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1 Journal of the Korean Ceramic Society Vol., No. 11, pp. 633~638, 007. Resistance of Alkali Activated Slag Cement Mortar to Sulfuric Acid Attack Kyung-San Min, Seung-Heun Lee Department of Material Science & Engineering, Kunsan National University, Kunsan , Korea (Received August 18, 007; Accepted October 30, 007) e y y p k üy Á x w œw œ ( ; ) ABSTRACT The setting time of alkali activated slag cement tends to be much faster than ordinary Portland cement, and its compressive strength had been higher from the 1 day but became lower than that of the cement on the 8 days. According to the results of the surface observation, weight loss, compressed strength, and erosion depth tests on the sulphuric acid solution. It has been drawn that alkali activated slag cement has a higher sulphate resistance than ordinary Portland cement, and in particular, the alkali activated slag cement added 5 wt% alumina cement has little deterioration on the sulphuric acid solution. The reason why the alkali activated slag cement has higher sulphate resistance than other hardened cement pastes is that it has no Ca(OH)greactive to sulphate ion, and there is little CaSO H O production causing volume expansion, unlike other pastes. And it is supposed that Al(OH) 3 hydrates with high sulphate resistance, which is produced by adding the alumina cement increases the sulfate resistance. Key words : Alkali activated slag cement, Sulphate resistance, Alumina cement, Cement sp pƒ z, p šd,,, w z š. ù y w z w w p» gj p w y x ƒ w š. gj p 1) š ù yy y yw wš w y š, gj p w ƒ w š y j x ü wš. ) w w kƒ œ w w yƒ w ƒ. w ù w w y w p y e š. ) ü w 0-30 Corresponding author : Seung-Heun Lee shlee@kunsan.ac.kr Tel : Fax : yx ƒ» w z š. w w pƒ x š. 3-6) š w e ƒw w e y y p e š, w w, w, ù t y w, üyw, w p š š. 7,8) w sp p w { w w š ƒƒe š w w. e y y p m s p p w ü e w w š š. 5,6) š w ü p e y y k š k ü w mw..1.. x 633
2 63 Á x Table 1. Chemical and Physical Properties of Raw Material Item Oxide composition (%) Setting time Blaine Specific Initial Final (g/cm ) gravity Type SiO Al O 3 Fe O 3 CaO MgO SO 3 TiO (min) (hr:min) Ordinary portland cement : 0 6: Blast furnace slag : Alumina cement : Table. Mix Proportions of Specimen Blast furnace slag Alumina cement Ordinary portland cement Activator Binder/Sand Alkali activated slag % 1: Alkali activated slag with alumina cement Ordinary portland cement :.5 š Ÿ š w Blaine t 5,000 cm /g w, w š.91 g/cm 3. e y y p» p»(3 :5MPa) w L ù p 5wt% ey ƒw ü w. w e y y p ü w» w m sp p S w. x w yw Table 1 t w. e y y NaOH 3y 15 wt% ƒw w... x Table ƒ r w ùkþ. KS L 510 e(vicat) e w, k KS L 5105 x w xw 1, 3, 7, 8 d w. üy x k xr( w / =1/, e y y w 0.55) 5wt% y 7, 8, 56, 91 e k z, e y, r y, e ¾ d w. m sp p r e e w t w z d w. sy w x» w syw w z d w. e ¾ r w w z 50 wt% r vk w yƒ œ¾ w. 50 wt% r vk k r vk 50 wt% ƒw w. ƒ r X z»(macscience Co. Japan) w d w. r e k w wš w ú e w. d Cu target w 0 kv, 100 ma 5-60 o¾ o /min d w. 3. š 3.1. e y y p» p e y y Table 1 m sp p w š, 1 ü wš, 30 ü p w p ƒ š. ù p 5wt% ƒw w ùkþ ù 15. ù p sp p ƒ ù, ù p y m sp p 1 wš,» y x 9) Al(OH) 3ƒ w ƒ. Fig. 1 e y y k ùkþ. e y y p 1 l m sp p ù p 5wt% ƒw 0 MPa ùküš, ƒw w ùkþ. ù p p sp p w x yww z 6-1 sp p 8 w z ƒ ùkù. 8 9) w wz
3 알칼리 활성화 슬래그 시멘트 모르타르의 내황산성 635 르의 XRD분석 결과이다. 주된 반응생성물은 Ca/Si비가 낮은 C-S-H(I)과 Hydrotalcite가 생성되었다. 재령기간이 길 어질수록 피크는 성장하는 경향을 나타내고 있다. 석영은 모르타르 제조 시 사용한 모래의 피크가 검출된 것으로 생각된다. 알칼리 활성화 슬래그의 내황산성 Fig. 3은 8일 수중 양생시킨 모르타르 시편을 5 wt% 황산수용액에 56일간 침지 시킨 후 시편 외관을 관찰한 사진이다. 보통 포틀랜드 시멘트 시편의 경우 침식 된 표 면에 침적된 하얀 용출물이 관찰 되었고, 침지 시간이 길 어짐에 따라 계속적인 시편의 열화에 의해 하얀 용출물 의 양이 많아지고 용액 속으로 떨어져 나가는 현상이 관 찰하였다. 알칼리 활성화 슬래그 모르타르의 경우 표면에 서 보통 포틀랜드 시멘트 시편과 같이 침식에 의한 하얀 용출물은 생성되지 않았으나, 표면이 약간 침식되는 열화 현상이 발생하였다. 침지시간이 경과함에 따라 시편 표면, 특히 모서리 부분에서의 열화현상이 강하게 발생하였다. 그러나 알루미나 시멘트를 5 wt% 첨가한 슬래그 모르타 르는 외관상의 변화가 거의 없었다. 알루미나 시멘트는 내황산염 포틀랜드 시멘트, 고로 시멘트 보다도 강한 화 학적인 저항성을 가지고 있는 것으로 보고되고 있다. 보 통 포틀랜드 시멘트 경화체는 불안정한 수화물인 Ca(OH) 를 함유하고 있으나, 알루미나 시멘트 경화체는 안정한 수화물인 Al(OH) 를 함유하고 있기 때문에 이러한 결과 가 나타난 것으로 추측할 수 있다. Fig. 는 시편의 종류에 따른 침지 날짜별 중량 감소율 을 나타낸 그림이다. 시편은 표면의 물기만을 제거하고 3.. Fig. 1. Compressive strength of alkali activated slag mortar: (a) alkali activated slag with alumina cement, (b) ordinary portland cement, and (c) alkali activated slag cement. 강도에서는 보통 포틀랜드 시멘트의 강도가 알칼리 활성 화 슬래그 시멘트의 강도를 추월하였다. 이것은 초기에 급격하게 진행된 슬래그의 수화반응에 의해 치밀하게 생 성된 수화물이 슬래그의 입자 주위를 피복하고 있어 7 일 이후의 수화반응 진행이 어렵기 때문으로 생각된다. Fig. 는 알칼리 활성화 슬래그 모르타르 및 알루미나 시멘트를 5 wt%를 첨가한 알칼리 활성화 슬래그 모르타 6) Fig.. 9) 3 9) X-ray diffraction patterns of hydrated products in alkali activated slag cement systems: (a) alkali activated slag cement, (b) alkali activated slag cement with alumina cement. 제 권 제 11호(007)
4 민경산이승헌 636 Fig. 3. Mortar specimens exposed to sulphuric acid solution for 56 days: (a) ordinary portland cement, (b) alkali activated slag cement, and (c) alkali activated slag with alumina cement. 중량을 측정하였고, 보통 포틀랜드 시편은 표면침식에 의 해 발생한 하얀 용출물을 흐르는 증류수를 이용하여 제 거하고 물기를 건조 후 중량을 측정하였다. 보통 포틀랜 드 시편은 시간이 경과됨에 따라 계속적인 침식과 하얀 용출물의 생성이 진행되어 계속적인 중량 감소를 보여 91 일에서 30 wt%의 중량 감소율을 보였다. 91일 경과된 보 통 포틀랜드 시멘트 모르타르에서 채취한 하얀 용출물의 XRD분석 결과를 Fig. 5에 나타냈다. 동정된 상은 석영, 이수석고, 에트링쟈이트, C-S-H로 나타났다. 석영은 모르 타르에 함유된 모래에서 기인된 것이고, C-S-H는 시멘트 수화의 결과로 나타난 상이다. 황산염의 침식에 의해 생 성된 상은 이수석고와 에트링쟈이트로 다음과 같은 기구 에 의해서 황산염에 의한 침식이 발생하여 하얀 용출물 이 박리되어 나온 것으로 생각된다. 즉, 시멘트 경화체 내 부로 SO 이온이 확산하고 시멘트의 수화에 의해 발생 Fig.. Weight loss of mortar specimens exposed to sulphuric acid solution: (a) alkali activated slag cement, (b) alkali activated slag with alumina cement, and (c) ordinary portland cement. 한국세라믹학회지 한 Ca(OH) 와 반응하여 CaSO H O를 생성함으로써 부 피팽창을 일으켜 용출된다. 또한 생성한 CaSO H O가 시멘트 수화물인 C A CaSO 1H O(모노설페이트)와 반 응하여 C A 3CaSO 3H O(에트링쟈이트)를 생성하여 팽 창파괴를 유발한다. 반면 알칼리 활성화 슬래그 모르타르는 중량의 증가를 보였다. 이것은 슬래그의 내부 속으로 침투한 황산이온, 수산이온과 슬래그 중의 칼슘과 결합하여 이수석고를 생 성하고 포틀랜드 시멘트 경화체와 다르게 용출되지 않고 내부에 존재하기 때문인 것으로 생각된다. 알루미나 시멘트를 첨가한 알칼리 활성화 시편은 무첨 가 시편보다 낮은 중량 증가율을 보였다. 원인으로는 알 루미나 시멘트의 수화로 경화체가 치밀하게 되어 황산이 온과 수산이온의 침투가 어렵기 때문으로 추측된다. Fig. 6은 황산용액 침지 후의 모르타르 압축강도 측정 결과이다. 압축강도 측정은 ASTM C 67-97의 Test Me 3 3 3) Fig. 5. Elution product from ordinary portland cement mortar exposed to sulphuric acid solution for 91 days.
5 e y y p k üy 637 Fig. 6. Compressive strength of mortar specimens exposed to sulphuric acid solution: (a) alkali activated slag with alumina cement, (b) alkali activated slag cement, and (c) ordinary portland cement. thod B w w. y w e 10) r d w š w d w. x» j d r syw w y w e r, t w e sy w w. td wš ù, w k syw w z d w. r e w. p m sp p r y w e w»œ ³ w w ùkþ. e y y k w m sp p k w x, ù p ƒw { ùkþ. Fig. 7 k 5wt% y e z t l e ¾ d w. e r w z 50 wt% r vk w ph ƒ 9 wš, phƒ 9 w yƒ, yƒ œ y w e w. m sp r, e w r vk x w š x r ¼ x z e w w r ¼ e ¾ d w. m sp Fig. 7. Evolution of ph in mortar specimens exposed to the sulphuric acid solution (depth of ph below 9): (a) ordinary portland cement, (b) alkali activated slag cement, and (c) alkali activated slag with alumina cement. r e w y en ¾ ƒ ƒw w ù, e y y k 8 z y enƒ š, t l mm ¾ y enƒ ù ùkû. wr ù p 5wt% ƒw k 7 z l Fig. 8. XRD patterns of alkali activated slag cement mortar exposed to sulfuric acid solution: (a) 91 days, (b) 56 days, and (c) 8 days. «11y(007)
6 638 Á x y enƒ š, t l 1mm ¾ y enƒ w. Fig. 8 e y y k 5wt% y» e k z y t e w XRD., C-S-H, š, p p,» š C-S-H y w. y e w š p p e š v j ƒw w ùkþ ù, p p vj w w ùkþ. e y y y w y w w e y w š w» w d. ù e y y m sp p Ca(OH) w wš, t yƒ wš šƒ. ù p 5wt% eyw e k e t XRD w ùkþ ù, t yx w.. š e y y k k w y w ü y sƒw. 1. e y y m sp p w, 1 l m sp p ù 8 m sp p û ùkþ.. e y y y w t, y,, e ¾ xw m sp p w üy w ùk û, p ù p 5wt% ƒw e y y y w yƒ. 3. e y y y w w m sp p y w y w Ca(OH) ƒ w vq w š». ù p ƒ ü y Al(OH) 3 üy ƒ. REFERENCES 1. H. M. Song, H. K. Hwang, and J. I. Choa, Properties of Concrete Pipe by Biochemical Corrosion and Performance Deterioration in Domestic, J. Kor. Concrete Institute., 18 [] 16-1 (006).. W. J. Lee, The Corrosion Appearance of Mortar by The Sulfuric Acid, J. Kor. Concrete Institute., 3-8 (00). 3. T. Bakharev, J. G. Sanjayan, and Y.-B. Cheng, Resistance of Alkali Activated Slag Concrete to Carbonation, Cement and Concrete Research., (001).. T. Bakharev, Resistance of Geopolymer Materials to Acid Attack, Cement and Concrete Research., (005). 5. T. Bakharev, J. G. Sanjayan, and Y.-B. Cheng, Sulfate Attack on Alkali Activated Slag Concrete, Cement and Concrete Research., (00). 6. T. Bakharev, J. G. Sanjayan, and Y.-B. Cheng, Resistance of Alkali Activated Slag Concrete to Acid Attack, Cement and Concrete Research., (003). 7. D. Krizan and B. Zivanovic, Effects of Dosage and Modulus of Water Glass on Early Hydration of Alkali Slag Cement, Cement and Concrete Research, (00). 8. C. T. Song and M. Daimon, Hydration of Granulated Blast Furnace Slag in the Presence of NaOH(in Korean), J. Kor. Ceram. Soc., 17 [3] 61-6 (1980). 9. S. Nagaoka, Sulphate Resisting and Heat Resisting Cement, Cement and Concrete, (1991). 10. Standard Test Methods for Chemical Resistance of Mortars, Grouts, and Monolithic Surfacings and Polymer Concretes, C w wz
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