Surface & Coatings Technology 190 (2005) 314 320 www.elsevier.

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Preparation and properties of a g-Al2O3 washcoat deposited on a ceramic honeycomb

Pingping Jianga,b, Guanzhong Lua,*, Yun Guoa, Yanglong Guoa, Shunhai Zhanga, Xingyi Wanga
a

Lab for Advanced Materials, Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai, 200237, P.R. China b School of Chemistry and Material Engineering, Southern Yangtse University, Wuxi, 214036, P.R. China Received 25 August 2003; accepted in revised form 21 May 2004 Available online 28 July 2004

Abstract Washcoat deposited on ceramic honeycomb was prepared using pseudoboehmite, the CeO2ZrO2La2O3 solid solution, pore enlarger and other additives. The microstructures and surface performances of washcoat/honeycomb were investigated by SEM, BET surface area, XRD, ultrasonic vibration and hot shock simulation. The results show that the performance and loading of washcoat are affected obviously by the properties of slurry gel, such as the apparent viscosity, solid content, particle size and its distribution. When the apparent viscosity of slurry is lower, the gel with a narrow particle size distribution and finer particles can be obtained, with which the coating having an excellent performance can be prepared. Adding a small quantity of the CeO2ZrO2La2O3 solid solution can promote the thermal stability of washcoat, such as, after calcined at 1000 8C for 5 h the sample exhibits mainly the g-Al2O3 phases and the u-Al2O3, a-Al2O3 and n-Al2O3 phases have not been detected in the XRD spectra. It is found also that the washcoat prepared has excellent properties of the vibration-resistant, heatresistant and its BET surface area reaches 50 m2/g. D 2004 Elsevier B.V. All rights reserved.
Keywords: Washcoat; Preparation; g-Alumina; Slurry gel; Cohesive strength; BET surface area

1. Introduction The three-way catalytic converter for purifying the automotive exhaust is made up of three basic parts [14]. The first one is the monolithic support of ceramic honeycomb, which consists of the crystalline magnesium alumosilicate with hexagonal framework and has high mechanical stability and low thermal expansion coefficient. But the monolithic ceramic honeycomb has a lower surface area (~0.5 m2/g [5]), and can not make the active elements of catalyst on the surface of support disperse highly. In order to increase the surface area of the monolithic support, a layer of oxide material with a high surface area, called the washcoat, is coated generally in the interior walls of the honeycomb support. Finally, the noble metals that catalyze
* Corresponding author. Tel.: +86-21-64252219; fax: +86-2164253703. E-mail address: gzhlu@ecust.edu.cn (G. Lu). 0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2004.05.029

the conversion reactions of the noxious emission gases to harmless ones are dispersed highly on the surface of the washcoat/monolithic ceramic. Alumina is often used as the washcoat material [6,7]. For the washcoat, the higher surface area is very desirable, and favorable to disperse the active components of precious metals (such as Pt, Pd and Rh) on the support, to increase the conversion of automotive pollutants. Besides the high surface area, washcoat should possess a high thermal stability, promoter, an excellent adhesion on honeycomb support etc. For an excellent three-way catalyst operated in the hot exhaust gases at high temperature, high velocity and mechanical vibrations, the excellent properties of washcoat are very important. Now the catalysts supported on the honeycomb ceramic carrier are so widely used in the exhaust purification. It is well known that the washcoat is a key part in the purification catalysts [8,9], but a few of the scientific literatures about its preparation and the studies of its

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properties have been reported. Here, we have studied the preparation of the washcoat deposited on a ceramic honeycomb and reported a novel method of preparing washcoat for the three-way catalyst. The studies show that it is possible to prepare the washcoat having excellent adhesion on a ceramic honeycomb, good thermal stability and high surface area.

2. Experimental 2.1. Materials The commercial monolithic cordierite cast of Corning, having 400 cells per square inch (cpsi), was used as the support and cut to a cylinder (40F 20 mm). Pseudoboehmite (g-AlOOH, BET surface area 180 m2/g) was used a precursor of g-Al2O3. Ceriazirconialanthana mixed oxides (Ce:Zr:La=1:1:0.6, mol) and ceriazirconia mixed oxides (Ce:Zr=1:1, mol) were synthesized by coprecipitation method, in which nitrates of Ce, Zr and La were used as precursors. The coprecipitates prepared were dried overnight at 120 8C in air, calcined at 600 8C for 4 h in air, and then crushed to 0.51.0 mm. 2.2. Preparation of washcoat on a ceramic honeycomb First, the slurry gel was prepared as follows: the mixture of pseudoboehmite powders with a desired particle size distribution, CeO2ZrO2La2O3, citric acid and water, was milled for 48 h at room temperature, and its pH value and viscosity were adjusted by 0.1 M HNO3, HCl and HAc aqueous solution. Then the slurry gel was coated on the ceramic honeycomb by impregnation method, and the excess gel inside the channels of honeycomb substrate was blown off by air. It was dried at 120 8C for 12 h in air. The loading of washcoat was determined by weighting. The Pd supported washcoat/ceramic honeycomb catalyst was prepared by impregnating the washcoat/honeycomb with an aqueous solution of Pd. Then it was dried and calcined at 600 8C for 4 h. The loading of Pd was controlled at 1.0 g Pd/l. 2.3. Analysis methods The viscosity of slurry gel was measured with the Brookfield Viscometer (NDT-179D). The particle size distributions were measured by the laser particle size analyzer (USA Beckman Coulter 230). The powder XRD of sample was recorded by the Japan Science D/max-RB instrument, with CuKa radiation. The surface morphology of sample was examined by the Japan electronics JSM6360LV scanning electron microscope (SEM). The BET surface area was determined with the ST-03A instrument (Beijing) at liquid nitrogen temperature.

The adhesion ability of washcoat on the ceramic honeycomb substrate was assessed through laundering in the KU200 ultrasonic vibration cleaner, power 220 W and frequency 40 kHz. After the sample calcined at 600 8C for 4 h was laundered in an aqueous medium under the ultrasonic vibration for 20 min, then the sample was dried and weighed. The peeling amount of washcoat out of honeycomb substrate was calculated primarily based on the decrease amount of the sample weight, by which the resistance to mechanical vibration was evaluated. Second, the samples were calcined inside the muffle at 500 8C for 1 h and 750 8C for 5 h, and then cooled down spontaneously to the room temperature for about 6 h. Hence, the resistance thermal shock of the coating was also qualitatively analyzed.

3. Results and discussion 3.1. Effect of apparent viscosity of slurry on the loading of coating The solid particles in slurry have an instinctive tendency to settle by gravitation, which makes the viscosity measurement difficult and vigorous stirring continuously to keep a homogenization of the slurry during the impregnation process. Our studies show that the stability of slurry can be improved obviously by adding the inorganic acid, such as hydrochloric acid, nitric acid or acetic acid, to keep the particles in the slurry not flocculating and settling, and the loading of coating on a ceramic honeycomb is related to the apparent viscosity of slurry. The relation between an apparent viscosity of slurry and the loading of coating are shown in Fig. 1. It is found that the apparent viscosity of slurry affects greatly the loading of coating, and the loading of coating increases almost linearly with increasing of apparent viscosity. For the first impregnation, using the slurry with 10mPa.s viscosity, the loading of coating was about 7.5 wt.%. When

Fig. 1. The loading of coating versus the apparent viscosity of slurry.

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Fig. 4. Particle size distribution in the gel (II) (pH 4.0, solid content 30%, apparent viscosity 30 mPa s). Fig. 2. The relation of the solids content in slurry gel to the loading of coating. The pH value of gel: (1) 2; (2), 4; (3), 5.

the viscosity of slurry was 20 or 30 mPa s, the loadings of coating could reach 11 or 15.2 wt.% respectively; the viscosity was 40 mPa s, its loading could be more than 18 wt.%. The suitable loading of washcoat on the support depends on the particular usage of catalyst and is generally 1025 wt.%, which can not be coated enough by a single impregnation. So the multiimpregnations are often required. For the second or the third run by an impregnation, the loading amount on the honeycomb was much lower than the first loading of coating, even if the same slurry was used. The results above show that the higher apparent viscosity in slurry is beneficial to enhance the loading of coating. In the first impregnation, thanks to the absorption of the particles in the slurry on the surface of ceramic honeycombs (2MgOd 2Al2O3d 5SiO2) and supports capillary attraction, the loading of coating is much higher than one of the second run or the third run. In the process of preparing washcoat, it has been found that the slurries containing some additives can be absorbed effectively by ceramic honeycomb and if the loading of

coating is too high the washcoat deposited the ceramic honeycomb can shell off easily from the honeycomb during the process of calcination. 3.2. Effect of solid content on the loading of coating The relation of the loading of coating and the solid content in the slurry gel are shown in Fig. 2. The three kinds of gels was adjusted by the HNO3, HCl and HAc aqueous solution to pH 2, 4 and 5, respectively. The results show that the solid content in the slurry gel affects greatly the loading of coating. The more solid content in the slurry, the more loading of coating is. The lower pH value of the slurry gel is available to enhance the loading of coating. It was found that the pH value and solid content affect also the slurry viscosity. The high solid content and using fine particles may increase the viscosity of gel. That is, with increasing the solid content, the slurry gel became thicker. Thus, the viscosity of slurry is one of the most important parameters. When the solid content of the slurry gel was 10 wt.% with pH value of 2 (4 or 5), the loading of coating prepared

Fig. 3. Particle size distribution in the gel (I) (pH 4.0, solid content 30%, apparent viscosity 10 mPa s).

Fig. 5. Particle size distribution in the gel (III) (pH 4.0, solid content 30%, apparent viscosity 40 mPa s).

P. Jiang et al. / Surface & Coatings Technology 190 (2005) 314320 Table 1 Particle size distribution and apparent viscosity of the slurry gel Volume (u%) Gel (I) 10 (mPa s)a Particle diameter (bd/Am) 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
a

317

Gel (II) 30 (mPa s) Particle diameter (bd/Am) 1.124 1.405 1.678 1.966 2.279 2.626 3.017 3.450 3.933 4.474 5.076 5.773 6.583 7.557 8.778 10.380 12.590 15.770 20.210 43.670

Gel (III) 40 (mPa s) Particle diameter (bd/Am) 1.968 2.477 2.927 3.359 3.795 4.250 4.747 5.301 5.947 6.737 7.868 10.060 34.810 45.820 55.490 63.620 70.940 78.670 88.560 146.800

0.079 0.095 0.111 0.127 0.144 0.163 0.185 0.211 0.243 0.283 0.338 0.425 0.962 1.202 1.392 1.561 1.723 1.893 2.119 3.206 Apparent viscosity.

by first impregnation was about 4% (2 or 3 wt.%); its solid content was 30 wt.% and pH value was 2 (4 or 5), the loading of coating reached 8 (11 or 12 wt.%). As the higher solid content of slurry was used, such as 40 to 50 wt.%, the capillary action of the support to a slurry gel was reduced, which makes that the coating layers inside channels of honeycomb were relatively thicker and poor distribution homogeneity. The suitable solid content in the slurry gel with pH value of 25 is about 30 wt.% and the first loading of coating can reach 812 wt.%. 3.3. Effect of particle size in gel on the performance of coating In studying the effect of particle size in the slurry gel on the loading of coating, the apparent viscosity of slurry was

controlled to 10, 30 and 40 mPa s, its solid content was 30 wt.% and pH 4.0. The milling time of wet slurry was 48 h. Figs. 35 and Table 1 show that the curve and data of the particle size distributions in the slurry gel. The results show that the diameter of ~90% particles in the slurry (I) with 10mPa.s apparent viscosity was smaller than 2 Am, and a ~5% particles had the diameter of 0.040.08 Am. The particle diameters were mainly 0.042.92 Am (0.040.6 and 0.62.92 Am of two peaks) in the slurry gel (I). At the operation condition of pH 4.0, solids content 30% and apparent viscosity 10 mPa s, the slurry gel with the narrow particle size distribution and smaller particles can be prepared. Compared with the gel (I), the gel (II) and gel (III) has higher apparent viscosity (30 and 40 mPa s), which leads to an increase of the particle sizes. The particle diameters of gel (II) and gel (III) were mainly 0.634 Am (one peak, Fig. 4) and 1.1123 Am (1.114, 14123 Am of two peaks, Fig. 5), respectively. The size distribution of particles in the slurry gel is affected greatly by the apparent viscosity of gel, the small grains in the slurry gel with high apparent viscosity, can coalesce to form a larger particles after wet-milling (Fig. 6 (a)), then that turns into high dense agglomerates. Fig. 6 shows the SEM photographs of slurry gel (III) and (I). The gel (III) has many large agglomerates made up of platelet-like units, which results from high apparent viscosity in slurry. In the gel (I), there are the particles with a narrow size distribution, small size of less than 10 Am and irregular shape. These results of SEM are in accordance with the respective particle size distribution curves in Figs. 3 and 5. The results above indicate that the apparent viscosity is a very important parameter for the excellent slurry gel, and the lower apparent viscosity is in favor of inhibiting conglomeration of the particles and breaking down the agglomerates in wet-milling. The BET surface areas of the washcoat/ceramic honeycomb prepared with different slurry gels were shown in Table 2. The surface area of the ceramic honeycomb was only about 1 m2/g, and that of the washcoat/ceramic honeycomb reached 2650 m2/g, such as that of the

Fig. 6. SEM photographs of the slurry gel (III) (a) and gel (I) (b).

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Table 2 BET surface area of washcoat/ceramic honeycomb Gel Apparent viscosity (mPa s) 10 30 40 S BET (m2 g-1) Honeycomb 0.90 0.96 1.20 Washcoat/ honeycomb 50.2 40.5 25.8 Fission or shelling (600 8C/4 h) No No Yes

I II III

washcoat/honeycomb (I) prepared with gel (I) is 50.2 m2/g. For the washcoat/honeycomb (I), the situation of fission and shelling has not been observed. But spallation of coating from the washcoat/ceramic honeycomb (III) was seen by naked eyes. Fig. 7 presents the SEM image of the washcoat/honeycomb(I) prepared with gel(I). Compared with SEM image of honeycomb (Fig. 7 (a)), it was observed clearly that a mass of fine particles were piled up dispersively on the ceramic honeycomb and the microstructure and pores of coating was ranked orderly and uniformly, and no cracking or spallation existed on the surface of the washcoat/ceramic honeycomb in Fig. 7(b). The smaller particles can penetrate into surface cavities of honeycomb to be interlocked and banchoredQ on the surface of honeycomb. Thus, it is possible to prepare a homogenous and excellent washcoat deposited on a ceramic honeycomb with high surface area by using the appropriate slurry gel. 3.4. Solid structure of coating Fig. 8 shows the XRD patterns of the coating calcined at 600 8C for 4 h in air. There are mainly the diffraction peaks of the g-Al2O3 and CeO2ZrO2La2O3 phases. Pseudoboehmite has translated into g-Al2O3 at the calcination temperature. The diffraction peaks of gAl2O3 are weaker at 2h=45.88 and 67.28. The diffraction peaks at 2h=28.78, 33.38, 47.88, 56.88 and 77.18 are ascribed to the presence of the CeO2ZrO2, CeO2ZrO2 La2O3 solid solution [10], which indicates that the storage oxygen materials of CeO2ZrO2, CeO2ZrO2La2O3 in the washcoat exists in the original state and has not

Fig. 8. XRD patterns of the coating (I). (j) g-Al2O3, (x) CeO2ZrO2 solid solution, (r) CeO2ZrO2La2O3 solid solution.

combined with alumina. The peaks of u-Al2O3, a-Al2O3 and n-Al2O3 in washcoat calcined at 800 8C has not been detected. It is possible there is a stabilizing effect of the CeO2ZrO2La2O3 solid solution on g-Al2O3 to inhibit the phase transformation of g-Al2O3. 3.5. Thermal stability of coating Fig. 9 shows the XRD patterns of the Pd/Al2O3 catalyst calcined at 600 8C/4 h and 1000 8C/5 h. The sample calcined at 6008C/4 h behaves mainly the g-Al2O3 phase. After the sample was aged at 10008C/5 h, phase transformation of g-Al2O3 occurred and the y-Al2O3, u-Al2O3 phases formed, in which Al2O3 exists mainly in the y-Al2O3 phase. The XRD spectra of the Pd/CeO2ZrO2(La2O3)/Al2O3 samples are shown in Fig. 10. The results show that the presence of the CeO2ZrO2(La2O3) solid solution can inhibit the phase transition of g-Al2O3 to y-Al2O3, u-Al2O3 and enhance the thermal stability of catalyst. For the Pd/ CeO2ZrO2La2O3/Al2O3 catalyst calcined at 1000 8C for 5 h, there is only the g-Al2O3 phase. These results above mentioned indicate that adding CeO2ZrO2La2O3 in the washcoat can increase the thermal

Fig. 7. SEM photographs of honeycomb (a) and washcoat/honeycomb (b) prepared with gel (I).

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Table 3 Weight loss of washcoat/ceramic honeycomb treated by ultrasonic vibration and thermal shock Washcoat Apparent viscositya (mPa s) 10 30 40
a

Weight loss (DW 1%) 1.9 12.4 48.6

Weight loss (DW 2%) 21.3 20.1 30.4

Total loss (DW %) 23.2 32.5 79.0

I II III

The apparent viscosity of gel, pH 4.0, solid content 30%.

Fig. 9. XRD patterns of Pd/Al2O3 calcined at 600 8C/4 h (a) and 1000 8C/5 h (b). (j) g-Al2O3, ( R ) y-Al2O3, ( ) u-Al2O3.

stability of washcoat/honeycomb to promote the performance of the three-way catalyst at higher temperature. 3.6. Cohesive ability and the heat resistance of coating In order to characterise the weight loss of sample after ultrasonic vibration and thermal shock, it was defined as follows: The weight loss of sample after ultrasonic vibration: DW 1= [(W 1-W 2)/W 1]100% The weight loss of sample after thermal shock: DW 2=[(W 3-W 4)/W 3]100% Total weight loss of sample: DW=DW 1+DW 2. W 1 is the washcoat weight before ultrasonic vibration, W 2 is the washcoat weight after ultrasonic vibration; W 3 is the washcoat weight before thermal shock, W 4 is the washcoat weight after thermal shock.

The cohesive ability of coating on the ceramic honeycomb was assessed by ultrasonic vibration and thermal shock, and the results are shown in Table 3. After the sample was treated by ultrasonic vibration and thermal shock, there was obviously weight loss of sample. For the weight loss of sample treated by ultrasonic vibration, washcoat (I) is the least (1.9%), washcoat (II) and washcoat (III) reach 12.4% and 48.6%, respectively. For the weight loss of sample treated by thermal shock, the situation is similar to that treated by ultrasonic vibration, washcoat (I) is the least (21.3%) and washcoat (III) is the largest (30.4%). The results herein show that, the washcoat (I) with a narrow particle size distribution and fine particles has been supported more tightly on the ceramic honeycomb. A large number of fine particles stacked on the honeycomb framework provide a firm cohesive ability between the aluminabase washcoat and the ceramic honeycomb and much higher resistance to mechanical vibration and thermal shock. The washcoat (II) and (III) prepared by using the gel with larger particles and broad particle size distribution, have a weak adhesion to the ceramic honeycomb. In order to prepare the excellent wachcoat on ceramic honeycomb, the key is to prepare a good slurry gel with a low apparent viscosity, narrow particle size distribution and smaller particles.

4. Conclusions The good performance washcoat of g-Al2O3 deposited on a ceramic honeycomb can be prepared and its performance is affected by the properties of slurry gel, such as the apparent viscosity, solid content and size distribution of particle, pH value etc. The suitable parameters of the slurry gel are 3040% solid content, lower apparent viscosity (such as, 10 mPa s), a narrower particle size distribution and smaller size of particle. The washcoat may be prepared by the multiimpregnations. The loading (815 wt.%) of coating prepared by first impregnation is more than that by the second run and the third run. The washcoat prepared with this method has excellent properties of the vibration-resistant, heat-resistant, high surface area (50 m2/g) etc. The presence of the CeO2 ZrO2La2O3 solid solution can promote the properties of washcoat (such as thermal stability), the sample calcined at 1000 8C for 5 h exhibits mainly the g-Al2O3 phases.

Fig. 10. XRD patterns of Pd/CeO2ZrO2La2O3/Al2O3 (a) and Pd/CeO2 ZrO2/Al2O3 (b) calcined at 1000 8C/5 h. (j) g-Al2O3, ( R ) y-Al2O3, ( ) uAl2O3, (x) CeO2ZrO2, (r ) CeO2ZrO2La2O3.

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Acknowledgement This study was supported financially by Shanghai Nanotechnology Promotion Center (No. 0123nm025), Science and Technology Committee of Shanghai Municipality (No. 03301200) and Rare Earths Office of shanghai Municipality (No. 2002-RE-03 and 2002-RE-10).

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