EFFECT OF PHOTOCATALYST TIO2 ON WORKABILITY,STRENGTH, AND SELF - CLEANING EFFICIENCY OF MORTARS FOR APPLICATIONS IN TROPICAL ENVIRONMENT

SMin-Hong Zhang, National University of Singapore, Singapore Davis Tanadi, National University of Singapore, Singapore Wei Li*, National University of Singapore, Singapore 35th Conference on OUR WORLD IN CONCRETE & STRUCTURES: 25 - 27 August 2010, Singapore

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35th Conference on OUR WORLD IN CONCRETE & STRUCTURES: 25 27 August 2010, Singapore

EFFECT OF PHOTOCATALYST TIO2 ON WORKABILITY, STRENGTH, AND SELF - CLEANING EFFICIENCY OF MORTARS FOR APPLICATIONS IN TROPICAL ENVIRONMENT
Min-Hong Zhang, National University of Singapore, Singapore Davis Tanadi, National University of Singapore, Singapore Wei Li*, National University of Singapore, Singapore

Abstract
This paper presents an experimental study to evaluate effect of TiO2 on self-cleaning performance of mortars exposed to controlled UV irradiation for up to 1500 hrs. Portland cement mortars and mortars with 50% slag as cement replacement were included, and w/cm of the mortars was 0.5. In addition, effect of TiO2 on rate of cement hydration, workability, and strength development of mortars were evaluated as well. Results indicated that the rate of cement hydration was increased with the increase in TiO2 dosage from 1 to 6 % by mass of cementitious materials in both pastes with or without slag. Workability of the fresh mortars was not affected significantly by 1% TiO2. However, the workability was decreased with further increase in TiO2 dosage. Compressive strength of the mortars at 28 days was decreased with the increased in TiO2 dosage up to 6%. The decrease was more pronounced for the Portland cement mortars than the mortars with slag. At 91 days, the compressive strength of the Portland cement mortars with TiO2 was only slightly lower than that without, and there was no significant difference for the slag mortars with or without TiO2. Mortars with 1% TiO2 showed good self-cleaning performance and faster rates of colour recovery of the contaminated specimens to their original colour of uncontaminated conditions. With a further increase in TiO2 dosage to 2%, the rate of colour recovery was further increased. However, the percentage of improvement was less significant compared with 1% TiO2. There was no obvious improvement in self-cleaning when the dosage of TiO2 is further increased beyond 2%. Self-cleaning efficiency of the mortars tended to decrease with increasing irradiation time. Further study is need for long-term performance and performance in tropical environment.
Keywords: hydration, photocatalyst, self-cleaning, slag, strength, titanium oxide, workability 1. Introduction Although the primary function of concrete is structural, increasing attention has been paid to aesthetic appearance of the concrete in situations where no coating is used. A new building material - photocatalytic concrete was developed by Italian scientists [1] in recent years. This type of concrete contains nano-size

photocatalyst that has the ability to self clean concrete surface and to remove pollutants when the concrete is exposed to sunlight. One of the most commonly used photocatalysts is titanium oxide (TiO2). Concretes, mortars, and coatings with this concept have been used in pilot projects for buildings and pavements in Europe and Japan [2]. Properties of the photocatalysts originate from their ability to initiate, when exposed to UV light, oxidationreduction reactions that lead to decomposition of organic molecules of contaminants adsorbed on their surfaces [1]. When incorporated in concrete, they can self clean the concrete surface. The catalytic reaction also prevents bacteria or dirt from sticking to a surface, making them easily removed by splash of water or rain. The application of such material is particularly useful for tropical climate like Singapore, where the annual rainfall volume is high. This paper reports an experimental study to evaluate effect of TiO2 on self-cleaning performance of mortars exposed to controlled UV irradiation in a Weather Tester QUV/se for up to 1500 hrs (equivalent to about 150 days assume 10 hrs light per day). Effects of TiO2 dosage, slag, surface texture of specimens, as well as wetting and drying during exposure are also assessed. In addition, effect of TiO2 on rate of cement hydration, workability, and strength development of mortars are evaluated as well. Long-term performance of specimens exposed to tropical environment will be reported at a later stage. 2. Experimental Details 2.1 Materials used Normal Portland cement, ground granulated blast-furnace slag, natural sand, and deionised water was used for mortars. Characteristics of the cement and slag are given in Table 1. Titanium dioxide (TiO2)1 with about 80% in anatase and 20% in rutile commercially available was used. Characteristics of the TiO2 were provided by manufacturer and is summarised in Table 2. 2.2 Proportion of mortar mixtures Ten mortar mixtures were included in the study (Table 3) with half of the mixtures contained 50% slag and the rest without. Dosages of the TiO2 in the mortars varied from 0 to 6% by mass of the cementitious materials. All the mortars had a water-to-cementitious materials ratio (w/cm) of 0.5 and a sand-to-cementitious materials ratio of 2.5. 2.3 Specimen preparation and curing Mortars were mixed in a Hobart mixer at an ambient temperature of about 30 oC. For each mixture, specimens listed in Table 4 were cast for various tests. The specimens were cured in moist condition at a temperature of about 28 30 oC for 7 days followed by exposure in laboratory air with relative humidity of about 80-85 % at a similar temperature until the time of testing. 3. Test methods 3.1 Rate of heat generation and cement hydration Effect of TiO2 dosages on the rate of heat generation in cement pastes was evaluated according to ASTM C1679-08 [3] using Thermometric TAM Air 3115 isothermal calorimeter at a temperature of 30 C. This temperature was selected to simulate weather conditions in tropical countries. The heat generation in the cement pastes reflects rate of cement hydration. The calorimeter was conditioned at 30 C for a day before experiments, and amplifier range was set at 600 mW. All the ingredient materials, mixing utensils, and sample ampoules were pre-conditioned to 30 C as well.

Degussa P-25, EVONIK Industries AG, Essen, Germany

The preconditioned ingredient materials were hand mixed for about 1 minute. The paste sample of about 10 grams was then transferred into a sample ampoule with the sample mass recorded. After capping the ampoule, the sample and reference ampoule were inserted into the calorimeter. The calorimeter started to record heat 10 minutes after the cementitious materials were in contact with water, thus the heat generated initially during mixing and preparation was not captured. The heat generated from the cement hydration was monitored continuously for 24 hours. The power output (in milliwatt) from the calorimeter due to the heat generated was recorded every 5 minutes. The power output was normalized based on sample mass. The normalized power output was then converted to heat generated in the sample (in joules/gram). 3.2 Workability Flow table test was conducted according to ASTM C 1437-07 [4] to evaluate the effect of TiO2 dosage on mortar flowability. 3.3 Compressive and Flexural Strength Compressive and flexural tensile strengths of the mortars were determined at 7, 28 and 91 days according to BS EN 196-1:2005 [5]. Flexural tensile strength was determined using three 40x40x160-mm prisms. The two portions of the prisms after the flexural strength test were used for the compressive strength test. 3.4 Self-cleaning Capability of mortars Self-cleaning capability of the mortars with various dosages of TiO2 was evaluated by monitoring the colour decay of the specimens contaminated by a pollutant dye exposed to UV irradiation. Rhodamine B dye was selected as it is related to polycyclic aromatic hydrocarbon (PAH) - a soiling substance in urban environments [6]. This dye has strong reddish colour, and is soluble in water and chemically stable in alkaline condition of the mortars. Mortar specimens were cast in Petri dishes with a diameter of 92 mm. After 7 days moist curing, the top casting surface of the specimen was ground to obtain a smooth surface. The specimens were then exposed to lab air for 21 days. At the age of 28 days, 5 ml of aqueous solution of Rhodamine B dye (concentration = 0.05 g/L) was sprayed evenly on the ground surface of each specimen. Sixteen hrs after the dye spray, the contaminated specimens were exposed to UV light irradiation in a Weather Tester QUV/se according to ASTM G 154-06 [7]. Wavelength of UVA lamps was 340 nm, which is suitable for the evaluation since photocatalysis of TiO2 occurs at the irradiation of wavelength < 380 nm [8]. The distance between the lamps and specimens was approximately 34 mm. Due to the photocatalysis effect of TiO2, colour intensity on the contaminated mortar surface will decrease with the increase in exposure time in UV irradiation. Colour change of the specimens was measured by a Konica Minolta Spectrophotometer CM 3500d at five different locations of each specimen as shown in Figure 1. The measurement area for each location was approximately 11 mm in diameter. Results presented are the average from the five locations. The results were expressed in Commission International d'Eclairage LAB system with L* a* b* diagram shown in Figure 2 [9]. Since the dominant colour of the Rodamine B dye was red, parameter +a* (red) was measured before and after the exposure of the specimens to UV irradiation and was used to assess the colour change of the specimens due to photocatalysis. The measurements were carried out at 1, 2, 3, 5, 10, 15, and 20 hrs after the exposure. During the spray of the dye, it was noticed that the intensity of the red colour on the mortar specimens of different mortar mixtures varied due to the difference on porosity of various mixtures. Therefore, relative colour change was used to evaluate the self-cleaning of the different mixtures as follows: % of colour change at nth hour = Where

[( a *) dn ( a * ) 0 ] [( a * ) d ( a * ) 0 ]

(+a*)0 red colour intensity of the original specimen without dye spray (for long-term test, this was the intensity for the specimens after 280, 980 or 1480 hrs of exposure to UV light), (+a*)d red colour intensity after dye spray but before the UV irradiation, (+a*)dn - red colour intensity of dye sprayed specimen at nth hr of irradiation. To evaluate the effect of surface texture of the specimens, both ground surface (top side) and cast surface (bottom side) were used. To evaluate the effect of wetting and drying, selected mortar specimens were exposed to UV and simulated rain according to a scheme shown in Figure 3. The results were compared with those from the specimens exposed to UV irradiation without rain. In addition to the effect of TiO2 dosages, surface texture of the specimens, and wetting and drying, longterm efficiency of self-cleaning of the mortars were also evaluated. After the initial exposure to the UV irradiation for 20 hrs, the specimens were exposed to lab air for approximately 1.5 months. After that, the specimens were placed in the Weather Tester and experienced 10 hrs of UV irradiation and 14 hrs rest to simulate daily routine for 26 cycles with a total UV exposure of 260 hrs. After that, the specimens were sprayed with the same dye and exposed to the UV irradiation for 20 hrs. During this 20-hr exposure, the colour change of the mortar specimens was measured and evaluated in the same way as in the first 20 hrs. Following this, the specimens were further exposed to the UV irradiation/rest/test in a scheme given in Table 5. 4. Results and Discussion 4.1 Effect of TiO2 Dosage on Rate of Cement Hydration Effects of TiO2 dosages on the rates of heat development of the control Portland cement pastes and pastes with 50% slag are shown in Figures 4 and 5, respectively. The results indicated that the rate of cement hydration was increased with increasing the dosage of TiO2 in both pastes with or without slag. This may be related to the nano size of the TiO2 particles which may increase inter-particle contacts and provide nucleation and growth sites in early cement hydration, thus accelerate the cement hydration [10, 11]. 4.2 Workability of Mortars Table 3 summarizes the results of flow table test for the control Portland cement mortars and mortars with the slag as cement replacement. The results indicated that the workability of the fresh mortars was not affected significantly by 1% TiO2 in the mortars. However, the workability was decreased with further increase in TiO2 dosages. At a given TiO2 dosage, the workability of mortars with or without slag was similar. The decreased workability of the mortars was probably due to extremely fine size of the TiO2 particles incorporated in the mortars. 4.3 Compressive and Flexural Tensile Strength of Mortars Compressive and flexural tensile strength developments of the mortars are shown in Figures 6 and 7, respectively. From Figure 6, it seems that 7-day compressive strength of the mortars was not affected by the TiO2 dosage significantly. However, 28-day compressive strength of the mortars was decreased with the increase in TiO2 dosage. The decrease was more pronounced for the Portland cement mortars than the mortars with slag. At the age of 91 days, the compressive strength of the Portland cement mortars with TiO2 was slightly lower than that without, whereas for the mortars with slag, there was no significant difference between those with or without TiO2. From Figure 7, no clear trend was observed as how the TiO2 dosage affected the flexural tensile strength of the mortars at various ages. Nevertheless, the flexural tensile strength did not seem to be affected significantly by the TiO2 dosage.

4.4 Self-Cleaning Capability of Mortars Self-cleaning performance of the mortars was evaluated by the rate of colour recovery from the contaminated condition to the original one. The mortar with a faster colour recovery rate under UV irradiation is considered to have better self-cleaning performance. 4.4.1 Effect of TiO2 dosage Effect of TiO2 dosage on self-cleaning capability of the mortars is shown in Figure 8. With the incorporation of 1% TiO2, the colour on the surfaces of the contaminated specimens recovered much faster due to the selfcleaning effect of TiO2 than the mortars without TiO2. With a further increase in the TiO2 dosage to 2%, the rate of colour recovery was further increased. However, the percentage of improvement was less significant compared with 1% TiO2. There was no significant improvement in self-cleaning when the dosage of TiO2 was further increased. 4.4.2 Effect of slag Effect of slag on the self-cleaning performance of the mortars is shown in Figure 9. It seems that in general the slag mortars showed similar or slightly lower rates of colour recovery, thus less efficient self-cleaning, than the Portland cement mortars. The different performance between the Portland cement mortars and the mortars with slag may be attributed to their different porosities. Poon and Cheng [12] suggest that decreased porosity of a sample will result in decreased surface area for photocalysis of TiO2, which results in slower decomposition of the dye. The mortars with slag probably had lower porosity due to pozzolanic reaction than the corresponding Portland cement mortars, thus less efficient self-cleaning performance. 4.4.3 Effect of surface texture of mortar specimens Effect of surface texture on self-cleaning capability of the mortars with 2% of TiO2 is shown in Figure. 10. The results indicated that the specimens with ground surface performed better than the corresponding specimens with casting surface (bottom surface in Petri dishes). However, the difference was not significant. Since the specimens with ground surface had higher porosity than those with the cast surface, the higher exposed surface of TiO2 in the former resulted in better self-cleaning performance than the latter. The specimens with 4% and 6% TiO2 showed similar trend. 4.4.4 Effect of intermittent wetting and drying Self-cleaning performance of the mortars with 2% TiO2 exposed to the wetting and drying to simulate natural exposure conditions was compared with the control specimens without wetting, and the results are shown in Figure 11. The wetting was achieved using water spray at a flow rate of 7 liters per minute in the testing machine to cover all the specimens over an area of 0.69 m2. The results indicated that short-term exposure to wetting did not affect self-cleaning performance of the mortars significantly. 4.4.5 Longer term efficiency of self-cleaning capability Self-cleaning efficiency of the Portland cement mortars with 2% TiO2 after 20, 300, 1000 and 1500 hrs of exposure in the UV irradiation is presented in Figure 12. The results indicated that self-cleaning efficiency of the specimens were reduced with the increased time. The Portland cement mortars with 4 and 6% TiO2 showed similar trend. Reduced photocatalytic activity of TiO2 with time has been reported in literature. Deactivation of TiO2 has been attributed to deposition of surfaces species, intermediates, by-products or pollutants which are difficult to decompose [13]. Some regeneration methods have been proposed to recover the photocatalytic ability of TiO2. However, only washing by water/rain is adopted as a practical way of regeneration, though some strongly adsorbed species cannot be removed by this method [13]. Figure 13 shows improved self cleaning performance of the mortar with 2% TiO2 after 100 hrs of water spray during a period of 4 months in comparison to that before the water spray. However, the performance was not recovered to its original capacity. Further research is needed in this aspect.

5. Summary and Conclusions Based on the results obtained for the Portland cement mortars and mortars with 50% slag as cement replacement, following conclusions can be drawn: 1. Rate of cement hydration was increased with the increase in TiO2 dosage from 1 to 6 % by mass of cementitious materials in both pastes with or without slag; 2. Workability of the fresh mortars was not affected significantly by 1% TiO2. However, the workability was decreased with further increase in TiO2 dosage. 3. Compressive strength of the mortars at 28 days was decreased with the increase in TiO2 dosage up to 6%. The decrease was more pronounced for the Portland cement mortars than the mortars with slag. At 91 days, the compressive strength of the Portland cement mortars with TiO2 was only slightly lower than that without, whereas there was no significant difference for the slag mortars with or without TiO2. 4. Mortars with 1% TiO2 showed good self-cleaning performance and faster rates of colour recovery of the contaminated specimens to their original colour of uncontaminated conditions. With a further increase in TiO2 dosage to 2%, the rate of colour recovery was further increased. However, the percentage of improvement was less significant compared with 1% TiO2. There was no obvious improvement in self-cleaning when the dosage of TiO2 is further increased beyond 2 %. 5. In general the slag mortars showed similar or slightly lower rates of colour recovery, thus less efficient selfcleaning, than the Portland cement mortars. 6. Self-cleaning efficiency of the mortars tends to decrease with increasing irradiation time. Water spay/rain improves the self-cleaning performance. 6. References [1] Cassar. L, Clean Buildings and Clean Air, Photocatalysis of Cementitious Materials, MRS Bulletin, 2004, pp. 328 331. [2] Bonafous. L, Photocatalysis: self-cleaning buildings and pollution abatement, presentation at American Institute of Architects meeting, April 2007. [3] ASTM C 1679 08 Standard Practice for Measuring Hydration Kinetics of Hydraulic Cementitious Mixtures Using Isothermal Calorimetry, ASTM International, West Conshohocken, PA (2009). [4] ASTM C 1437- 07, Standard Test Method for Flow of Hydraulic Cement Mortar, ASTM International, West Conshohocken, PA (2008). [5] BS EN 196:1- 05 Methods of Testing Cement. British Standards Institution. [6] PICADA project (Photocatalytic Innovative Coverings Applications for Depollution Assessment), 2006. [7] ASTM G 154 06 Standard Practice for Operating Fluorescent Light Apparatus for UV Exposure of Nonmetallic Materials, ASTM International, West Conshohocken, PA (2007). [8] Li. M.S, Zhang. S.J, L. J, Liu. T.Z, Zhou. Z.H, Ying. G.L, Hu. C.Y, Li. W.K Deposition of photocatalytic TiO2 and N-doped TiO2 films by arc ion platingTransactions of Nonferrous Metals Society of China 17, 2007, s827-s830. [9] Handbook: The Essentials of Imaging, Precise Colour Communication: Colour Control from Perception to Instrumentation, Konica Minolta Instrument Division, Japan, 1998. [10] Jiang. S.P, Mutin, J.C. and Nonat. A, Effect of Fillers (Fine Particles) on the Kinetics of Cement Hydration, Proc. 3rd Beijing Internation Symposium on Cement and Concrete, China Building Materials Academy, 1993, pp. 132-137. [11] Kadri, E. H. And Duval. R, Effect of Ultrafine Particles on Heat of Hydration of Cement Mortars, ACI Mater. J, 2002, pp. 138 142. [12] Poon, C. S. And Cheung. E, NO Removal Efficiency of Photocatalytic Paving Blocks Prepared with Recycled Materials, Construction and Building Materials 21, 2006, pp. 1746-1753. [13] Guo. S, Wu. Z.B & Zhao. W.R, TiO2-based building materials: Above and beyond traditional applications, Chinese Science Bulletin, April, 2009, vol. 54, no.7, pp. 1137-1142.

Table 1 - Physical properties and chemical compositions of cement and slag Cement* Properties Initial Setting Time, min 120 Final Setting Time, min 175 Physical Properties* Blaine Fineness, m2/kg 393 Calcium Oxide, CaO 62.3 Silica, SiO2 19.2 Aluminium Oxide, Al2O3 Iron Oxide, Fe2O3 Magnesia, MgO Chemical Composition, % Sodium Oxide, Na2O Potassium Oxide, K2O Total Alkalinity as Na2O+0.658K2O Sulphuric Anhydride as SO3 Insoluble Residue Loss on Ignition (LOI) Tricalcium Silicate, C3S Mineral Composition According to Bogue Calculation, % Dicalcium Silicate, C2S Tricalcium Aluminate, C3A Tetracalcium Alumninoferrite, C4AF * Information Provided by Manufacturer Table 2- Properties of TiO2* Properties Unit Specific surface area (BET) m2/g Average primary particle size nm Density g/l wt.% Ignition loss ( 2 hrs at 1000 C) pH-value TiO2-content (based on ignited material) wt.% * Information provided by manufacturer 4.4 3.4 3.5 0.20 0.43 0.48 2.2 0.18 2.3 67.4 4.1 5.9 10.3

slag 180 500 41.8 33.1 13.7 0.7 4.9 0.20 0.50 0.53 0.7 1.7 -

Typical Value 50 15 21 Approximately 130 2.0 3.5 4.5 99.5

Table 3 Mix proportions of mortars (w/cm = 0.5) and flow values Proportions (by weight) Mix Notation TiO2, % of (cement Water Cement Slag Sand +slag) 0.5 OPC 1 0 2.5 0 0.5 2.5 OPC + 1% TiO2 1 0 1 0.5 2.5 OPC + 2% TiO2 1 0 2 0.5 2.5 OPC + 4% TiO2 1 0 4 0.5 2.5 OPC + 6% TiO2 1 0 6 0.5 2.5 OPC + Slag 0.5 0.5 0 0.5 2.5 OPC + Slag + 1% TiO2 0.5 0.5 1 0.5 2.5 OPC + Slag + 2% TiO2 0.5 0.5 2 0.5 2.5 OPC + Slag + 4% TiO2 0.5 0.5 4 0.5 2.5 OPC + Slag + 6% TiO2 0.5 0.5 6

Flow value (%) 113 119 92 85 68 118 119 86 88 59

Table 4 Mortar specimens used for various tests and their curing conditions Properties to be determined Flexural strength Compressive strength Self cleaning capability Test age(day) 7, 28, 91 7, 28, 91 28 7-day moist curing; followed by exposure in lab air, (RH 80~85%) Curing & Conditioning Size of specimens 40 x 40 x 160 mm prisms Using the 2 portions from flexural strength test 92 x 16 mm disk No of specimen 3 6 1

Table 5 Test scheme of self cleaning performance of mortars Staring time of UV Exposure cycles in the test Exposure under UV irradiation of dye machine with 10-hr UV with colour recovery treated specimens, irradiation & 14-hr rest, monitored, hrs hrs cycles 0 20 26 280 20 68 980 20 48 1480 20 -

Time of UV exposure, hrs 260 680 480 -

+ L* = white - L* = black + a* = red - a* = green + b* = yellow - b* = blue Figure 1 Measurement location and size on specimen surface. Figure 2 - L* a* b* colour spaces [9]

Figure 3 - UV and simulated rain scheme during wetting and drying cycles

Figure 4 - Rate of heat development of Portland cement pastes with different TiO2 dosages.

Figure 5 Rate of heat development from cement pastes with 50% Slag and different TiO2 dosages.

Figure 6(a) - Compressive strength of Portland cement mortars.

Figure 6(b) - Compressive strength of mortars with 50% slag.

Figure 7(a) - Flexural tensile strength of Portland cement mortars.

Figure 7(b) - Flexural tensile strength of mortars with 50% slag.

Figure 8 (a) Self-cleaning performance of Portland cement mortars with different TiO2 dosages.

Figure 8 (b) - Self-cleaning performance of mortars with 50% slag and with different TiO2 dosages.

Figure 9 - Comparison of self-cleaning performance between the mortars with and without slag, (a)1% TiO2, (b) 2% TiO2, (c) 4% TiO2, and (d) 6% TiO2.

Figure 10 - Effect of surface texture on self-cleaning performance of mortars with 2% TiO2.

Figure 11 - Effect of wetting and drying on self-cleaning performance of mortars.

Figure 12 Effect of exposure time on self - cleaning performance of the Portland cement mortar with 2% TiO2.

Figure 13 Self cleaning performance of the mortar with 2% TiO2 after 100 hrs of water spray in comparison to that before the water spray.