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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National University of Singapore. titanium oxide. However. The decrease was more pronounced for the Portland cement mortars than the mortars with slag. strength. increasing attention has been paid to aesthetic appearance of the concrete in situations where no coating is used. Singapore Davis Tanadi.photocatalytic concrete was developed by Italian scientists [1] in recent years. There was no obvious improvement in self-cleaning when the dosage of TiO2 is further increased beyond 2%. With a further increase in TiO2 dosage to 2%. 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.35th Conference on OUR WORLD IN CONCRETE & STRUCTURES: 25 – 27 August 2010. Keywords: hydration. This type of concrete contains nano-size . the workability was decreased with further increase in TiO2 dosage. self-cleaning. However. the percentage of improvement was less significant compared with 1% TiO2. the compressive strength of the Portland cement mortars with TiO2 was only slightly lower than that without. Workability of the fresh mortars was not affected significantly by 1% TiO2. photocatalyst. Singapore EFFECT OF PHOTOCATALYST TIO2 ON WORKABILITY. and strength development of mortars were evaluated as well. effect of TiO2 on rate of cement hydration. and there was no significant difference for the slag mortars with or without TiO2. Introduction Although the primary function of concrete is structural. Portland cement mortars and mortars with 50% slag as cement replacement were included. Compressive strength of the mortars at 28 days was decreased with the increased in TiO2 dosage up to 6%. and w/cm of the mortars was 0. Self-cleaning efficiency of the mortars tended to decrease with increasing irradiation time.CLEANING EFFICIENCY OF MORTARS FOR APPLICATIONS IN TROPICAL ENVIRONMENT Min-Hong Zhang. slag. AND SELF . National University of Singapore. In addition. STRENGTH. workability 1. workability. Singapore Wei Li*. National University of Singapore. 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. A new building material . the rate of colour recovery was further increased.5. At 91 days. Further study is need for long-term performance and performance in tropical environment. 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.

All the ingredient materials. 3. mortars. specimens listed in Table 4 were cast for various tests. In addition. and sample ampoules were pre-conditioned to 30 °C as well. and amplifier range was set at 600 mW. All the mortars had a water-to-cementitious materials ratio (w/cm) of 0. One of the most commonly used photocatalysts is titanium oxide (TiO2). EVONIK Industries AG. Dosages of the TiO2 in the mortars varied from 0 to 6% by mass of the cementitious materials. The application of such material is particularly useful for tropical climate like Singapore. surface texture of specimens. 2.                                                              1 Degussa P-25. when exposed to UV light. Characteristics of the TiO2 were provided by manufacturer and is summarised in Table 2. where the annual rainfall volume is high. Long-term performance of specimens exposed to tropical environment will be reported at a later stage. and strength development of mortars are evaluated as well. Concretes. 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. effect of TiO2 on rate of cement hydration. Experimental Details 2. 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).1 Materials used Normal Portland cement. When incorporated in concrete.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.photocatalyst that has the ability to self clean concrete surface and to remove pollutants when the concrete is exposed to sunlight.3 Specimen preparation and curing Mortars were mixed in a Hobart mixer at an ambient temperature of about 30 oC. The heat generation in the cement pastes reflects rate of cement hydration.5 and a sand-to-cementitious materials ratio of 2.5. Germany .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. Effects of TiO2 dosage. they can self clean the concrete surface. 2. as well as wetting and drying during exposure are also assessed. and deionised water was used for mortars. natural sand. Test methods 3. For each mixture. Titanium dioxide (TiO2)1 with about 80% in anatase and 20% in rutile commercially available was used. Properties of the photocatalysts originate from their ability to initiate. mixing utensils. The catalytic reaction also prevents bacteria or dirt from sticking to a surface. oxidationreduction reactions that lead to decomposition of organic molecules of contaminants adsorbed on their surfaces [1]. The calorimeter was conditioned at 30 °C for a day before experiments. 2. workability. and coatings with this concept have been used in pilot projects for buildings and pavements in Europe and Japan [2]. making them easily removed by splash of water or rain. Essen. ground granulated blast-furnace slag. slag. Characteristics of the cement and slag are given in Table 1. This temperature was selected to simulate weather conditions in tropical countries.

3. and 20 hrs after the exposure. Flexural tensile strength was determined using three 40x40x160-mm prisms. 3. The heat generated from the cement hydration was monitored continuously for 24 hours. The distance between the lamps and specimens was approximately 34 mm. The normalized power output was then converted to heat generated in the sample (in joules/gram). Rhodamine B dye was selected as it is related to polycyclic aromatic hydrocarbon (PAH) . The specimens were then exposed to lab air for 21 days. Results presented are the average from the five locations. 3. The power output (in milliwatt) from the calorimeter due to the heat generated was recorded every 5 minutes. The measurement area for each location was approximately 11 mm in diameter. the contaminated specimens were exposed to UV light irradiation in a Weather Tester QUV/se according to ASTM G 154-06 [7]. During the spray of the dye. the top casting surface of the specimen was ground to obtain a smooth surface.a soiling substance in urban environments [6].05 g/L) was sprayed evenly on the ground surface of each specimen. 15.4 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. This dye has strong reddish colour. The power output was normalized based on sample mass.The preconditioned ingredient materials were hand mixed for about 1 minute. 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. 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. 28 and 91 days according to BS EN 196-1:2005 [5]. 10. After 7 days moist curing. which is suitable for the evaluation since photocatalysis of TiO2 occurs at the irradiation of wavelength < 380 nm [8]. and is soluble in water and chemically stable in alkaline condition of the mortars.3 Compressive and Flexural Strength Compressive and flexural tensile strengths of the mortars were determined at 7. The results were expressed in Commission International d'Eclairage LAB system with L* a* b* diagram shown in Figure 2 [9]. After capping the ampoule. 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. thus the heat generated initially during mixing and preparation was not captured. Since the dominant colour of the Rodamine B dye was red. At the age of 28 days. the sample and reference ampoule were inserted into the calorimeter. Mortar specimens were cast in Petri dishes with a diameter of 92 mm. 3. The calorimeter started to record heat 10 minutes after the cementitious materials were in contact with water. 5. Wavelength of UVA lamps was 340 nm. 2. The paste sample of about 10 grams was then transferred into a sample ampoule with the sample mass recorded. 5 ml of aqueous solution of Rhodamine B dye (concentration = 0. 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. Sixteen hrs after the dye spray. The two portions of the prisms after the flexural strength test were used for the compressive strength test. The measurements were carried out at 1.2 Workability Flow table test was conducted according to ASTM C 1437-07 [4] to evaluate the effect of TiO2 dosage on mortar flowability. 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 ] .

. the workability was decreased with further increase in TiO2 dosages. and wetting and drying.red colour intensity of dye sprayed specimen at nth hr of irradiation. 4. whereas for the mortars with slag. no clear trend was observed as how the TiO2 dosage affected the flexural tensile strength of the mortars at various ages. From Figure 6. However. selected mortar specimens were exposed to UV and simulated rain according to a scheme shown in Figure 3. the specimens were sprayed with the same dye and exposed to the UV irradiation for 20 hrs. After that. At the age of 91 days. From Figure 7. respectively. it seems that 7-day compressive strength of the mortars was not affected by the TiO2 dosage significantly. respectively. The results were compared with those from the specimens exposed to UV irradiation without rain. Following this.(+a*)0 – red colour intensity of the original specimen without dye spray (for long-term test. Nevertheless. surface texture of the specimens. 28-day compressive strength of the mortars was decreased with the increase in TiO2 dosage. However. After that. The results indicated that the workability of the fresh mortars was not affected significantly by 1% TiO2 in the mortars. 4. The decreased workability of the mortars was probably due to extremely fine size of the TiO2 particles incorporated in the mortars.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 specimens were exposed to lab air for approximately 1. (+a*)d – red colour intensity after dye spray but before the UV irradiation. 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. 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. 4. The decrease was more pronounced for the Portland cement mortars than the mortars with slag. there was no significant difference between those with or without TiO2. longterm efficiency of self-cleaning of the mortars were also evaluated. the compressive strength of the Portland cement mortars with TiO2 was slightly lower than that without. After the initial exposure to the UV irradiation for 20 hrs. In addition to the effect of TiO2 dosages. (+a*)dn . 980 or 1480 hrs of exposure to UV light). During this 20-hr exposure. the workability of mortars with or without slag was similar. At a given TiO2 dosage.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. the specimens were further exposed to the UV irradiation/rest/test in a scheme given in Table 5. the flexural tensile strength did not seem to be affected significantly by the TiO2 dosage. 11]. this was the intensity for the specimens after 280. To evaluate the effect of surface texture of the specimens. the colour change of the mortar specimens was measured and evaluated in the same way as in the first 20 hrs. Results and Discussion 4. both ground surface (top side) and cast surface (bottom side) were used.3 Compressive and Flexural Tensile Strength of Mortars Compressive and flexural tensile strength developments of the mortars are shown in Figures 6 and 7. To evaluate the effect of wetting and drying.5 months. The results indicated that the rate of cement hydration was increased with increasing the dosage of TiO2 in both pastes with or without slag.

4. The different performance between the Portland cement mortars and the mortars with slag may be attributed to their different porosities. 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. 4. though some strongly adsorbed species cannot be removed by this method [13]. thus less efficient self-cleaning performance. than the Portland cement mortars.4. 4.4. 1000 and 1500 hrs of exposure in the UV irradiation is presented in Figure 12. Since the specimens with ground surface had higher porosity than those with the cast surface. the rate of colour recovery was further increased. However. and the results are shown in Figure 11. The Portland cement mortars with 4 and 6% TiO2 showed similar trend. Reduced photocatalytic activity of TiO2 with time has been reported in literature. Poon and Cheng [12] suggest that decreased porosity of a sample will result in decreased surface area for photocalysis of TiO2. the difference was not significant. 300. thus less efficient self-cleaning. the performance was not recovered to its original capacity. The results indicated that self-cleaning efficiency of the specimens were reduced with the increased time. The specimens with 4% and 6% TiO2 showed similar trend. It seems that in general the slag mortars showed similar or slightly lower rates of colour recovery. the percentage of improvement was less significant compared with 1% TiO2. The results indicated that the specimens with ground surface performed better than the corresponding specimens with casting surface (bottom surface in Petri dishes).4. However.2 Effect of slag Effect of slag on the self-cleaning performance of the mortars is shown in Figure 9.1 Effect of TiO2 dosage Effect of TiO2 dosage on self-cleaning capability of the mortars is shown in Figure 8.3 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. The mortars with slag probably had lower porosity due to pozzolanic reaction than the corresponding Portland cement mortars. However. 10.69 m2. There was no significant improvement in self-cleaning when the dosage of TiO2 was further increased. 4. The results indicated that short-term exposure to wetting did not affect self-cleaning performance of the mortars significantly. The mortar with a faster colour recovery rate under UV irradiation is considered to have better self-cleaning performance. the higher exposed surface of TiO2 in the former resulted in better self-cleaning performance than the latter. only washing by water/rain is adopted as a practical way of regeneration. 4. Further research is needed in this aspect. Deactivation of TiO2 has been attributed to deposition of surfaces species. intermediates.5 Longer term efficiency of self-cleaning capability Self-cleaning efficiency of the Portland cement mortars with 2% TiO2 after 20.4.4 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. However. which results in slower decomposition of the dye. With a further increase in the TiO2 dosage to 2%.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.4. 4. by-products or pollutants which are difficult to decompose [13]. 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. Some regeneration methods have been proposed to recover the photocatalytic ability of TiO2. 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.

British Standards Institution. 4. Photocatalysis: self-cleaning buildings and pollution abatement. L. 2009. West Conshohocken.R. 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. . the percentage of improvement was less significant compared with 1% TiO2. 1993. [8] Li. s827-s830. Zhou. With a further increase in TiO2 dosage to 2%. ASTM International. 1998. E. J. 5. than the Portland cement mortars. M. J.C.05 Methods of Testing Cement. Hu. April. L. Ying. R. MRS Bulletin.B & Zhao. pp. Proc. China Building Materials Academy. 2. Liu.S. E. Effect of Fillers (Fine Particles) on the Kinetics of Cement Hydration. 6. [3] ASTM C 1679 – 08 Standard Practice for Measuring Hydration Kinetics of Hydraulic Cementitious Mixtures Using Isothermal Calorimetry. Precise Colour Communication: Colour Control from Perception to Instrumentation. Water spay/rain improves the self-cleaning performance. 1137-1142. pp. [5] BS EN 196:1. Clean Buildings and Clean Air.K, Deposition of photocatalytic TiO2 and N-doped TiO2 films by arc ion plating,Transactions of Nonferrous Metals Society of China 17. H. At 91 days. Summary and Conclusions Based on the results obtained for the Portland cement mortars and mortars with 50% slag as cement replacement. J. References [1] Cassar. pp. L. G. [2] Bonafous. Compressive strength of the mortars at 28 days was decreased with the increase in TiO2 dosage up to 6%. pp. following conclusions can be drawn: 1. S. 132-137. Zhang. PA (2007). vol. And Duval.Z. ASTM International. Construction and Building Materials 21. There was no obvious improvement in self-cleaning when the dosage of TiO2 is further increased beyond 2 %. 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. Chinese Science Bulletin. [6] PICADA project (Photocatalytic Innovative Coverings Applications for Depollution Assessment). Effect of Ultrafine Particles on Heat of Hydration of Cement Mortars. W. Wu. Z. Li. TiO2-based building materials: Above and beyond traditional applications. 2006. 54.J. whereas there was no significant difference for the slag mortars with or without TiO2.H. no. [9] Handbook: The Essentials of Imaging. Self-cleaning efficiency of the mortars tends to decrease with increasing irradiation time. Z. W. the workability was decreased with further increase in TiO2 dosage. 2007. West Conshohocken. S. [11] Kadri. Konica Minolta Instrument Division.5. thus less efficient selfcleaning. [12] Poon. S. [10] Jiang. Workability of the fresh mortars was not affected significantly by 1% TiO2. West Conshohocken. Standard Test Method for Flow of Hydraulic Cement Mortar. the compressive strength of the Portland cement mortars with TiO2 was only slightly lower than that without. And Cheung. A. C. However. 328 – 331. [4] ASTM C 1437.07. 1746-1753. NO Removal Efficiency of Photocatalytic Paving Blocks Prepared with Recycled Materials. However. PA (2009). Japan. ACI Mater. In general the slag mortars showed similar or slightly lower rates of colour recovery. presentation at American Institute of Architects meeting. 6. [7] ASTM G 154 – 06 Standard Practice for Operating Fluorescent Light Apparatus for UV Exposure of Nonmetallic Materials.Y. 3rd Beijing Internation Symposium on Cement and Concrete. [13] Guo.L. The decrease was more pronounced for the Portland cement mortars than the mortars with slag. pp. 2004.P. 2006. April 2007. T. S. C. Photocatalysis of Cementitious Materials. Mutin. 2002. 3. PA (2008).7. ASTM International. 138 – 142. the rate of colour recovery was further increased. and Nonat.

5 6 Flow value (%) 113 119 92 85 68 118 119 86 88 59 .5 0.5 2. % Sodium Oxide.5 1 0.4 3.5 2.20 0.3 67. C2S Tricalcium Aluminate.5 OPC + Slag + 2% TiO2 0.5 4 0.48 2.5 Table 3 – Mix proportions of mortars (w/cm = 0.Properties of TiO2* Properties Unit Specific surface area (BET) m2/g Average primary particle size nm Density g/l wt.5) and flow values Proportions (by weight) Mix Notation TiO2.9 0. K2O Total Alkalinity as Na2O+0.Table 1 .1 13. m2/kg 393 Calcium Oxide.7 0. min 120 Final Setting Time.5 0 0.20 0.5 2. % Dicalcium Silicate.5 2. Al2O3 Iron Oxide.0 3.5 0.5 2 0. SiO2 19.4 3. C3A Tetracalcium Alumninoferrite. % of (cement Water Cement Slag Sand +slag) 0.5 2. MgO Chemical Composition.5 OPC + Slag 0.5 2.53 0. C4AF * Information Provided by Manufacturer Table 2.5 ≥ 99. CaO 62.5 – 4.5 OPC + Slag + 6% TiO2 0. Fe2O3 Magnesia.2 0.% Ignition loss ( 2 hrs at 1000 ⁰C) pH-value TiO2-content (based on ignited material) wt.5 2.5 0.2 Aluminium Oxide.5 2.Physical properties and chemical compositions of cement and slag Cement* Properties Initial Setting Time.5 OPC + 2% TiO2 1 0 2 0.5 OPC + 1% TiO2 1 0 1 0.3 Silica.4 4.5 0 0.5 OPC + 6% TiO2 1 0 6 0. C3S Mineral Composition According to Bogue Calculation.50 0.43 0. min 175 Physical Properties* Blaine Fineness.7 - Typical Value 50 ± 15 21 Approximately 130 ≤ 2.5 0.% * Information provided by manufacturer 4.18 2.5 OPC + Slag + 4% TiO2 0.8 33.5 0.3 slag 180 500 41.7 4.658K2O Sulphuric Anhydride as SO3 Insoluble Residue Loss on Ignition (LOI) Tricalcium Silicate.5 OPC 1 0 2.5 OPC + Slag + 1% TiO2 0. Na2O Potassium Oxide.7 1.1 5.5 2.9 10.5 OPC + 4% TiO2 1 0 4 0.5 0.

91 28 7-day moist curing. monitored. (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.b* = blue Figure 1 – Measurement location and size on specimen surface. 28.a* = green + b* = yellow .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. irradiation & 14-hr rest. 91 7. hrs hrs cycles 0 20 26 280 20 68 980 20 48 1480 20 - Time of UV exposure.UV and simulated rain scheme during wetting and drying cycles .L* a* b* colour spaces [9] Figure 3 . 28. hrs 260 680 480 - + L* = white . followed by exposure in lab air. Figure 2 .L* = black + a* = red .

Rate of heat development of Portland cement pastes with different TiO2 dosages.Figure 4 . Figure 6(a) . Figure 5 – Rate of heat development from cement pastes with 50% Slag and different TiO2 dosages.   .Compressive strength of mortars with 50% slag. Figure 6(b) .Compressive strength of Portland cement mortars.

Figure 7(a) . Figure 7(b) .Self-cleaning performance of mortars with 50% slag and with different TiO2 dosages.   .Flexural tensile strength of Portland cement mortars. Figure 8 (a) – Self-cleaning performance of Portland cement mortars with different TiO2 dosages. Figure 8 (b) .Flexural tensile strength of mortars with 50% slag.

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

Effect of wetting and drying on self-cleaning performance of mortars. Figure 12 – Effect of exposure time on self . Figure 11 .   . 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.Figure 10 .cleaning performance of the Portland cement mortar with 2% TiO2.Effect of surface texture on self-cleaning performance of mortars with 2% TiO2.