48.7 60.2 40.3 51.8 33 43.9

F 5.7 3.7 20.5 14.1 49.8 39 58.8 47.7 66.2 55.6

O 2.6 2.0

Si 0.8 0.3 1.1 0.5 0.5 0.2 1.5 0.8 0.9 0.5 0.8 0.5

Total 100 100 100 100 100 100

Table 4. Hardness of the EPDM/FKM Blends

Sample E10 E7F3 E5F5 E2F8 E1F9 F10

Hardness (Shore A) 54.3ยฑ0.42 55.4ยฑ0.60 56.2ยฑ0.48 56.2ยฑ0.60 56.4ยฑ0.56 57.1ยฑ0.74

Figure 4. Tensile stress-strain curves of EPDM/FKM blends.

Figure 5. Tensile strength of EPDM/FKM blends as a function of

FKM content.

Figure 6. Elongation at break of EPDM/FKM blends as a function

of FKM content.

Page 6: Phase Morphology and Mechanical Properties of Ethylene

์—ํ‹ธ๋ Œ-ํ”„๋กœํ•„๋ Œ-๋””์—”-๋ชจ๋…ธ๋จธ/๋ถˆ์†Œ๊ณ ๋ฌด ๋ธ”๋ Œ๋“œ์˜ ์ƒ ๋ชจํด๋กœ์ง€์™€ ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ 759

Polymer(Korea), Vol. 39, No. 5, 2015

์•ž์—์„œ ์–ธ๊ธ‰ํ•œ ๊ฒƒ๊ณผ ๊ฐ™์ด FKM์ด EPDM๋ณด๋‹ค ์šฐ์ˆ˜ํ•œ ๊ธฐ๊ณ„์ 

๋ฌผ์„ฑ์„ ๋‚˜ํƒ€๋‚ด๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค. ๋˜ํ•œ ์ €์žฅ ๋ชจ๋“ˆ๋Ÿฌ์Šค๋Š”

์—ฐ์†์ƒ์˜ ์ข…๋ฅ˜์— ๋”ฐ๋ผ ๋‹ค๋ฅธ ๊ณก์„  ํ˜•ํƒœ๋กœ ๋‚˜ํƒ€๋‚ฌ๋‹ค. FKM์˜

ํ•จ๋Ÿ‰์ด ์ ์€ ์กฐ์„ฑ์—์„œ๋Š” EPDM๊ณผ ๋น„์Šทํ•œ ๊ณก์„  ํ˜•ํƒœ๋ฅผ ๋ณด์˜€

์œผ๋‚˜ FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ•จ์— ๋”ฐ๋ผ FKM๊ณผ ๋น„์Šทํ•œ ๊ณก์„  ํ˜•

ํƒœ๋ฅผ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ํŠนํžˆ FKM์ด ๋ถ„์‚ฐ์ƒ์—์„œ ์—ฐ์†์ƒ์œผ๋กœ ์ „ํ™˜

๋˜๋Š” E1F9์˜ ๊ฒฝ์šฐ, FKM๊ณผ ๊ฑฐ์˜ ์œ ์‚ฌํ•œ ์ €์žฅ ๋ชจ๋“ˆ๋Ÿฌ์Šค ๊ณก์„ 

ํ˜•ํƒœ๋ฅผ ๋‚˜ํƒ€๋‚ด๊ณ  ์žˆ๋‹ค. ๋”ฐ๋ผ์„œ EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ์ €์žฅ

๋ชจ๋“ˆ๋Ÿฌ์Šค๋Š” ์—ฐ์†์ƒ์„ ๋‚˜ํƒ€๋‚ด๋Š” ๊ณ ๋ถ„์ž์˜ ์˜ํ–ฅ์„ ํฌ๊ฒŒ ๋ฐ›๋Š”

๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค. ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ์˜ ์œ ๋ฆฌ์ „์ด์˜จ๋„(Tg)๋Š” DMA

์˜ tanฮด ์ธก์ •์„ ํ†ตํ•ด ํ™•์ธํ•˜์˜€๋‹ค. ๋ธ”๋ Œ๋“œ๋ฅผ ์ด๋ฃจ๊ณ  ์žˆ๋Š” ๋‘

๊ณ ๋ถ„์ž๊ฐ€ ์™„์ „ํžˆ ํ˜ผํ•ฉ๋˜์–ด ํ•˜๋‚˜์˜ ์ƒ๋งŒ์ด ์กด์žฌํ•  ๊ฒฝ์šฐ, ํ•˜๋‚˜

์˜ Tg ๊ฐ’์ด ๋‚˜ํƒ€๋‚˜์ง€๋งŒ ๋‘ ๊ณ ๋ถ„์ž๊ฐ€ ํ˜ผํ•ฉ๋˜์ง€ ์•Š์•„ 2๊ฐœ์˜ ์ƒ

์ด ์กด์žฌํ•  ๊ฒฝ์šฐ, ๊ณ ๋ถ„์ž ๊ฐ๊ฐ์˜ Tg ๊ฐ’์ด ํ•จ๊ป˜ ๋‚˜ํƒ€๋‚œ๋‹ค. ์ด๋•Œ,

๋‘ ๊ณ ๋ถ„์ž๊ฐ€ ์™„์ „ํžˆ ํ˜ผํ•ฉ๋˜์ง„ ์•Š์•˜์ง€๋งŒ ๋ถ€๋ถ„์ ์œผ๋กœ ํ˜ผํ•ฉ๋˜์–ด

์žˆ๋‹ค๋ฉด 2๊ฐœ์˜ Tg๊ฐ€ ์„œ๋กœ ๊ฐ€๊นŒ์›Œ์ง€๋Š” ํ˜„์ƒ์ด ์ผ์–ด๋‚œ๋‹ค.40

Figure 8์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด EPDM์˜ Tg๋Š” -35 oC, FKM์˜

Tg๋Š” -6 oC๋กœ ๋‚˜ํƒ€๋‚ฌ์œผ๋ฉฐ ๋ธ”๋ Œ๋“œ์˜ ๊ฒฝ์šฐ, EPDM ์ƒ๊ณผ FKM

์ƒ์— ์˜ํ•ด 2๊ฐœ์˜ Tg ๊ฐ’์ด ๋‚˜ํƒ€๋‚˜๋ฉด์„œ ์ „ํ˜•์ ์ธ ๋น„ํ˜ผํ™”์„ฑ ๊ณ 

๋ถ„์ž ๋ธ”๋ Œ๋“œ์˜ tanฮด ๊ณก์„ ์„ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ๋ธ”๋ Œ๋“œ์˜ Tg ํ”ผํฌ๋Š”

๋ธ”๋ Œ๋“œ์˜ ์กฐ์„ฑ์— ๋”ฐ๋ผ ๋‹ค๋ฅด๊ฒŒ ๋‚˜ํƒ€๋‚ฌ๋Š”๋ฐ, ์กฐ์„ฑ์ด ๋งŽ์€ ๊ณ ๋ถ„

์ž์˜ Tg ํ”ผํฌ๋Š” ํฌ๊ณ  ๊ฐ•ํ•˜๊ฒŒ ๋‚˜ํƒ€๋‚ฌ์œผ๋ฉฐ, ์ ์€ ์กฐ์„ฑ์˜ Tg ํ”ผ

ํฌ๋Š” ์ž‘๊ณ  ์™„๋งŒํ•˜๊ฒŒ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ๋˜ํ•œ ๊ณ ๋ถ„์ž์˜ ์กฐ์„ฑ์ด ์ฆ๊ฐ€ํ• 

์ˆ˜๋ก ๊ณ ๋ถ„์ž ๋ณธ๋ž˜์˜ Tg ํ”ผํฌ์™€ ์œ ์‚ฌํ•œ ํ”ผํฌ๋ฅผ ๋‚˜ํƒ€๋ƒˆ๋‹ค. ์ฆ‰,

EPDM/FKM ๋ธ”๋ Œ๋“œ์—์„œ EPDM ์ƒ์— ์˜ํ•ด ๋‚˜ํƒ€๋‚˜๋Š” Tg ํ”ผํฌ

๋Š” EPDM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ์ˆœ์ˆ˜ EPDM์˜ Tg์ธ -35 oC

์— ๊ฐ€๊นŒ์›Œ์ง€๊ณ , FKM ์ƒ์— ์˜ํ•ด ๋‚˜ํƒ€๋‚˜๋Š” Tg ํ”ผํฌ๋Š” ์ˆœ์ˆ˜

FKM์˜ Tg์ธ -5 oC์— ๊ฐ€๊นŒ์›Œ์ง€๋Š” ๊ฒฝํ–ฅ์ด ๋‚˜ํƒ€๋‚ฌ๋‹ค. EPDM/

FKM ๋ธ”๋ Œ๋“œ์—์„œ๋Š” ๋‘ ๊ณ ๋ถ„์ž์˜ ๋ถ€๋ถ„์  ํ˜ผํ•ฉ์œผ๋กœ ์ธํ•œ Tg์˜

์ด๋™์ด ๋‚˜ํƒ€๋‚˜์ง€ ์•Š์•˜๋Š”๋ฐ, ์ด๋Š” ๋น„๊ทน์„ฑ์ธ EPDM๊ณผ ๊ทน์„ฑ์ธ

FKM์˜ ์ƒ์šฉ์„ฑ์ด ๋งค์šฐ ์ž‘์•„ ํ˜ผํ•ฉ์ด ์ผ์–ด๋‚˜๊ธฐ ์–ด๋ ต๊ธฐ ๋•Œ๋ฌธ์ธ

๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค.

๊ฒฐ ๋ก 

EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ์กฐ์„ฑ์— ๋”ฐ๋ฅธ ๋ชจํด๋กœ์ง€์™€ ๊ธฐ๊ณ„์  ๋ฌผ

์„ฑ์„ ์•Œ์•„๋ณด๊ธฐ ์œ„ํ•ด ๋‹ค์–‘ํ•œ ์กฐ์„ฑ์— ๋”ฐ๋ฅธ ๋ธ”๋ Œ๋“œ๋ฅผ ์ œ์กฐํ•˜๊ณ 

๊ฐ€๊ตํŠน์„ฑ, FE-SEM, EDS ๋ถ„์„, ์ธ์žฅํŠน์„ฑ, ๊ฒฝ๋„ํŠน์„ฑ ๊ทธ๋ฆฌ๊ณ 

๋™์  ์ ํƒ„์„ฑ์„ ์กฐ์‚ฌํ•œ ๊ฒฐ๊ณผ ๋‹ค์Œ๊ณผ ๊ฐ™์€ ๊ฒฐ๊ณผ๋ฅผ ์–ป์—ˆ๋‹ค.

EPDM/FKM ๋ธ”๋ Œ๋“œ๋Š” FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ๊ฐ€๊ต์†

๋„๊ฐ€ ๋นจ๋ผ์กŒ์œผ๋‚˜, ๊ฐ€๊ต๋ฐ€๋„๋Š” ๊ฐ์†Œํ•˜์˜€๋‹ค. ์Šค์ฝ”์น˜ ์‹œ๊ฐ„์€ ๋ธ”

๋ Œ๋“œ ์กฐ์„ฑ์— ์ƒ๊ด€์—†์ด ์ผ์ •ํ•œ ๊ฐ’์„ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ๋ชจํด๋กœ์ง€ ๋ฐ ์ƒ์ „์ด ๊ฑฐ๋™ ๊ด€์ฐฐ์„ ์œ„

ํ•ด FE-SEM๊ณผ EDS์˜ ์›์†Œ๋ถ„์„ ๋ฐ mapping์„ ํ†ตํ•˜์—ฌ ๋ชจ๋“ 

๋ธ”๋ Œ๋“œ ์กฐ์„ฑ์—์„œ ์ „ํ˜•์ ์ธ ์—ฐ์†์ƒ-๋ถ„์‚ฐ์ƒ ๋ชจํด๋กœ์ง€๋ฅผ ๋ณด์˜€์œผ

๋ฉฐ, E2F8์˜ ๋ธ”๋ Œ๋“œ ์กฐ์„ฑ์—์„œ ๊ณต๋™์—ฐ์†์ƒ ๋ชจํด๋กœ์ง€, E1F9์—

์„œ ์ƒ์ „์ด ๊ฑฐ๋™์ด ๊ด€์ฐฐ๋˜์—ˆ๋‹ค.

EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ๊ฒฝ๋„, ์ธ์žฅ๊ฐ•๋„, ํŒŒ๋‹จ์‹ ์žฅ๋ฅ  ๊ทธ๋ฆฌ๊ณ 

๋ชจ๋“ˆ๋Ÿฌ์Šค ๋ชจ๋‘ FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ์ฆ๊ฐ€ํ•˜๋Š” ๊ฒฝํ–ฅ์„

๋ณด์˜€์œผ๋ฉฐ, ์ธ์žฅ๊ฐ•๋„์˜ ๊ฒฝ์šฐ, E1F9์—์„œ ๊ธ‰๊ฒฉํ•œ ์ฆ๊ฐ€๋ฅผ ๋ณด์˜€๋‹ค.

์ด๋Š” ๋ธ”๋ Œ๋“œ์˜ ์—ฐ์†์ƒ์ด EPDM์—์„œ FKM์œผ๋กœ ๋ณ€ํ™˜๋˜๋Š” ์ƒ

์ „์ด๊ฐ€ ์ผ์–ด๋‚˜๋ฉด์„œ ๋‚˜ํƒ€๋‚œ ๊ฒฐ๊ณผ๋กœ ํ•ด์„๋˜์—ˆ๋‹ค.

EPDM/FKM ๋ธ”๋ Œ๋“œ์˜ ์ €์žฅ ๋ชจ๋“ˆ๋Ÿฌ์Šค๋Š” FKM์˜ ํ•จ๋Ÿ‰์ด ์ฆ

๊ฐ€ํ• ์ˆ˜๋ก ์ฆ๊ฐ€ํ•˜๋Š” ๊ฒฝํ–ฅ์„ ๋ณด์˜€์œผ๋ฉฐ, EPDM๊ณผ FKM์˜ ๊ทน์„ฑ

์ฐจ์ด๋กœ ์ธํ•ด ํ˜ผํ•ฉ์ด ์–ด๋ ค์šฐ๋ฏ€๋กœ ๋‘ ๊ณ ๋ถ„์ž์˜ Tg๋ฅผ ํ•จ๊ป˜ ๊ฐ–๋Š”

์ „ํ˜•์ ์ธ ๋น„ํ˜ผํ™”์„ฑ ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ์˜ tanฮด ๊ฑฐ๋™์ด ๊ด€์ฐฐ๋˜์—ˆ๋‹ค.

๋ณธ ์—ฐ๊ตฌ์—์„œ ์‹œ๋„๋œ EDS ์›์†Œ๋ถ„์„ ๋ฐ mapping ๋ถ„์„๋ฒ•์€

๊ตฌ์„ฑ ์›์†Œ๊ฐ€ ๋‹ค๋ฅธ ๊ณ ๋ถ„์ž ๋ธ”๋ Œ๋“œ ์‹œ์Šคํ…œ์˜ ์ƒ๊ฑฐ๋™ ๋ถ„์„์— ๋งค

์šฐ ์œ ์šฉํ•  ๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค.

Figure 7. Storage modulus (E') of EPDM/FKM blends as a function

of temperature.

Figure 8. Tanฮด of EPDM/FKM blends as a function of temperature.

Page 7: Phase Morphology and Mechanical Properties of Ethylene

760 ์ด๊ธฐ์จยท๊น€์Šน๊ฒธยท์œ ์šฉํ™˜ยท๊ฐ•์„์ธยท์˜ค์ข…๊ฐ‘ยทํ—ˆ์–‘์ผยท์ •๋ณ‘ํ—Œยท๋‚˜์ฐฝ์šด

ํด๋ฆฌ๋จธ, ์ œ39๊ถŒ ์ œ5ํ˜ธ, 2015๋…„

๊ฐ์‚ฌ์˜ ๊ธ€: ๋ณธ ์—ฐ๊ตฌ๋Š” ํ•œ๊ตญ์‚ฐ์—…๊ธฐ์ˆ ํ‰๊ฐ€๊ด€๋ฆฌ์›์˜ ์ง€์›์„

๋ฐ›๋Š” ์‚ฐ์—…์›์ฒœ๊ธฐ์ˆ ๊ฐœ๋ฐœ์‚ฌ์—…(๊ณผ์ œ๋ฒˆํ˜ธ 1004003)์„ ํ†ตํ•ด ์ˆ˜ํ–‰

๋œ ์—ฐ๊ตฌ์ด๋ฉฐ, ์ด์— ๊ฐ์‚ฌ๋“œ๋ฆฝ๋‹ˆ๋‹ค.

์ฐธ ๊ณ  ๋ฌธ ํ—Œ

1. A. Parthasarathy and S. Srinivasan, Electroanal. Chem., 339, 101

(1992).

2. K. A. Mauritz and R. B. Moore, Chem. Rev., 104, 4535 (2004).

3. S. Mitra, A. Ghanbari-Siahkali, P. Kingshott, K. Almdal, H. K.

Rehmeier, and A. G. Christensen, Polym. Degrad. Stab., 83, 195

(2004).

4. M. Schulze, T. Knori, A. Schneider, and E. Gulzow, J. Power

Sources, 127, 222 (2004).

5. A. Husar, M. Serra, and C. Kunusch, J. Power Sources, 169, 85

(2007).

6. W. S. Choi, G. W. Kim, J. S. Do, M. H. Yoo, and S. H. Ryu, Elast.

Compos., 46, 132 (2011).

7. K. H. Seo, K. S. Cho, I. S. Yun, W. H. Choi, B. K. Hur, and D.

G. Kang, Elast. Compos., 45, 212 (2010).

8. S. J. C. Cleghorn, D. K. Mayfield, D. A. Moore, J. C. Moore, G.

Rusch, T. W. Sherman, N. T. Sisofo, and U. Beuscher, J. Power

Sources, 158, 446 (2006).

9. J. St-Pierre and N. Jia, J. New Mater. Electrochem. Syst., 5, 263

(2002).

10. N. Sammes, Fuel Cell Technology: Reaching Towards

Commercialization, Springer Publishers, New York, 2006.

11. V. Neburchilov, J. Martin, H. Wang, and J. Zhang, J. Power

Sources, 169, 221 (2007).

12. Y. Wang, K. S. Chen, J. Mishler, C. C. Sung, and C. A. Xavier,

Appl. Energ., 88, 981 (2011).

13. M. R. Ashraf Khorasani, S. Asghari, A. Mokmeli, M. H.

Shahsamandi, and B. Faghih Imani, Inter. J. Hydrogen Energ.,

35, 9269 (2010).

14. H. G. Kim and S. C. Nah, New Renewable Energy & Fuel Cell,

Studies Information, 2006.

15. U. Basuli, J. Jose, R. H. Lee, Y. H. Yoo, K.-U. Jeong, J.-H. Ann,

and C. Nah, J. Nanosci. Nanotechnol., 12, 7641 (2012).

16. U. Basuli, J. Jose, R. H. Lee, Y. H. Yoo, K.-U. Jeong, J.-H. Ahn,

C. Nah, J. Nanosci. Nanotechnol., 12, 7641 (2012).

17. D. H. Kim, S. H. Hwang, and B. S. Kim, J. Appl. Polym. Sci.,

125, 1625 (2012).

18. A. B. Nair, P. Kurian, and R. Joseph, Mater. Design, 36, 767

(2012).

19. Y. Wang, L. Liu, Y. Luo, and D. Jia, Polym. Degrad. Stab., 94,

443 (2009).

20. A. B. Nair, P. Kurian, and R. Joseph, Eur. Polym. J., 49, 247

(2013).

21. Y.-K. Chung, S.-G. Lee, B. R. Cho, and K.-Y. Choi, Polym.

Korea, 29, 166 (2005).

22. A. L. N. da Silva and F. M. B. Coutinho, Polym. Test., 15, 45

(1996).

23. J.-C. Lee, T.-G. Kim, K.-S. Hwang, and K.-R. Ha, Elastomer, 43,

8 (2008).

24. E. Gomaa, J. Appl. Polym. Sci., 105, 2564 (2007).

25. R. Chowdhury, M. S. Banerji, and K. Shivakumar, J. Appl.

Polym. Sci., 100, 1008 (2006).

26. S. Kole, A. Bhattacharya, D. K. Tripathy, and A. K. Bhowmick,

J. Appl. Polym. Sci., 48, 529 (1993).

27. J. Konar, S. Kole, N. Avasthi, and A. K. Bhowmick, J. Appl.

Polym. Sci., 61, 501 (1996).

28. S. Kole, S. Roy, and A. K. Bhowmick, Polymer, 36, 3273 (1995).

29. B. D. Favis, J. Appl. Polym. Sci., 39, 285 (1990).

30. S.-G. Lee, J. H. Lee, K.-Y. Choi, and J. M. Rhee, Polym. Korea,

22, 258 (1998).

31. S.-S. Choi and O.-B. Kim, Elast. Compos., 46, 138 (2011).

32. S.-S. Choi, K.-J. Hwang, and B.-T. Kim, J. Appl. Polym. Sci., 98,

2282 (2005).

33. S.-S. Choi, B.-H. Park, and H. Song, Polym. Adv. Technol., 15,

122 (2004).

34. B. Amรฉduri, B. Boutevin, and G. Kostov, Prog. Polym. Sci., 26,

105 (2001).

35. C.-H. Chen, J. C. LaRue, R. D. Nelson, L. Kulinsky, and M. J.

Madou, J. Appl. Polym. Sci., 125, 3134 (2012).

36. H. Wang and R. J. Composto, Europhys. Lett., 50, 622 (2000).

37. L. Li, X. Shen, S. W. Hong, R. C. Hayward, and T. P. Russell,

Angew. Chem. Int. Ed., 51, 4089 (2012).

38. M. V. Novelloa, L. G. Carreiraa, and L. B. Canto, Mater. Res., 17,

1285 (2014).

39. S.-S. Choi, C. W. Joo, and D. C. Kim, Elastomer, 37, 14 (2002).

40. D. R. Paul and S. Newman, Polymer Blends, Academic Press,

New York, 1978.