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Available online at www.sciencedirect.com Solar Energy 82 (2008) 206–211 www.elsevier.com/locate/solener Photocatalysis

Available online at www.sciencedirect.com

Available online at www.sciencedirect.com Solar Energy 82 (2008) 206–211 www.elsevier.com/locate/solener Photocatalysis

Solar Energy 82 (2008) 206–211

at www.sciencedirect.com Solar Energy 82 (2008) 206–211 www.elsevier.com/locate/solener Photocatalysis of

www.elsevier.com/locate/solener

Photocatalysis of 4-chlorophenol mediated by TiO 2 fixed to concrete surfaces

Michael J. Watts 1 , Adrienne T. Cooper *

Department of Civil and Environmental Engineering, University of South Carolina, 300 S. Main Street, Columbia, SC 29208, United States Department of Civil and Environmental Engineering, Temple University, 1947 North 12th Street, Philadelphia, PA 19122, United States

Received 3 March 2006; received in revised form 3 March 2006; accepted 1 August 2007 Available online 29 August 2007

Communicated by: Associate Editor Dr. Gion Calzaferri

Abstract

Titanium dioxide (TiO 2 ) powder was mixed with varying concrete sealer formulations and applied to prepared concrete surfaces within PVC batch reactors. A solution of 4-chlorophenol in de-ionized water, with an initial 4-chlorophenol concentration of 4 mg/L, was added to each open reactor. The photocatalytic efficiency of each TiO 2 -sealer was determined through bulk solution sampling while a reactor was exposed to continuous UV light. Through analysis of mean 4-chlorophenol concentrations, the disappearance of 4-chloro- phenol from solution was attributed solely to the presence of TiO 2 in the sealed concrete surface of a UV exposed reactor. The rate of disappearance increased when the mass percent of TiO 2 in the sealer was increased. The zero-order reaction rate constants ranged from 0.135 to 0.2873 mg L 1 h 1 . 2007 Elsevier Ltd. All rights reserved.

Keywords: Oxidation of organic pollutants; Photocatalytic efficiency

1. Introduction

As a method for oxidation of critical water-borne organic pollutants, heterogeneous photocatalysis with tita- nium dioxide (TiO 2 ) has been widely researched ( Teichner and Formenti, 1985; Sakata, 1989 ). Japanese researchers were the first to explore the use of self-cleaning TiO 2 sur- faces and surface coatings ( Nakajima et al., 2000 ). Self- cleaning pavements have also been explored (Murata et al., 1999 ). These self-cleaning pavements were a combi- nation of TiO 2 and a cement mortar that formed a paving

* Corresponding author. Address: Department of Civil and Environ- mental Engineering, Temple University, 1947 North 12th Street, Phila-

delphia, PA 19122, United States. Tel.: +1 215 204 7802; fax: +1 215 204

4696.

E-mail address: acooper@temple.edu (A.T. Cooper). 1 Present address: Duke University, Department of Civil and Environ-

mental Engineering, Durham, NC 27708, United States.

0038-092X/$ - see front matter 2007 Elsevier Ltd. All rights reserved.

doi:10.1016/j.solener.2007.08.001

block with a surface layer capable of removing NO x gases from the surrounding air. Jones and Watts (1997) demonstrated the dry-phase photodegradation of the hydrocarbon, 2,4,6-tri-chlorophe- nol (TCP) loaded on the surface of dry TiO 2 . As a potential pavement border, TiO 2 immobilized in both a paint base and concrete sealer, and applied to glass plates, has been an effective catalyst for the photodegradation of dry-phase hexadecane and anthracene, hydrocarbons commonly found in nonpoint highway runoff (Jones et al., 1998 ). However, a storm event will produce dilute solutions con- taining an array of dissolved organics deposited on con- crete surfaces. To our knowledge, no efforts have been reported in the literature on the aqueous-phase degrada- tion of a model hydrocarbon for environmentally exposed surfaces. The use of nonporous glass as a substrate, how- ever, does not make full use of the benefits derived from silane and siloxane sealers for TiO 2 immobilization. These sealers make a concrete surface impermeable by filling

M.J. Watts, A.T. Cooper / Solar Energy 82 (2008) 206–211

207

available pore space, leaving the thinnest possible surface film relative to the volume of pores. The research reported in this paper explores the effectiveness of TiO 2 immobilized in concrete sealers for catalyzing the photodegradation of 4-chlorophenol (4CP) in aqueous solution. In addition, this paper compares three formulations of concrete sealer (water-based tri-siloxane, solvent-based tri-silane, and solvent-based tri-siloxane). Both the tri-silane and tri-siloxane are chemically bonded to the surface of the concrete through hydrolysis reactions influenced by the moisture present in the concrete sub- strate. An advantage unique to concrete sealers (as opposed to other potential TiO 2 -fixants that can adhere to Portland cement concrete (PCC) surfaces) is that once adhered to a concrete surface, the sealer does not form an impenetrable physical barrier, but instead creates a hydrophobic surface layer by filling all available pores and imperfections in the cured concrete surface ( Bush, 1998 ). Tri-silane and tri-siloxane penetrating sealers can be applied to parking structures, bridge decks, piers and pilings, bridge seats, commercial buildings and warehouses, and any other precast or poured concrete structures. The biodegradation of herbicides in the environment can lead to the release of chlorophenols ( Czaplicka, 2004 ). In a 1986 survey of Canadian surface waters, con- centrations of chlorophenols ranged from 2 to 2000 ng/L, with 4-chlorophenol (4CP), 2,4-di-chlorophenol, and 2,4,6-tri-chlorophenol among the detected species (Czapli- cka, 2004 ). Chlorophenols are a class of chlorinated organic compounds that are environmentally persistent and can have adverse human health effects. Chlorophenols have been detected globally in soils, surface and ground waters, sediments, and air. Oxidation processes for removing chlorophenols from contaminated soil, water, and air include photolysis, hydrogen peroxide plus ultraviolet (H 2 O 2 + UV), Fenton and photo-Fenton reagents, ozonation, photo-ozonation, ozonation plus catalysis, and heterogeneous photocatalysis ( Pera-Titus et al., 2004 ). Recent studies have shown the potential for photodegradation of 4CP in aqueous solu- tions in reactors containing nano-sized particles of TiO 2 (either immobilized in a thin-film or as a colloidal suspen- sion) activated by near UV light (Stafford et al., 1997; Chang et al., 2000; Hitchman and Tian, 2002; Pandiyan et al., 2002; Kim et al., 2003 ). Because of their resistance to biological degradation and toxicity to aquatic organ- isms, chlorophenols, as well as other hydrocarbons, are deserving of the attention. The simplified reaction that describes the photooxidation of 4CP mediated by TiO 2 can be represented by Eq. (1)

ClC 6 H 4 OH þ 13

2

O 2

h m P3: 2 eV

!

TiO 2

6CO 2 þ 2H 2 O þ HCl

ð1 Þ

The selection of 4CP as the model hydrocarbon in this study was due to its environmental significance, ease of analysis, and its relative solubility in water (when compared to other

chlorinated-phenols). From 1 to 5 g/100 ml are soluble in water. This research explores the fixation of TiO 2 to con- crete surfaces with silane and siloxane concrete sealers to prevent further transport of aqueous-phase nonpoint source pollutants. Bench-scale experiments were performed to demonstrate the photodegradation of aqueous 4CP on TiO 2 -sealer-coated concrete surfaces. The application of a TiO 2 -sealer mixture on the surfaces of existing structures could make them photocatalytically-active; this working in tandem with photocatalytic masonry blocks used in any new construction could reduce contamination of water resources by nonpoint source pollutants.

2. Experimental

2.1. Materials

The TiO 2 used throughout was Degussa P-25. The Port- land cement concrete (PCC) supports for the TiO 2 -con- crete-sealer coating were mixed using a sand-cement batch (Setcrete Inc., Gilbert, SC). The three concrete seal- ers, a water-based tri-siloxane (TK-290 WB), a solvent- based tri-siloxane (TK-290), and a solvent-based tri-silane (TK-590) were provided by TK Products (Minnetonka, MN). The 4CP (99.8%) used was purchased from Sigma– Aldrich in crystalline-form. The clear, non-UV resistant, PVC pipe (4 inches in diameter) and white PVC end caps were purchased from W P Law, Inc. (Columbia, SC). De- ionized water (17.9 M X cm) was prepared using a NANO pure Diamond Analytical ultrapure water system (Barn- stead). The UV light was provided by a bank of 26 photo- chemical lamps (RPR-3500) from Southern N E Ultraviolet (Branford, CT).

2.2. Reactor construction

Clear PVC pipe (4 ft in length) was cut so that 12, 3.5 in., pieces remained. Clear PVC was used so that side walls of the reactors allowed UV penetration. Pigmented PVC has been shown to degrade under continuous UV exposure (Gesenhues, 2000; Kemp and McIntyre, 2000 ). The effects of UV on nonpigmented PVC are unknown. On each of the 12 pieces, a bottom portion was primed with a PVC cleaning solution, and glue was applied to the primed surfaces. The clear PVC pieces were then fit evenly and securely in 12 PVC caps ( Fig. 1 ). Cleaning of the interior PVC surfaces was done using a wire brush, mild detergent, and cold water. Sand-cement and distilled water were mixed until desired workability was achieved. From this mix, 275 ml was added to each PVC reactor and worked with a knife until surfaces were level. After 24 h, water was added to the surface of the PCC in each reactor to form a shallow pond; this pond was maintained for 7 days. After 7 days of continuous curing, PCC achieves 80% of the compres- sive strength of a full 28-day curing period ( Mamlouk and Zaniewski, 1999 ).

208

M.J. Watts, A.T. Cooper / Solar Energy 82 (2008) 206–211

M.J. Watts, A.T. Cooper / Solar Energy 82 (2008) 206–211 Fig. 1. PVC and concrete photoreactor.

Fig. 1. PVC and concrete photoreactor.

2.3. TiO 2 -sealer-coatings

The coating preparation and application process began by completely mixing 30 ml of the selected concrete sealer (colorless liquid) with a measured amount of TiO 2 (fine, white powder). To the cured concrete surface of one reac- tor, 5 ml of 10% (by mass) TiO 2 -TK-290-WB sealer solu- tion were applied and allowed to cure for at least three days. The cured, sealed surface contained an even distribu- tion of TiO 2 nanoparticles across the surface and depth of sealer. Similarly, another two reactors were treated with a 0% TiO 2 -TK-290-WB sealer solution; two more with 1%; two with 5%; and two were left untreated. The remaining three reactors were treated with either a 2% TiO 2 -TK- 290-WB sealer solution, a 2% TiO 2 -TK-290-sealer solution, or a 2% TiO 2 -TK-590-sealer solution. A total of 12 reactors were used in the study.

2.4. Analysis

The initial concentration of 4CP, in de-ionized water, in each reactor was 4 mg/l, with a volume of 200 ml used for each reactor. Samples of 1.2 ml each were taken over a per- iod of up to 14 h. The samples were analyzed using a Var- ian CP-3380 gas chromatograph with a Varian 8200 solid phase micro extraction (SPME) autosampler and a 100 l m polydimethyl siloxane (PDMS) SPME fiber assem- bly. After an initial sorption phase, the sorbed analyte was front injected, and the capillary column temperature was raised from 100 to 180 C at a rate of 20 C/min. The front injector temperature was 250 C with a hold time of 12 min. The prescribed FID temperature was 275 C.

2.5. Experimental matrix

A full factorial experimental design was used for each of the sealers. Each set of experiments included three reactor treatments duplicated in darkness and under UV illumina- tion. The three reactor treatments were (1) no TiO 2 and no- sealer; (2) sealer alone (no TiO 2 ); and (3) sealer with TiO 2 .

Dark experiments ‘‘No TiO 2 –No Sealer’’ were used to explore the possible 4CP degradation pathways of infiltra- tion or absorption in the concrete substrate, and air–water partitioning. Likewise, the darkness-exposed ‘‘No TiO 2 – Sealer’’ and ‘‘TiO 2 –Sealer’’ were designed to show possible adsorption of the contaminant to sealer and/or photocata- lyst-sealer. These dark experiments occurred under identi- cal conditions to the UV experiments, with no visible or UV light. Under UV exposure, these reactors aided in iden- tification of photolysis and/or photocatalysis reactions occurring in the bulk solution.

3. Results and discussion

3.1. Photocatalytic experiments

For a single trial, a set of batch reactors were exposed to either darkness or UV light for a maximum of 14 h. Sam- ples were taken for analysis of 4CP concentration in bulk solution on the hour or bi-hourly during these exposure periods. Three sets of PVC batch reactors were used. The first two sets (I & II) used TK-290 WB as the sealer and each set included reactors with an untreated concrete sur- face, a sealed concrete surface with no TiO 2 , a sealed con- crete surface with 1% TiO 2 by weight in sealer and a sealed concrete surface with 5% TiO 2 in sealer. The first set (I) also included a sealed concrete surface with 10% TiO 2 by weight in sealer. The final set (III) of PVC batch reactors included a reactor with a sealed concrete surface using TK-290 WB, a reactor sealed with TK-290, and a reactor sealed with TK-590. All three reactors from this set con- tained 2% TiO 2 by weight in their sealed concrete surfaces. The greatest reduction of 4CP concentration in reactors using TK-290 WB (the first two sets) was observed in a reactor containing 5%-TiO 2 in the sealant after exposure to 12 h of continuous UV (40% of initial 4CP concentra- tion remaining). Fig. 2 shows the normalized mean concentration of 4CP as a function of time, in the first two reactor sets, where TK-290 WB sealant was used. From visual observation it appears that the dark (black marks) and UV-exposed (white marks) 4CP concentrations begin to stratify after approximately 4 h of continuous exposure. Very little, if any, 4CP degradation appears to occur in the dark reactors (black marks). The presence of TiO 2 in the sealed-concrete surface has a noticeable effect on the 4CP concentration in the bulk solution, with the lowest observed 4CP concentra- tions found in those reactors. However, due to the observa- tion of a reduction of 4CP concentration over time in the reactors without TiO 2 that were exposed to UV light, 4CP photolysis must also be considered as a possible deg- radation pathway.

3.2. Kinetic analysis

The generalized rate equation for degradation of 4CP can be written as

M.J. Watts, A.T. Cooper / Solar Energy 82 (2008) 206–211

1.2 1 0.8 0.6 0.4 0.2 0 0 2 4 6 8 10 12 14
1.2
1
0.8
0.6
0.4
0.2
0
0
2
4
6
8
10
12
14
4CP, [C] / [C 0 ]

time, hr.

Dark - No SealerUV - No Sealer Dark - 0% TiO2-Sealer UV - 0% TiO2-Sealer Dark - 1%

UV - No SealerDark - No Sealer Dark - 0% TiO2-Sealer UV - 0% TiO2-Sealer Dark - 1% TiO2-Sealer

Dark - 0% TiO2-SealerDark - No Sealer UV - No Sealer UV - 0% TiO2-Sealer Dark - 1% TiO2-Sealer

UV - 0% TiO2-SealerDark - No Sealer UV - No Sealer Dark - 0% TiO2-Sealer Dark - 1% TiO2-Sealer

Dark - 1% TiO2-SealerUV - No Sealer Dark - 0% TiO2-Sealer UV - 0% TiO2-Sealer UV - 1% TiO2-Sealer

UV - 1% TiO2-Sealer- 0% TiO2-Sealer UV - 0% TiO2-Sealer Dark - 1% TiO2-Sealer Dark - 5% TiO2-Sealer UV

Dark - 5% TiO2-Sealer- 0% TiO2-Sealer Dark - 1% TiO2-Sealer UV - 1% TiO2-Sealer UV - 5% TiO2-Sealer Dark

UV - 5% TiO2-Sealer Dark - 10% TiO2-Sealer

UV - 10% TiO2-SealerTiO2-Sealer Dark - 5% TiO2-Sealer UV - 5% TiO2-Sealer Dark - 10% TiO2-Sealer Dark - 2%

Dark - 2% TiO2-Sealer1% TiO2-Sealer Dark - 5% TiO2-Sealer UV - 5% TiO2-Sealer Dark - 10% TiO2-Sealer UV -

UV - 2% TiO2 - Sealer1% TiO2-Sealer Dark - 5% TiO2-Sealer UV - 5% TiO2-Sealer Dark - 10% TiO2-Sealer UV -

209

Fig. 2. Observed normalized mean concentrations of 4CP in TK-290 WB reactors.

d ½ C 4CP

d t

¼ k ½ C 4CP n

ð2 Þ

where [C 4CP ] is the concentration of 4CP in the bulk solu- tion at any time, t . Using a graphical method, the reaction order, n , was determined for the 1% TiO 2 -sealer, 2% TiO 2 -sealer, and 5%-TiO 2 -sealers. Values for n of 0, 1, and 2 were evaluated by comparing regression coefficients from data sets repre- senting each of the three catalyst-sealers. For all three cat- alyst-sealers, the closest linear-fit was found when n = 0. Reaction rate constants for the zero-order reaction are shown in Table 1 . Zero-order reactions for the destruction of aqueous organics have also been observed in the presence of TiO 2 sol-gel films exposed to UV ( Minabe et al., 2000; Mills et al., 2003 ). Based on the above analysis, increasing the mass% of TiO 2 in the sealer appears to increase the rate of photodegradation of 4CP. However, when the rate con- stant is calculated per unit mass of TiO 2 , increasing the mass of TiO 2 in the sealer leads to a decrease in the reaction rate constant (Table 1 ). These results suggest that the limiting factor for the pho- tocatalytic oxidation of 4CP is not related to the surface kinetics, but to mass transfer of 4CP between bulk solution and catalyst. In these experiments, the reaction could be rate-limited by the lack of a mixing mechanism and/or slow

Table 1 Zero-order reaction rate constants for photodegradation of 4CP on photocatalyst-sealers

 

Rate constant, k, (mg/(L h))

Rate constant, k , (mg/(L h g TiO 2 ))

R

2

1% TiO 2 -sealer 2% TiO 2 -sealer a 5% TiO 2 -sealer 10% TiO 2 -sealer

0.166

4.116

0.9207

0.242

2.818

0.9633

0.277

1.373

0.9752

0.276

0.685

0.9673

a These rate constants were calculated using data from all three sealer formulations.

diffusion across the sealer coating. The thickness of the sea-

ler coating, presumably greater in the sealers with a greater mass of TiO 2 , exacerbates the problem of slow diffusion. Results of similar experiments that employed a mixing mechanism were inconclusive and are therefore not reported here. Moreover, the absence of induced mixing is

a practical constraint for applications of this type of system. Since the intensity of artificial UV light used in this study was weak relative to solar UV, it is anticipated that the reaction rate would be greater in the presence of sun- light. Using a radiometer with a UV filter the intensity measured under the photochemical lamps used in this study was 145 l W/cm 2 , while outside on a partly cloudy afternoon in Columbia, South Carolina (33 57 0 N 81 7 0 W) the intensity was 600 l W/cm 2 .

3.3. Treatment effects

Analysis of group means was employed to identify pho- tocatalytic effects of the sealant/TiO 2 surface treatment. Each experimental data point collected in this study was classified according to reactor set (I–III), light exposure (Dark or UV), presence of TiO 2 in the sealed-concrete sur- face (w/ or w/o), mass-% of TiO 2 present in sealer (no sea- ler, 0, 1, 2, 5, 10), sealer formulation (no sealer, TK-290 WB, TK-290, TK-590), and length of exposure time at sampling. Group means were calculated and compared using the statistical analysis package, JMP 5.0 (SAS Insti- tute). Multiple group means were compared simulta- neously using Tukey–Kramer adjusted t -tests for one-way analysis of variance, or Tukey–Kramer honestly significant

difference. Tukey–Kramer is an adjusted t -test that includes

a statistical factor of safety (standard error used to deter- mine least significant difference is larger) to account for the possible error of declaring a difference significant when

it is most likely null. Due to the lack of a balanced data set,

this method was better suited than an F-test for determina- tion of significant differences between group means.

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M.J. Watts, A.T. Cooper / Solar Energy 82 (2008) 206–211

Table 2 Values of ‘Abs(Dif)–LSD’ for group means of normalized 4CP concen- tration, [4CP]/[4CP] 0 , by exposure to darkness or UV

 

Dark

UV

Dark

0.0376

0.0556

UV

0.0556

0.0379

Data not segregated by presence of TiO 2 . Abs(Dif)–LSD.

In this method the difference (Dif) and the least signifi- cant difference (LSD), between two group means, are calculated. The difference between the absolute value of Dif and LSD for a comparison of two group means is then determined. If Dif is a smaller value than LSD, the differ- ence between the group means is not statistically signifi- cant, at the 95% level of confidence. If Dif is larger than LSD, then the difference between the group means is signif- icant (see Table 2 ).

3.3.1. Photocatalysis vs. photolysis With all data points grouped by either exposure to dark- ness or UV light, the effect of UV light on the 4CP concen- tration in bulk solution can be seen. The mean 4CP concentration in samples from reactors exposed to UV is significantly lower than the mean of samples taken in a dark environment. To determine the significance of photol- ysis reactions on the observed photodegradation of 4CP, data points were grouped by Dark or UV exposure, how- ever, only samples taken from reactors without TiO 2 were considered for means comparison, as shown in Table 3 . Negative values of Abs(Dif)–LSD for group mean compar- ison in Table 3 , indicate that photolysis reactions do not significantly impact the overall photodegradation of 4CP. Determining the effect the presence of TiO 2 in the sealer has on the photodegradation of 4CP in the batch reactor system requires grouping data points by sealers with and sealers without TiO 2 exposed to UV. Table 4 indicates that the mean concentration of 4CP in batch reactors contain- ing TiO 2 was significantly lower than in reactors without TiO 2 , when exposed to UV light. This would indicate that the photodegradation of 4CP in the PVC batch reactors is TiO 2 -catalyzed. The lowest mean normalized 4CP concentrations were observed in the bulk solution of PVC batch reactors contain- ing TiO 2 in the sealed concrete surface and exposed to con- tinuous UV. While UV alone appeared to contribute to the disappearance of 4CP from solution, an analysis of means showed this contribution to be insignificant. The possible degradation pathways of adsorption to sealed-surface, and

Table 3 Values of ‘Abs(Dif)–LSD’ for group means of normalized 4CP concen- tration, [4CP]/[4CP] 0 , by UV or Dark exposure without the presence of TiO 2

 

Dark

UV

Dark

0.0563

0.0471

UV

0.0471

0.0547

Abs(Dif)–LSD.

 

Table 4 Values of ‘Abs(Dif)–LSD’ for group means of normalized 4CP concen- tration, [4CP]/[4CP] 0 , in reactors exposed (10 h) to UV by ‘w/’ TiO 2 and ‘w/o’ TiO 2

 

w/o

w/

w/o

0.0649

0.0978

w/

0.0978

0.0616

Abs(Dif)–LSD.

volatilization also did not appear to contribute significantly to 4CP disappearance during 10 h exposure periods.

3.3.2. Impact of sealant concentration

Table 5 provides further evidence of the TiO 2 -catalyzed photooxidation of 4CP in the batch reactors. The mean 4CP concentration in reactors without sealed concrete sur- faces (UV exposed) is significantly higher than the mean concentrations for reactors with 1%, 5%, and 10% TiO 2 - sealers. However, the mean 4CP concentration for 0% TiO 2 -sealers is not significantly different than the mean concentration for 1%. Furthermore, the mean 4CP concen- trations for 5% and 10% TiO 2 -sealers are not significantly different from each other. It is likely that the optimum amount of TiO 2 in concrete sealers for this system lies in the range of 1–5% by mass. Increasing the mass% of TiO 2 in the sealed concrete sur- face exposed to UV increased the overall rate of disappear- ance of 4CP in the bulk solution; however, the effect was the opposite when the rate of disappearance of 4CP in the bulk solution was determined per unit mass of catalyst, decreasing with an increase of mass percent TiO 2 in the sea- ler. For the photodegradation of aqueous 4CP, it is likely that an optimum mass% of TiO 2 in the sealed concrete sur- face exists. A correlation may also exist (in terms of maxi- mizing photocatalytic activity) between thickness of TiO 2 - sealer film and mass% of TiO 2 that was not uncovered by this work. Since coating thickness on sealed concrete sur- faces can be a function of the porosity of the substrate, esti- mates of the available surface-pore space will be relevant to future optimization studies.

3.3.3. Solvent-based vs. water-based sealant

Mean concentrations of 4CP in reactors containing 2% TiO 2 with either TK-290 WB, TK-290, or TK-590 were ana- lyzed to determine any significant differences in photoreactor performance between solvent-based (TK-290 and TK-590) and water-based sealers (TK-290 WB) (see Table 6 ).

Table 5 Values of ‘Abs(Dif)–LSD’ for group means of normalized 4CP concen- tration, [4CP]/[4CP] 0 , by mass% of TiO 2 present in TK-290 WB sealer under UV exposure (10 h)

 

No sealer

0

 

1

5

10

No sealer

0.1238

0.1126

0.0027

0.0534

0.0390

0

0.1126

0.1283

0.0130

0.0377

0.0234

1

0.0027

0.0130

0.1371

0.0864

0.1001

5

0.0534

0.0377

0.0864

0.1382

0.1518

10

0.0390

0.0234

0.1001

0.1518

0.1840

M.J. Watts, A.T. Cooper / Solar Energy 82 (2008) 206–211

211

Table 6 Values of ‘Abs(Dif)–LSD’ for group means of normalized 4CP concen- tration, [4CP]/[4CP] 0 , by sealer formulation; dark exposure (10 h)

TK-590

TK-290

TK-290 WB

TK-590

TK-290

TK-290 WB

0.0557

0.0035

0.0728

0.0557

0.0728

0.0136

0.0035

0.0136

0.0702

Abs(Dif)–LSD.

Table 7 Values of ‘Abs(Dif)–LSD’ for group means of normalized 4CP concen- tration, [4CP]/[4CP] 0 , by sealer formulation; UV exposure (10 h)

 

TK-290 WB

TK-590

TK-290

TK-290 WB

0.1373

0.0813

0.0402

TK-590

0.0813

0.1373

0.0962

TK-290

0.0402

0.0962

0.1373

Abs(Dif)–LSD.

 

In darkness, varying the sealer formulation does not appear to affect the mean 4CP concentration by either increased adsorption to film or some unidentified reaction between sealer constituents and 4CP. While there is a detectable difference in mean 4CP concentrations in reac- tors TK-290 WB than in reactors with TK-590, this differ- ence is statistically significant by only 0.3% of the initial 4CP concentration (see Table 7 ). Under UV lamps, no one sealer formulation had a signif- icantly lower mean 4CP concentration than another. How- ever, TK-290 and TK-590 contain an unspecified aliphatic hydrocarbon and 2-propanol, respectively; both of which are regulated by OSHA in regards to airborne exposure. Future experiments could be designed to determine the maximum mass of TiO 2 and also determine impact, if any, TiO 2 has on silane and siloxane sealer’s ability to pro- tect interior steel from corrosion. Concrete coupons treated with TiO 2 -sealer could be tested for chloride diffusion rates ( Bush, 1998; Zhang et al., 1998 ). The potential of TiO 2 impregnated siloxane sealers for preparation of photocatalytically active concrete has been demonstrated. The use of solvent-based siloxane sealers does not appear to enhance the photodegradation of 4CP relative to water-based siloxane sealers, and the emission of harmful organics associated with their use makes it unlikely that they could be used to make existing concrete surfaces ‘self-clean- ing’. Therefore, additional work should focus on the com- parison of photocatalytic degradation performance of varying formulations of water-based concrete sealers.

Acknowledgements

This material is based upon work supported by the Na- tional Science Foundation under Grant No. BES-0092921. Michael Watts was supported by the National Science Foundation’s Graduate Teaching Fellows in K-12 Educa- tion program under Grant No. 0086427. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not neces- sarily reflect the views of the National Science Foundation.

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