1. 서 론 이에 이 연구에서는 TiO 의 저온도포가 가능한 Sl-gel법 으로 TiO 를 제조하였으며(Jng Kyu Kim, 008), 펄라이 트 사용 경량골재콘크리트에 TiO 를 저온도포시켜 고온에서 발생할 수 있는 콘크리트의 균열 및 붕괴 등의 문제점을 해 결하고
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1 ª Œª Œ 1ƒ A Á 011 œ pp. 19 ~ 16 gj p ª Sl-gel ypk(tio ) s k gj p p (CH CHO) p The CH CHO Remval Characteristics f Lightweight Aggregate Cncrete with TiO Spreaded by Lw Temperature Firing using Sl-gel Methd wá Á Á Lee, Seung HanÁYe, In DngÁJung, Yng WkÁJang, Suk S Abstract Recently studies n functinal cncrete with a phtcatalytic material such as TiO have actively been carried ut in rder t remve air pllutants. The absrbtin f TiO frm thse studies is applied by it being directly mixed int cncrete r by suspensin cated n the surface. When it cmes t the effectiveness, the frmer prcess is less than that f the latter cmpared with the TiO use. As a result, the direct cating f TiO n materials' surface is mre used fr effectiveness. The Surface spread f it needs t have a mre than 00 C heat treat dne t stimulate the activatin and adhesin f phtcatalysis. Heat treat cnsequently leads hydratin prducts in cncrete t be dehydrated and shrunk and is the cause f cracking.gthe study prduces TiO used Sl-gel methd which enables it t be cated with a lw temperature treat, applies it t pearlite using Lightweight Aggregate Cncrete fixed with a lw temperature treat and evaluates the spread perfrmance f it. In additin t this, the size f pearlite is divided int tw types: One is.5gmm t 5.0Gmm and the ther is mre than 5.0Gmm fr the benefit f finding ut the remval characteristics f CH CHO whether they are affected by pearlite size, mixing methd and rati with TiO and elapsed time. The result f this experiment shws that althugh TiO prduced by Sl-gel methd is treated with 10 temperature, it maintains a high spread rate n the XRF(X ray Flrescence) quantitative analysis which ranks TiO 8 percent, SiO 9 percent and CaO 18 percent. In the size f perlite frm.5 mm t 5.0 mm, the remval characteristic f CH CHO frm a lw temperature heated Lightweight cncrete appears 0 percent higher when TiO with Sl-gel methd is spreaded n the 7 percent f surface. In ther wrds, the remval rate is 9 percent cmpared with the 7 percent where TiO is mixed in 10 percent surface. In mre than 5.0 mm sized perlite, the remval rate f CH CHO, when TiO is mixed with 10 percent, is 69 percent, which is similar with that f the previus case. It suggests that the size f pearlite has little effects n the remval rate f CH CHO. In terms f Elapsed time, the remval characteristic seems apparent at the early stage, where the average remval rate fr the first 10 hurs takes up 8 percent cmpared with that f 0 hurs. Keywrds : sl-gel methd, lw temperature firing, TiO, lightweight aggregate cncrete, CH CHO» w» w TiO Ÿ w» gj p w ƒ y š. TiO gj p yww ù, xk t sw wš. gj p TiO yww TiO w z t sw. TiO t s Ÿ y y w 00 C š w, gj p y k Á ü ³ j» w. TiO sƒ ƒ w Slgel TiO w r p gj p š yw TiO s sƒw. w r p.5~5.0 mm 5.0 mm w r p, TiO y y CH CHO p mw. x, Sl-gel w TiO 10 C sw XRF TiO 8%, SiO 9%, CaO 18% ùkù TiO s ùkû. w r p.5~5.0 mm TiO sw gj p CH CHO p Sl-gel TiO 7% t sw 9% ùkù 10% y w 7% w 0% ùkû. w r p 5.0 mm TiO 10% eyw yww CH CHO 69% r p.5~5.0 mm w 7% w ùkù r p CH CHO e w j. CH CHO p xr 10 s³ 0 8% ùkù» ùkû. w : Sl-gel,, ypk(tio ), gj p, p (CH CHO) z Á w œ w m œw ( lsh@kmu.ac.kr) w œ w m œw ( yeindng@kmu.ac.kr) z Á Á w x l ( jyw@kmu.ac.kr) w x l ( dhfl1@kmu.ac.kr) 1ƒ A 011 œ 19
2 1. 서 론 이에 이 연구에서는 TiO 의 저온도포가 가능한 Sl-gel법 으로 TiO 를 제조하였으며(Jng Kyu Kim, 008), 펄라이 트 사용 경량골재콘크리트에 TiO 를 저온도포시켜 고온에서 발생할 수 있는 콘크리트의 균열 및 붕괴 등의 문제점을 해 결하고자 하였다. 또한, 휘발성 유기화합물(VOCs)의 대표적 인 물질인 아세트알데히드(Acetaldehyde, 이하 CH CHO 라 약함) 제거 특성을 평가하고자 하였다. 이를 위하여 경량골재콘크리트에 Sl-gel법으로 제조한 TiO 를 저온도포 후 공시체의 화학적 성분 분석을 위하여 XRF 정량분석을 실시하였다. 또한, 경량골재로 사용한 펄라 이트의 입경, TiO 의 혼입방법, 혼입량에 따른 CH CHO 제 거 성능평가를 실시하였다. 최근 정부의 친환경 녹색성장 정책에 따라 건설 산업에서 도 환경부하를 저감시킬 수 있는 콘크리트 제품 개발이 요 구되고 있다. 이러한 요구에 부합하는 기능성 재료 중 하나 가 이산화티탄(이하 TiO 라 약함)을 광촉매 재료로 사용하 여 대기오염물질을 제거할 수 있도록 한 기능성콘크리트이다. 광촉매 재료를 이용한 환경오염물질 처리기술은 TiO 를 코 팅한 재료 표면의 초친수성(super hydrphilicity)이 발견되면 서 기능성 재료의 개발과 콘크리트에의 적용이 활발하게 진 행되어 왔다(A. Fujishima, K. Hnda, 197). 그러나 TiO 단 독으로는 기층 소재의 표면에 강한 내구성을 가질 수 있도 록 흡착시키기 어렵기 때문에 적절한 결합재(Binder)나 코팅 할 수 있는 기술 개발이 필요하다. 일반적으로 TiO 를 콘크리트에 고정화하는 방법은 콘크리 트에 직접 혼합하거나, 현탁액을 표면에 합성, 도포하는 방 법이 있다. 이 중 콘크리트에 TiO 를 직접 혼합하는 방법은 TiO 의 사용량에 비하여 효능이 떨어져 표면에 직접 도포하 는 방법이 많이 이용된다. TiO 의 표면도포는 광촉매의 활성 화와 접착성 증대를 위하여 00 C 이상의 고온 열처리를 실시하고 있다. 그러나 콘크리트의 경우 50~50 C의 고온 에 노출되면 Al O 와 Fe O 를 함유한 수화생성물의 탈수 수축으로 인한 균열이 발생하게 되며, 00~700 C의 고온에 노출되면 Ca(OH) 가 탈수되어 CaO로 변화하게 되고, 수분 이 공급되면 탈수 수축에 의한 내부균열의 원인이 되기도 한다(송종진, 00).. 실험개요 사용재료.1.1 시멘트 시멘트는 분말도,6 cm /g인 보통포틀랜드시멘트를 사 용하였으며, 물리 화학적 성질은 Table 1과 같다..1. 펄라이트 실험에 사용한 펄라이트는 최대 입경 10 mm 미만, 공극 률 90% 내외인 국내 K사 제품으로 화학성분을 Table 에 나타내었으며, 물리적 성질을 Table 에 나타내었다. 펄라이트는 입경에 따른 영향을 검토하기 위하여 체가름을 실시하여.5~5.0 mm 미만과 5.0 mm 이상으로 구분하여.1 Table 1. Chemical cmpsitin and physical prperties f cement Fineness (cm/g) Density (g/cm) Ig.lss, SiO.9 Chemical cmpsitin FeO CaO MgO AlO 5.57 SO 0.61 Basicity - Table. Chemical cmpsitin f perlite Cmpnents Cntent rati(%) SiO 7.8 AlO 1.57 KO.8 NaO.1 CaO 1.0 FeO 0.9 MgO 0.7 Table. Physical prperties f perlite Density (g/cm) Prsity (%) 90 r s Thermal cnductivity (kcal/mhc) 0.0~0.05 Usable temperature (C) -50~1,000 ph Clr 6.5~7.5 Light gray Fig. 1 Pht f perlite particle size 10 大韓土木學會論文集
3 Table 6. Experiment plan Table. Chemical prperties f using reagent Mlecular Purity(%) Menufacturer frmula 97.0 Fluka Tetrabutyl rthtitanate C16H6OTi 99.0 ALDRICH Diethanlamine CH11NO 99.0 DUKSAN Ethyl alchl CH5OH Cmpnents Series Pe.5-T 0주 1 Mlecular frmula TiO Mlecular weight Crystal frm Anatase Clr white 1) Pe.5-T15.0 Pe.5-T110 Pe.5-T.5 Pe.5-T7.0 Pe5.0-T10 0Pe5.0-T110 Table 5. Physical prperties f TiO(Anatase) Density (g/cm).8~.6 Perlite particle(mm).5~5 Mre than 5 TiO Mixed methd Mixed weight 0 Mixture Cating Mixture 10 사용하였다. Fig. 1에 펄라이트의 입경에 따른 전경을 나타 내었다..1. 이산화티탄(TiO ) 이 연구에서는 TiO 의 저온도포를 위하여 Sl-gel법으로 TiO 를 제조하였다. TiO 제조에 사용된 시약은 Tetrabutyl rthtitanate, Diethanlamine 및 Ethyl alchl로 사용 시약 의 화학적 성질을 Table 에 나타내었다. Table 의 시약을 사용하여 Sl-gel법으로 TiO 를 제조하 였으며, 제조된 TiO 와 펄라이트로 제조된 경량골재콘크리트 를 10 C에서 저온 도포하여 CH CHO 제거 특성을 검토하 였다. 또한 저온도포할 때의 TiO 도포성능 및 광촉매 효과 를 비교 검토하기 위하여 국내 D사의 Chride methd로 제조된 Anatase형 TiO 를 사용하였으며, 사용 TiO 의 물리 적 특성은 Table 5와 같다.. 실험계획 및 방법 실험계획 경량골재콘크리트를 제조할 때 사용한 펄라이트의 입경변 화, TiO 의 혼입방법, 혼입량에 따른 CH CHO의 제거 성 능을 검토하기 위한 것으로 이를 위한 실험계획은 Table 6 과 같다. TiO 를 혼합할 때의 CH CHO 제거 특성을 검토 하기 위한 TiO 량은 단위시멘트량에 0, 5, 10%의 비율로 혼합하였으며, Sl-gel법으로 제조한 TiO 의 사용량은 단위 시멘트량에 0,.5, 7% 사용하였다. Sl-gel법으로 제조한 TiO 의 사용량은 몰(Ml)비를 변화시켜 몰비에 따라 생성 되는 TiO 고형물의 양을 단위시멘트량에 대한 비율로 환산 한 것이다. 펄라이트를 사용한 경량골재콘크리트의 제조는 프리웨팅 (Pre-wetting)한 펄라이트를 시멘트와 0초간 건비빔하고, 혼 합수를 투입하여 60초간 혼합하여 φ 및 mm시편을 제작하였다. 펄라이트를 사용하여 제작된 경량골 재콘크리트를 Fig. 에 나타내었다..1 실험방법..1 시멘트페이스트의 유동성 경량골재콘크리트를 제조할 때 시멘트 페이스트의 유동성 평가는 KS F 주입모르타르의 컨시스턴시 시험방법 에 준하여 실시하였으며, 사용 페이스트의 유동성 기준은 18± sec로 하였다... XRF 분석 Sl-gel법으로 제조한 TiO 의 표면도포 성능을 알아보기 위하여 X-Ray Flurescence Spectrmeter(XRF) 분석을 실 시하였다. XRF 분석을 위해 완전히 건조된 공시체의 표면 에서 시료를 채취하여 Disk mill로 분쇄한 후 전량이 00 µm체를 통과한 미립분 시료를 사용하였다... 광촉매 성능평가 CH CHO 제거성능 평가 시험은 한국광촉매협회 광촉매 성능평가 시험방법-가스백 B법 에 준하여 실시하였다.. Fig. A tester f phtcatalyst perfrmance Fig. Prductin f lightweight aggregate cncrete specimens 第1卷 第A號 011年 月 11
4 CH CHO 표준가스를 사용한 광촉매 성능평가 시험기 전경 을 Fig. 에 나타내었다. 일반적으로 광촉매 성능평가 시험방법-가스백 B법 에서 는 시험편의 흡착평형 조건인 초기농도와 암조건용 시험농 도를 구하여 그 값이 시험 성립조건을 만족하여야 한다. 이 연구에서는 광촉매 성능평가 시험의 유효성 판단을 위하여 다음의 성립조건을 검토하였다. ① 양조건 시험농도 개가 모두 초기농도 의 80% 이 상일 것 ② 초기농도 개를 식 (1)에 따라 계산하여 그 값이 0.5 이하일 것 최고초기농도 초기농도 (1) 산술평균값. 실험결과 및 분석 이 연구에서는 펄라이트를 사용한 경량골재콘크리트에 Sl제조한 TiO 를 저온 도포시켜 CH CHO 제거 특 성을 평가하고자 하였다. 이를 위하여 경량골재콘크리트에 Sl-gel법을 이용하여 TiO 를 제조하였으며, 제조된 TiO 를 표면 도포시킨 공시체의 XRF 정량분석을 실시하여 TiO 도 포성능을 평가하였다. 또한, TiO 의 혼입방법 및 혼입량의 변화에 따른 CH CHO 제거 성능평가를 실시하였다. gel법으로 법에 의한 TiO.1 Sl-gel 제조 및 10 C 저온 도포 고 이 때의 몰(Ml)비는 C H O Ti:C H NO :H O:C H OH =1:::5.6이 된다. Sl-gel법에 의해 제조된 TiO 의 표면 도포 과정을 Fig. 5에 나타내었다. Sl-gel법에 의해 제조된 TiO 의 표면도포는 Fig. 5와 같 이 Gel과 공시체를 초음파진동기(Ultra Snic)에 침지시켜 완전히 응고시킨 후 응고된 공시체를 10 C 오븐에서 시간 저온소성시키면 콘크리트의 공시체 표면에 얇은 막을 가진 TiO 가 코팅되게 된다. TiO 의 도포성능을 평가하기 위하여 일반 경량골재콘크리트와 Sl-gel법으로 제조한 TiO 가 표면 도포된 경량골재콘크리트의 표면시료를 채취하여 XRF 정량 Sl-gel법에 의한 TiO 제작 전경을 Fig. 에 나타내었다. Sl-gel법으로 TiO 를 제조하기 위한 출발물질로는 Tetrabutyl rthtitanate(c H O Ti)를 사용하였다. C H O Ti 8.51 ml와 Diethanlamine(C H NO ).6 ml를 교반기에서 5분간 교반 후 Ethyl alchl(c H OH) 6.8 ml를 첨가하여 약 시간동안 교반 후 증류수(H O) 0.9 ml와 C H OH 10 ml를 추가로 첨 가하면 안정한 Gel 상태가 된다. 이러한 반응을 가수분해라 하 16 Fig. 5 The flwchart f TiO cating by Sl-gel methd Fig. TiO prduct by Sl-gel methd Fig. 6 The flwchart f TiO cating by Sl-gel methd 1 大韓土木學會論文集
5 Table 7. Chemical cmpsitin f materials Cmpnents Chemical cmpsitin Materials Cement Perlite Pe.5T 1-0 Pe.5T -7.0 SiO Al O Fe O CaO MgO TiO Other Fig. 7 Chemical cmpsitin f materials w. Fig. 6 TiO sw gj p TiO 10 C sw gj p XRF ùkü. TiO sw gj p SiO 7%, CaO 9%, Al O 1% ùkû. Sl-gel w TiO sw gj p TiO 8%, SiO 9%, CaO 18%, Al O 7% ùkù TiO t s. XRF k p, r p, gj p, Sl-gel w TiO ƒ t s gj p yw Table 7 ù kü š, yw Fig. 7 ùkü. Fig. 7 Cement z(cao) 6.05%, Fig. 8 Cntent rait f TiO (%) with time lapse e(sio ).9%, ù(al O ) 5.57%ƒ š y (Fe O ) (MgO) w wš ùkû, r p SiO 7.8% wš ùkû. Pe.5T 1-0 SiO 6.6%, CaO 8.69% p r p yw gj p. TiO 7% sw Pe.5T -7.0 TiO w 8% ƒ ùkû. TiO ƒ t s gj p TiO w y» w XRF w. Sl-gel w TiO ƒ 7% t s Pe.5T -7.0 œ 1, 1, 1, z t w XRF w TiO w Fig. 8 ùkü. Fig. 8 Sl-gel TiO t sw TiO y XRF w 1 8.1%, 1 z 8.1%, 1 z 7.87%, z 7.59% ùkû. Sl-gel w TiO 10 C s TiO t s 8% ùkû TiO w y t s z y 0.5% ùkû. Sl-gel TiO gj p sw t s š, yƒ ùkù Ÿ l Series Table 8. Results f experiment Dark cnditin CH CHO cncentratin(ppm) Intial cncentratin Dark cnditin test cncentratin Cncentratin (%) Cnditin Cncentratin (%) Cnditin 1 (%) Light cnditin remval efficiency(%) 5 hr. 10 hr. 15 hr. 0 hr. Pe.5T Pe.5T Pe.5T Pe.5T Pe.5T Pe5.0T Pe5.0T ƒ A 011 œ 1
6 y j Ÿ z xw q.. CH CHO p TiO y w gj p CH CHO sƒw» w gj p w TiO 0, 5, 10% yww Sl-gel TiO 0,.5, 7.0% sw TiO y CH CHO sƒw. œ CH CHO Table 8 ùkü. Table 8 xr sx» x r» w x ƒ 9.75% 95.1% 80% ùk û,» 0.5 w ùkù x w ùkû...1 CH CHO p Fig. 9 UV-A q ƒ 0W Black Light Lamp xr š 0 CH CHO y d w CH CHO p ùk ü. Fig. 9 CH CHO TiO y, y, r p 10 ¾ ƒw ƒ 10 z ƒs j ùkû. ƒ Pe.5T %, 10 79% x 0 9% 8%ƒ 10 ü û. w ƒ û Pe5.0T % 10 1% 85% ùkû. xr 10 s³ 0 8% ùkù» ùkû. ù xr CH CHO w w, x s» CH CHO ƒ 90 ppm w w... TiO y CH CHO p TiO y CH CHO p mw» w gj p w TiO yww Sl-gel w t s y g. gj p TiO p 0, 5, 10% eyw yww CH CHO p Fig. 10 ùkü. Fig. 10 TiO y w Pe.5T CH CHO 0% ùkû. TiO yww xr CH CHO ùkù r p x w œ w z» w q., TiO 5% y w Pe.5T 1-5 %, TiO 10% y w Pe.5T % ùkù CH CHO Pe.5T 1-0 w Pe.5T 1-5 1%, Pe.5T % ƒw ùkû. Sl-gel TiO gj p t 10 C sw CH CHO p Fig. 11 ùkü. Fig. 10 Remval efficiency f CH CHO with TiO mixing Fig. 9 Remval efficiency f CH CHO with time Fig. 11 Remval efficiency f CH CHO with TiO cating 1 ª Œª Œ
7 Fig. 1 Remval efficiency f CH CHO with perlite particle Fig. 11 TiO t sw CH CHO Pe.5T %, Pe.5T % ùk ù Pe.5T -0 w Pe.5T -.5 0% ùk û, Pe.5T % ùkû. w Pe.5T -7.0 TiO 10% y w Pe.5T % % ùkù TiO t sw ƒ gj p w y w eyw CH CHO ùkû. Ÿ Ÿ y j gj p ü w TiO y ù»., Sl-gel TiO t sw gj p š s ³ ü w q, TiO CH CHO q... r p CH CHO p gj p CH CHO p mw» w r p.5~5.0 mm 5 mm y g CH CHO mw, Fig. 1 r p TiO y CH CHO p ùkü. Fig. 1 r p y 0 CH CHO TiO y r p.5~5.0 mm Pe.5T 1-0 Pe.5T 1-10 r p 5 mm Pe5.0T 1-0 Pe5.0T 1-10 % ùkû. r p CH CHO ùkù r p t Ÿ š, Ÿ y ùkù CH CHO ùkù q. 5. Sl-gel w TiO gj p 10 C s g {»yw (VOCs) t CH CHO p sƒw. 1. Sl-gel w TiO 10 C sw XRF TiO 8%, SiO 9%, CaO 18% ùkù Sl-gel w TiO sƒ ƒ w.. CH CHO p TiO y, y, r p 10 s³ 0 8% ùkù» ùkû.. TiO gj p t sw CH CHO Pe.5T %, Pe.5T % ùkù Pe.5T -0 w Pe.5T -.5 0% ùkû, Pe.5T % ùkû. w Sl-gel sw Pe.5T -7.0 TiO 10% y w Pe.5T % % ùkù TiO t sw ƒ gj p w y w TiO CH CHO ùkû.. r p y 0 CH CHO TiO y r p.5~5.0 mm Pe.5T 1-0 Pe.5T 1-10 r p 5 mm Pe5.0T 1-0 Pe5.0T 1-10 t ƒ % ùkû. ƒ w» (KREONET) y w ww w w» (KISTI) w ¾. š x ½ z, û»(007) y» x w gj p» w, w wz z wz, w wz, Vl. 9, N., pp. 7-. ½ (000) Ÿ,. (00) y gj p w w, w, w w, p. 15. y (008) z Ÿ l w s, wm wz, wm wz, 9«5By, pp ,,, x, ½y (00) ypk(tio ) Ÿ w p k y (Nx) p w», ª ª Œ -, w wz, Vl. 18, N. 8, pp w Ÿ xz(005) Ÿ sƒ x -ƒ B. : x, ½z, û»(006) ypk Ÿ w l y p w». ª ª Œ -, w wz, Vl., N. 11, pp Fujishima, A. and Hnda, K. (197) Electrchernical phtlysis f water at A semicnductr electrde[j]. NATURE, 558(), 7. Kim, J.K. (008) Remval f Pharmaceuticals and Persnal Prd- 1ƒ A 011 œ 15
8 ucts frm Water using Phtcatalysis and Adsrptin Prcess. Thesis f Mphil, University Cllege Lndn, Lndn. Chitharanjan, N. and Sundararajan, R., and Manharan, P.D. (1988) a new lightweight high strength material, The Internatinal Jurnal f Cement Cmpsites and Lightweight Cncrete. Develpment f Aercrete. Carp, O. Huisman, C.L., and Reller, A. (00) Phtinduced reactivity f titanium dixide, Prgress in Slid State Chemistry, Nv. (000) swytkÿ Žrs Š. swytá ryrxžt. š œ (1998) Œ(NOx) jryrxžt. ry rxžt ª. (1998) j «j Ÿvxtrl. uwytá ryrxžt. ˆ (1996) tty l igœ. ž. ( : / : / : ) 16 ª Œª Œ
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