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Advanced Powder Technol., Vol. 17, No. 6, pp.

681 688 (2006) VSP and Society of Powder Technology, Japan 2006.
Also available online - www.brill.nl/apt

Translated paper 05 SPTJ Young Researchers Award Direct observation of powder agglomerated structure in ceramic slurries using optical microscopy
HIROYA ABE 1, , MAKIO NAITO 1 , KENJI OKAMOTO 2 , TADASHI HOTTA 3 , SATOSHI OHARA 4 and TAKEHISA FUKUI 5
1 Joining

and Welding Research Institute, Osaka University, Mihogaoka 11-1, Ibaraki 567-0047, Japan 2 R&D Laboratories, NipponDenko Co., Ltd, 1-62, Kouno, Tachibana, Anan, Tokushima 774-0023, Japan 3 Japan Fine Ceramics Center, Mustuno 2-4-1, Atsutaku, Nagoya 456-8587, Japan 4 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira 2-1-1, Aobaku, Sendai 980-8577, Japan 5 Hosokawa Powder Technology Research Institute, Shoudai 9-1, Tajika, Hirakata 573-1132, Japan Japanese version published in JSPTJ Vol. 41, No. 1 (2004); English version for APT received 26 June 2006.

AbstractDirect observation of the powder structure in aqueous alumina slurry was investigated using optical microscopy in the transmission mode. In this technique, the slurry was sandwiched by two glass plates kept a 100 m apart and the structure of powder agglomerates in the slurry was projected under optical transmission mode. It was revealed that the technique is powerful for examining large-scale heterogeneity in aqueous ceramic slurry of which the solid concentration is up to 10 vol.%. Keywords: Optical microscopy; slurry; alumina; polymer dispersant; occulation.

1. INTRODUCTION

Concentrated ceramic particulate suspensions (slurries) are often prepared and used for material production in many industrial areas. For example, most ceramic parts are shaped from slurries [1]. In the semiconductor industry, they are used as polishing material for chemical mechanical planarization [2]. Since their agglomerated
* The
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paper was chosen from the research papers representing the awarded work. whom correspondence should be addressed. E-mail: h-abe@jwri.osaka-u.ac.jp

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state strongly inuences the nal microstructures [2 6], characterization of the state is quite important. In general, the agglomerated state of slurry can be characterized from macroscopic properties such as slurry rheology and microscopic properties such as the potential of particles in solvent [7, 8]. Direct observation of the agglomerated structure also presents an important structure, because the structure relates to the powder packing structures in the ceramic green body [4 6]. The structures within slurry can be visualized by means of cryo-scanning electron microscopy (SEM) [9]. This presents a freeze-dried powder structure. Recently, Takahashi et al. xed particles in slurry by gelation and directly observed their structure [10]. The sample obtained in this method can be sliced into a transparent specimen and then the three-dimensional particle agglomerated structure characterized using optical microscopy in the transmission mode. It is interesting to directly observe slurry structure without particle immobilization under various conditions such as shear stress and temperature change. In llers/polymer composite materials, the internal ller structure can be examined without ller immobilization using optical microscopy. However, the approach has not been applied to ceramic slurries. In this study, therefore, direct observation of the powder structure in aqueous alumina slurry was investigated using optical microscopy in the transmission mode.

2. EXPERIMENT

Alumina powder (AL160-SG4; Showadenko) was used for this study. Figure 1 shows a SEM image of the powder. The particle size distribution of the powder was measured by X-ray sedimentation (SediGraph 5100; Micromeritics) and its average particle size was 0.6 m. Aqueous alumina slurries were prepared by ball milling of the mixture of the powder, distilleddeionized water and polymer dispersant (ammonium polyacrylate, CERUNA-D305; Chukyoyushi). The solid concentration of the slurry was set to be 1, 5, 10 and 30 vol.%. The time of the ball milling was 24 h. The slurry agglomerated state was controlled by changing the amount of dispersant added. The dependence of shear rate on apparent viscosity was measured using a rotational viscometer (VT 550; HAAKE) at 25 C for characterization of slurry agglomeration. The powder structure in aqueous alumina slurry was directly observed using optical microscopy in the transmission mode. In this technique, the slurry was sandwiched by two glass plates kept 100 m apart. The optical transmitted image reected the structure of powder agglomerates in the slurry. To examine the applicability of the technique to moderately concentrated slurries, the slurry concentration was changed from 1 to 10 vol.%. In addition, the structure was observed under shear stress. For these experiments, a commercial tool (Linkam; CSS450) was used. Figure 2 shows the schematic diagram of the tool. It uses two polished quartz plates that are parallel to within 2 m. The bottom plate, on

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Figure 1. SEM micrograph of the alumina powder used in this study.

Figure 2. Direct observation technique of powder agglomerate structure in slurry (Linkam; CSS450).

which the slurry is placed, operates in step shear mode programmed within a motorcontrolled spread sheet. The gap between the two glass plates can be precisely varied from 5 to 2500 m.

3. RESULTS AND DISCUSSION

Figure 3 shows the viscosity versus shear rate curves of the two slurries with a solid loading of 10 vol.%. When 0.2 mass% dispersant was added, the viscosity decreased with increasing shear rate, indicating a pseudoplastic uid. On the other hand, the viscosity curve behaved as a Newtonian liquid with much lower viscosities when 0.4 mass% dispersant was added. It is suggested that the formation of aggregates in slurry was mediated by polymeric species under 0.2 mass%

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Figure 3. Flow curves for aqueous alumina suspensions with different dispersant content (solid loading 10 vol.%).

dispersant, resulting in occulated slurry, and the net repulsive force between particles became high under 0.4 mass% dispersant, resulting in deocculated slurry. Figure 4a and b shows transmission optical micrographs of the thinned slurries with 0.2 and 0.4 mass% dispersant, respectively. No clear contrast was seen in Fig. 4b, because the transparent image was out of focus due to the limited resolution power of optical microscopy when the sub-micron particles were well dispersed. On the other hand, Fig. 4a shows the inhomogeneous image that resulted from inhomogeneous transparency in the observation window due to the inhomogeneous distribution of the particles. It suggests that aggregates with a size of about several microns connected with each other and form a network powder structure in slurry, relating to the pseudoplastic uid. As can be seen, the microscopic heterogeneity of ceramic slurry (the agglomeration structure) can be visualized without particle immobilization using optical microscopy in the transmission mode. The technique, however, has a limitation in terms of resolution and therefore use of microscopic observation tool-based particle immobilization [10] is also important for the systematic structural examination of slurry. Figure 5 shows the inuence of solid loading on powder agglomeration structure in alumina occulated slurry. In the experiments, the slurries were prepared by adding 0.2 mass% dispersant, and their solid loadings were 1, 5 and 10 vol.%. In 1 vol.% slurry, many particle aggregates with a size of several to tens of microns are seen and some of them are connected. There are also regions with very high transparency among aggregated particles. These were the regions occupied with

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Figure 4. Transmitted images of slurry with 10 vol.% solid loading with dispersant content: (a) 0.2 and (b) 0.4 mass%.

solvent (water in this case). With increasing solid loading, distances among the aggregates became smaller and the size of connected aggregates (network structure) became larger. When solid loading was over 30 vol.%, the image was out of focus due to very low transparency. There is a limitation in solid loading for the observation technique. The thickness of slurry is quite important for observation. In the present case, the thickness of slurry was set to be 100 m. This value is almost the same as the thickness when the green or sintered bodies are observed in the optical transparent technique [4, 6]. Figure 6 shows the inuence of shear stress on powder agglomerate structure in 30 vol.% alumina occulated slurry with 0.2% dispersant. Transmission optical micrographs in Fig. 6a and b are those obtained just after the applied shear stress and after leaving for 1 min, respectively. The shear stress was applied for 1 min

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Figure 5. Inuence of solid loading on powder agglomerate structure in alumina slurries with 0.2 mass% dispersant with solid loading: (a) 1, (b) 5 and (c) 10 vol.%.

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Figure 6. Inuence of shear stress on powder agglomerate structure in 30 vol.% alumina slurry with 0.2 mass% dispersant: (a) just after applying shear stress and (b) after 1 min.

by rotating one glass plate with a shear rate of 20 s1 . Large heterogeneity was not observed just after applying the shear stress. Then, the powder agglomerate structure was formed after leaving for 1 min. Thus, the technique can also present direct examination of a dynamic structural change of the powder structure in occulated slurry. To improve transparency, the slurry thickness was controlled to be about 100 m by sandwiching it using two glass plates. In this case, it is noted that the agglomerate structure may be changed by compression. The inuences of slurry thickness on the agglomerate structure of slurry will be investigated. The surface condition of the glass plates such as wettability between slurry and the plate is also one of the key factors for the observation.

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The dynamic examination of slurry structure can be useful for analyzing the relationship between the ceramic formation process and slurry heterogeneity. For example, it may be a powerful tool in process characterization for tape casting with a Doctor blade.

4. CONCLUSION

The following results were obtained through the direct observation of aqueous alumina slurries using optical microscopy in the transmission mode: (1) Agglomeration structure in slurry can be visualized for slurry specimens with a thickness of about 100 m. (2) The technique can examine large-scale heterogeneity in aqueous ceramic slurry of which the solid concentration is up to 10 vol.%. (3) It also presents direct examination of powder structures in slurry under shear stress. Acknowledgements This work was partially supported by the Multi-client Project organized by Japan Fine Ceramics Center (JFCC).

REFERENCES
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