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1 Jurnal f the Krean Ceramic Sciety Vl. 45, N. 7, pp. 387~394, A Study n the Infrared Emissin Prperties and Freeze-thaw Resistance fr Calcined Clay by Carburizatin Treatment Kih Kim, Sangmyung Kim*, Byungchul Kang* Department f Materials Engineering, Chungbuk Natinal University, Chengju , Krea *Krea Institute f Cnstructin Materials, Seul , Krea (Received May 7, 2008; Accepted July 2, 2008) m ek w w p ½»yÁ½ * Á * w œw *w x ( ; ) Abstract The Physical prperty changes f calcined clay by carburizatin were investigated studied. The carburizatin mechanism is the penetratin f carbn which ccurred during incmplete fuel cmbustin int crevice f clay structure. The experiments fr elasticity and freeze-thaw resistance were cnducted, and the results can be summarized as fllws: Dynamic mdulus f elasticity and als freeze-thaw resistance f calcined clay by carburizatin treatment increased mre than 92% after testing 300 cycle, which was mre imprved than 88% f calcined clay. Therefre, it can decrease the pssibility f winterswing, which is ne the weakness f calcined clay. It is n the basis f the fact that the prsity f calcined clay by carburizatin treatment is abut 12%, which indicates smaller pre spaces cmparing with the 14% f prsity f calcined clay and thse values were calculated by apparent prsity shw and als supprted by SEM images. Infrared emissivity f calcined clay by carburizatin treatment and calcined clay were respectively 0.92 and 0.91 at 80 C. Hwever, thse values were 0.91 and 0.88 at 200 C, which means infrared emissivity f calcined clay by carburizatin treatment shws 3.6% higher than the calcined clay. Mrever, within the wavelength range frm 3 t 7 µm, while the calcined clay had lw infrared emissivity, the calcined clay by carburizatin treatment had increased infrared emissivity. It is inferred that it was affected by carbn element that has high infrared absrptivity within this wavelength range. Key wrds : Calcine clay, Carburized treatment, Crystalline graphite, Freeze-thaw, Dynamic mdulus f elasticity, Thermal analysis, Infrared, Emissity, Emissive pwer 1. m,»,,», y m w. ù p» ƒ wš Á» q w. w p wš ek w m w p ü m x ww, ek k w k, w ƒ tw. m ek 1) w w p w x Crrespnding authr : Sangmyung Kim ksm@kicm.re.kr Tel : Fax : twš w. m w w ü w t œ 9.1% ƒ q w x š, ü sw w ü j w ³ w ù td ƒ ü w ƒ ùkù. w 2) w m j ù ü œ ã q z ƒ q. ek w z ek m w p w ww. wr, t»q w w, 387

2 388 ½»yÁ½ Á w š z y w p.», t v w w ƒ w w ƒ w,, tƒœ, ƒ ƒœ, ù š. 3) ek m m w œ œ», w ƒ k (Carbn) m ü œ (Pre) en, n w f mw w. ek m k e n w œ e w w w w k w p yƒ q wš x y w, ek mƒ w w w w p w ek m w ü w ww. 2. x 2.1. ek k ƒ j, w w. œ w k j yk (CO 2 )ƒ, ƒ w ƒ COƒ ƒ. ek m v w œ» œ» œ w COƒ Buduard reactin w w Carbn m t sy kƒ y w t ƒ w m ü œ k ƒ enw f mw. 4), ü» k sy kƒ» (Sting) w Ì š, w ƒ» w m ü œ wì en. ek ü 800 C 1 g m m k w» y m w, m ek m w KS L 4007 m Rigaku PRIMUS XRF w w. k y KS M 0014 LECO CS-444 C-S» w, m ek m 1400 C¾ k z ƒ s w w. q Hitachi TM0 x w. 2.3.»»œ w w x»œ w w w y w» w KS L 3114»»œ xw x. (110 ±5) C w» wš w (W1) d w. s e w ò ƒ 3 ò š ¾ þ ƒw z s w., ƒw þ ƒw w. 1 mm w d w z s (W 2 ) w. s Éü t š, d w s (W 3 ) w.»»œ (1) w w Table 1. W»»œ 3 W 1 (%) P 0 = (1) W 3 W 2» W 1 : (g) W 2 : s (g) W 3 : s (g) w w ü w ü sw w, ü û q w ü j, ³ w ù td ƒ, ü wƒ ùkù. w y dw» w w j x z k d w k (2) w. P c =(n 1 2/n 2 ) (2)», P c : w C j z k (%) n : w» j ƒ 1 q n 1 : w C j z ƒ 1 q Table 1. Apparent Prsity Test carburized clay =11.8% W 1 : 111.3(g) W 2 : 67.1 (g) W 3 : 118.0(g) calcined clay P 0 = P 0 = =13.8% W 1 : (g) W 2 : 61.4 (g) W 3 : (g) w wz

3 m ek w w p 389 Table 2. Cnditin f Freeze-thew Test Test Methds Temperature Range Time f Cycle KS F 2456 (Methd B ) 18 C~4 C 3 h 20 min w x t KS F 2456 A (» w, ) B (», w) ƒ x š, x Table 2 B x ³ ww x ƒ» p, p w x v m ek y» w x w. x ƒ 60 mm 90 mm j» m ek m r ƒƒ 3 w KS L 3115 x w, x Shimadzu m x» w. w w ù kü, MPa t w X z p d m ek m w ü» w Rigaku XRD D/MAX- 2500PC w X z w. d e FT-IR(MIDAC M2410-C, MIDAC, USA), Ÿw, (I.S.D. Crp. Mdel 563), 40 C~400 C¾ r ƒ. d ƒ ƒ E bλ d wš, E sλ d w (3) w w. ε s E s E b = » E s E b t. (4) v j e(plank s law) w 4) w. E b C 1 = λ 5 C 2 exp λt» C 1 = [W µm 4 /m 2 ], C 2 = [µm K]. λ 1 λ 2¾ s w T ƒ. (3) (4) 3. š 3.1. w m ek m w XRF(X-Ray Flurescence) Table 3. Table 3 SiO 2ƒ 68 ƒ š Al 2 O 3, K 2 O, Fe 2 O 3, ek z m yƒ ùkû. 3.2.»»œ w w m x w ƒw m» w ù m ü œ (Pre) x w. w œ»ù w, w w, q w m w ³ w. w w 2) m ü w»,, w w w m œ œ ƒ w. m ek m œ y w» w KS L 3114»»œ d w, m»œ 13.8% š ek mƒ 11.8% ùkù ek mƒ ek w m œ y w, ek w m w œ (Pre), q Table 3. Cmpsitin f Clay Sample Result (wt%) Cmpnent calcined clay carburized clay SiO AI 2 O K 2 O Fe 2 O Na MgO TiO CaO P 2 O MnO «7y(2008)

4 김기호 김상명 강병철 390 Relative Dynamic Mdulus f Elasticity by Each Specimen Relative dynamic mdulus specimen weight (kg) 0 cycle 150 cycle 300 cycle calcined clay (1) calcined clay (2) brken brken carburized clay (1) carburized clay (2) carburized clay (3) Table 4. Fig. 1. Relative dynamic mdulus f elasticity by cycle. Fig. 2. 한국세라믹학회지 result acceptable level nrmal fail pass pass pass 80 되는 동파의 문제점을 침탄처리를 통해 어느정도 개선할 수 있을 것으로 판단된다. 동결융해 저항성을 예측하기 위해서는 먼저 동 탄성계 수를 측정하게 되며, 측정 결과는 Table 4에서 보는 것과 같이 침탄 소성점토벽돌이 일반적인 소성점토벽돌보다 우 수한 결과를 나타내었다. 일반적으로 상대 동 탄성계수는 정량적인 판단보다는 양호/불량 등의 정성적인 결과를 판 단하기 위한 것이기 때문에, 단지 표에 나타낸 수치를 그 대로 믿어서는 안 될 것이며 단지, 침탄소성점토가 일반 적인 소성점토와 비교할 때 동등 이상의 동해 저항성을 가지고 있다고 보는 것이 타당할 것으로 사료된다. Fig. 1은 사이클에 따른 상대 동 탄성계수를 계열별로 나타낸 것이다. 아래와 같이, 침탄 소성점토는 상대 동 탄 성계수가 300 사이클 가동 후에 90 이상으로 우수한 결 과를 나타내었으나, 일반 소성점토 2계열 중 한 계열은 실험 중에 손상이 나타났으며, 다른 시편은 손상은 가지 Surface bservatin by cycle.

5 소성 점토의 침탄에 따른 동결융해 저항성 및 적외선 방사특성 연구 Test Result f Cmpressin Strength specimen specimen width (mm) number n= calcined clay n= n= n= carburized clay n= n= Table 5. length (mm) Press (N) , , , , , ,610 않았지만, 침탄 소성점토벽돌 보다 저조한 결과를 나타내 었다. 상대 동 탄성계수 판단기준(80)은 300 사이클 시험 후 의 값이며(규격으로 제정된 값은 아니며, 일반적으로 통 용되는 기준임.), 본 실험에서 정량적인 값을 분석할 수는 없으며, 단지 침탄처리 된 소성점토가 일반 소성 점토보 다 동결융해저항성면에서 약간 우수하다고 판단할 수 있 다. Fig. 2와 같이 동결융해 저항성을 측정하면서, 사이클 에 따른 표면의 변화상을 관찰하였다. 관찰 결과, 침탄처 리 된 소성점토와 일반 소성 점토(1)은 외관 상으로 보기 에 특별한 손상이 발견되지 않았다. 그러나, 일반 소성 점 토(2)는 사진에서 보는 것처럼 파손되어 상대 동 탄성계 수를 측정하지 못하였다. 본 실험을 통해서는 단지, 침탄 처리 된 소성점토의 동결융해저항성이 소성 점토벽돌보 다 약간 우수하다는 정성적인 분석 결과만을 도출하는 것 이 옳을 것이라고 판단된다. 압축강도 압축강도는 재료의 물성 중에 가장 기본적인 특성으로 Table 5에 압축강도 시험결과를 나타내었다 Fig. 3. Cmpressin Strength (MPa) average 압축강도 시험결과를 살펴볼 때 침탄처리 된 소성점토 가 일반 소성점토보다 약 2% 정도 압축강도가 향상된 것 으로 나타났으나, 시험편차를 고려하면 침탄에 의한 압축 강도 상승효과는 미미한 것으로 판단된다. 그러나 일반적으로 건축용 조적재로 많이 사용하는 시 멘트블록의 압축강도가 20 MPa정도 인 것에 비하면 침탄 처리 된 소성점토의 압축강도는 71.3 MPa로 약 3배 정도 강도가 높은 것을 알 수 있다. 현미경 분석 일본 Hitachi사의 TM0 모델의 현미경을 이용하여 가 속전압 15 kv 조건으로 관찰한 소성점토와 침탄 처리된 소성점토의 파단면 사진을 Fig. 3에 나타내고 있다. (a)는 소성점토의 사진으로, 사진에서 볼 수 있듯이 개 개 입자의 단면에 많은 공극을 포함하고 있음을 확인할 수 있었고 이 공극들은 소성점토 제조 시 천연의 점토 원 료에 존재하던 유기물질과 원료 성형 시 점성을 부여하 기 위해 첨가한 수분 등이 소성 시 강열에 의하여 증발 되면서 형성된 것으로 판단되며, 이러한 내부의 공극들은 침탄 처리 과정에서 탄소가 침착되는 장소를 제공하게 된 3.4. Pht f SEM fr clay. (a) calcined (b) carburized. 제 45 권 제 7호(2008)

6 392 ½»yÁ½ Á Fig. 4. X-ray diffractin curves fr clay. (a) calcined (b) carburized.. (b) m ek w q w SEM m w m w œ š e w ƒ. m š œ k ƒ en œ q œ k k w enw ƒ m w û. 1) 3.5. X z m ek m y y w» w XRD Fig. 6 ùkü. Fig. 4 (a) m mullite(3al 2 O 3 2SiO 2 ) ùkùš ù vj Intensityƒ w xk, SiO 2, Al 2 O 3 ùk ùš y w. (b) ek m m š ek w w z vjƒ ùkùš. XRD, ek w ky q, m œ k ƒ enw q. 1) 3.6. p z w» w p w. y j w ù x» w 6,7) - w t gqw w wš. 8,9) Figs. 5, 6 m ek m ƒƒ 80 C, 200 C ƒ w t d w, Fig. 5. IR emittance prperties fr calcined clay measured at 80 C. (a) emissivity, (b) emissive pwer. ùkü, 1.0 wš t 0~1. Fig. 5 (a) 80 C d w m ek m v 4µm~20 µm q m š ek m ù kü ek mƒ µm q ƒ w ùkü 4µm~7 µm q e k m ùkü ùkü m w 3.8%. w Fig. 5 (b) 4µm ~20 µm q 5) v j e (Plank s law) s ùkü š. 4 µm~20 µm q m W/m ek m 647 W/m ùkü ek mƒ 6W ƒ. 80 C m ek m j w wz

7 Fig. 6. IR emittance prperties fr calcined clay measured at 200 C. (a) emissivity, (b) emissive pwer. ƒ. Fig. 6 (a) 200 C d m ek m w v 3~20 µm q m ek m ù kü ek mƒ 3.6%. 7 µm q ƒ w ùkü 4~7 µm q e k m ùkü m w 9.4%. 200 C d w 80 C d w 1.0» 4) ƒ w v j e(plank s law) q s, m ek m q š». w 3µm~20 µm q Fig. 6 (b) ùküš. 3 µm~20 µm q m ek w w p 393 m W/m ek m W/m ùkü ek mƒ 92 W ƒ. 200 C d s ek mƒ 200 C m w z ƒ w š q w. 4. m j œ v w œ» œ» œ w w n k w ek m w ü w w p y w. k w x, ek mƒ e k m w w w y m q x w q.»»œ d m»œ 13.8%, ek m»œ 11.8% ek m œ (Pre)» š q. ek SEM m œ swwš ù ek m k en w w œ š e w y w. m w ek mƒ 2% ek z w ù kû ù, p 3 ƒ y q. w w X-ray z, SiO 2, Al 2 O 3, Fe 2 O 3 š, ek w ky y w, ek m 80 C m w 1% w, 200 C d w m w 3.6% w. w ek z 7µm w q w, m q û ùkù, ek w m k k w q. 80 C m ek mƒ j ù, 200 C ek m ƒ m w y ƒ w š q w. 45«7y(2008)

8 394 ½»yÁ½ Á REFERENCE 1. K. H. Kim and S. M. Kim, Characteristics f Calcined Clay by Carburizatin Methd(in Krean), J. Institute f Surface Engineering, 41 [2] 63-8 (2008). 2. S. G. Yang, The Prperty f Freeze-thaw and the Strength f Recycled Aggregate Cncrete Mixed with Fly Ash(in Krean), pp. 11-3, Master s treatise, Chungbuk University, ChengJu, S. A. Hujiya, The Effect f Heating n Infrared Radiatin(in Jpn.), Painting Technlgy; 3 95 (1990). 4. S. K. Dng, Develpment f Prcess Technlgy fr Lw Pressure Vacuum Carburizing(in Krean), KOSCO Sym., (2004). 5. S. M. Kawaguchi, Infrared Radiating Elements(in Jpn.), Ceramics., (1988). 6. K. Kawamt, Applicatin f Far Infrared Radiatin t the Field f Lighting and Eletr-Heating(in Jpn.), Ceramics., (1988). 7. H. Takashima, Infrared Radiant Ceramics and their Utilizatin(in Jpn.), Ceramics Cmmittee, 10 [7] 373 (1982). 8. Y. Yamamt, K. Makita, K. Kamiya, and S. Sakka, Optical Absrptin f Transitin Element Oxide-Silica Cating Films Prepared by Sl-Gel Methd(in Jpn.), Ceramics Cmmittee., 91 [5] (1983). 9. N. J and J. Arfsten, Nn-cryst, Slid., (1984). w wz

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