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J. Am. Ceram. Soc., 94 [1] 4248 (2011) DOI: 10.1111/j.1551-2916.2010.04019.x r 2010 The American Ceramic Society

Spray Granulation of Nanometric Zirconia Particles

Bala P. C. Raghupathyw and Jon G. P. Binner
Department of Materials, Loughborough University, Leicestershire LE11 3TU, U.K.

Granulation is an essential step to improve the owability of submicrometer and nanometric ceramic powders to make them suitable for industrial die pressing. Controlled agglomeration of yttria-stabilized zirconia nanopowders with a primary particle size of B16 nm was carried out using two different routes, viz. spray drying (SD) and spray freeze drying (SFD). SD yielded owable, but hard granules while SFD produced owable and crushable (soft) granules suitable for die pressing applications. The owability was characterized using the Carr index and Hausner ratio and benchmarked with commercially available granulated submicrometer powder. Better owability was achieved when SFD was performed from a high solid content suspension. The fracture surface of uniaxially die-pressed green bodies from spray freeze-dried granules showed a homogeneous microstructure, while the spray-dried granules had not lost their identity even when compacted at high applied pressures in the range of 380 MPa. The granule strength was studied from the compaction curves. Mercury intrusion porosimetry showed interagglomerate and intraagglomerate pores in the case of spray-dried powder compacts. The presence of hard granules resulted in extensive grain growth during the sintering stage and was deleterious for the nal properties of the ceramics. I. Introduction
ANOSTRUCTURED ceramics have been shown to display a range of enhanced properties compared with their submicrometer counterparts, including high-temperature superplasticity and optical transparency. It has also been found that a number of other properties, including electrical, electronic, and magnetic are inuenced by the presence of a nanograin structure in these materials.1 Further, nanopowders can be sintered at relatively low temperatures,2 opening up possibilities of cosintering with lower cost metals. As a result, nanostructured advanced ceramics are likely to have a positive impact in a range of industries, including aerospace, transport, communications, and medical, in the future. The large-scale industrial production of nanocrystalline ceramics still remains a challenge, however. While wet forming routes have been shown to yield very homogeneous, high green density bodies,3 the drying stage is particularly slow as the component becomes larger due to the ne nature of the porosity in a body made of nanoparticles. Dry pressing is a well-established fabrication technique for ceramic component manufacture owing to its attractive attributes, including ease of automation, relatively low energy consumption, high material utilization, and ability to convert powders into moderately complex shapes with high precision and close tolerances at low cost. Die-pressed ceramic components are used widely in a wide range of industries including automotive, aeronautical, nuclear, and electronics. The technique is versatile and it is possible to achieve good quality components at very high production rates.4 The main challenges in ceramic nanopowder

consolidation by die pressing are the high tendency to agglomerate of the nanopowder, with van der Waals adhesion between particles becoming far more important than gravitational forces as the particle size reduces,5 and the consequent poor owability. Spray drying (SD) is widely used in the advanced ceramic industry to improve the owability of ne powders,6 although it can lead to hard granules. All the granules must break down into their primary particles during the compaction stage with no remnants of the initial granule structure present in the nal green body7 because a single remnant can result in a severe loss of strength by acting as a Grifth aw.8 The presence of remnants can also lead to excessive grain growth during the sintering stage. It is therefore important to control the granule strength so that crushable as well as owable granules are obtained, leading to a ne pore size distribution in the green body.9 Spray freeze drying (SFD) has been reported to yield soft granules from nanosized ceramics,10 eliminating the formation of a segregated binder layer commonly found in spray-dried granules.11 To address the scientic and technical challenge of developing a nanopowder that can be used successfully for dry pressing, i.e. both ows and is crushable, this paper compares and contrasts the use of spray drying and spray freeze drying as granulation steps and the subsequent die pressing of nanoparticulate zirconia. Compaction curves were used to observe the granule deformation characteristics during die pressing12 while mercury intrusion porosimetry and nitrogen adsorption isotherms were used to distinguish between interagglomerate and intraagglomerate pores in the die-pressed green compacts. The owability was measured using the Carr index and Hausner ratio and benchmarked with a commercial submicrometer-sized powder.

II. Experimental Procedure

A well-dispersed suspension of 3 mol% yttria-stabilized zirconia with an average particle size of B16 nm was supplied by MEL Chemicals (Swinton, Manchester, U.K.). It had a solids content of 5.5 vol% (26 wt%) in water and no other additives. The pH varied slightly between batches but was always between 2 and 3. The suspensions were concentrated using a route described elsewhere13 but which essentially involved changing the suspension pH to a value of B10 using tetra-methyl ammonium hydroxide (TMAH, Aldrich Chemicals Ltd., Dorset, U.K.) and then adding B1.5 wt% Dispex A40 (Ciba Speciality Chemicals, Bradford, U.K.) by active content. The latter is a 43% by weight solution of an ammonium salt of an acrylic polymer in water. The suspension was subsequently heated gently at 601C in a water bath until the solid content of the suspension reached 14.3 vol% (50 wt%). Throughout the concentration process, the suspension was kept under vigorous stirring to maintain homogeneity and at appropriate intervals14 it was exposed to ultrasonics (Soniprep 150, MSE Instruments, Manchester, U.K.; ultrasonic frequency 23 kHz; maximum power 150 W; amplitude 12 mm) to break down any agglomerates present into the primary particles. Typically, 2 min of ultrasound for every 30 mL of the suspension was found to be sufcient. The viscosity of the suspension was required to be lower than 0.5 Pa s at a shear rate of 100 s1 to be able to spray the suspension.

A. Krellcontributing editor

Manuscript No. 27476. Received January 28, 2010; approved June 30, 2010. w Author to whom correspondence should be addressed. e-mail: balapraveen2000@


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Spray Granulation of Nanometric Zirconia Particles Table I. Powder Coding

Starting suspension Code Solid content (vol%) Dispersant Drying route


The zeta potential of the suspensions was measured using an Accoustosizer II (Colloidal Dynamics, Sydney, Australia). Suspension ow behavior was monitored using a Bohlin Visco 88 viscometer (Bohlin Instruments U.K., Cirencester, U.K.), a controlled speed device that measured shear stress and viscosity as a function of shear rate. Measurements were recorded in a sweep cycle of continuous increasing and then decreasing shear rate ranging from 56 to 1000 s1. SD of the suspensions was carried out in a spray dryer (Production Minort, GEA Niro, Copenhagen, Denmark) with a rotary atomizer with the inlet and outlet stream temperatures maintained at 2101 and 1201C, respectively. SFD was carried out by spraying the slurry into liquid nitrogen using a twin uid nozzle. The frozen granules were dried by sublimation in a benchtop freeze dryer (Virtis benchtop SLC, NY) at o240 K under vacuum of B0.2 mbar. The drying path for the different powders is represented in Fig. 1; the moisture was removed by evaporation in SD while sublimation was used during SFD. An oven dried (OD) powder was also obtained for comparison by drying the as-received nanosuspension in an oven at 601C and subsequently micronizing it for 4 min in a micronizing mill (McCrone Scientic, London, U.K.). A benchmark submicrometer powder (TZ-3YSB-C, Tosoh Corporation, Tokyo, Japan) was used as-received. The weight loss from the powders over a temperature range from 251 to 6001C was studied using a thermogravimetric analyzer (TA Instruments Inc., DE) at 101C/min heating rate. The granule size distribution was analyzed using a Malvern Mastersizer 2000 (Malvern Instruments Ltd., Malvern, Worcestershire, U.K.) by suspending the powder in deionized water. Although the instrument had the capability of applying ultrasound during measurements (normally used to ensure dispersion of particles), this facility was not used in the present work because ultrasound could break up the granules. Even though the granules were suspended in deionized water, they appeared unaffected by the process as long as ultrasound was not used. The Hausner ratio and Carr index were measured as per the relevant British Standard.15 Briey, the untapped/initial density, Du was obtained by allowing it to fall freely into a stationary container, avoiding vibrations. To measure the tap density, Dt, the powders were tapped 1000 times with a constant amplitude of 3 mm; it was observed that there was no appreciable change in the tap density after approximately 300 taps. The Hausner ratio and Carr index were then calculated from: Hausner ratio Dt =Du Carr index 100 Dt Du =Dt


5.5 5.5 14.3 5.5 14.3

None Oven drying None Spray drying Dispex A40 Spray drying None Spray freeze drying Dispex A40 Spray freeze drying

ameter die and a load was applied to the top punch using a mechanical testing machine (L10000 Tensometer, Lloyds Instruments, Fareham, U.K.) with a computer interface to record load versus cross head position continuously. The density of the compact at any given pressure was deduced from the cross head position and data on elastic compliance of the testing system at the particular load. The die and punch were cleaned thoroughly before every measurement using acetone. The maximum pressure applied was 380 MPa. Green compacts in the form of disks were also made in a uniaxial press at the same pressure. The green density of the cylindrical compacts was calculated by measuring the volume and mass of the compacts. The granules and the fracture surface of the green bodies were observed using a eld-emission gun scanning electron microscope (Leo 1530 VP, Elektronenmikroskopie GmbH, Oberkochen, Germany). The pore size distribution within the compacts was measured using a mercury intrusion porosimeter (model 9310, Micromeritics Instrument Corporation, Norcross, GA). Both the low-pressure (r0.1 MPa) and high-pressure (0.7210 MPa) penetration data were collected manually and volumediameter data were calculated according to the Washburn equation 4g cos y P

The granule yield strength was investigated using compaction curves. About 1 g of each powder was placed into a 10 mm di-

where P is the applied pressure, d is the diameter of the pores, g is the surface tension of the mercury (474 mN/m), and y ( 5 1301) is the wetting angle used.16 Nitrogen adsorption isotherms were obtained for both the granules and compacts using a Tristart 3000 (Micromeritics Instrument Corporation) gas adsorption analyzer. All the powders and compacts were heated to 4001C in air and then degassed in a nitrogen atmosphere for 30 min at 4001C before testing. The surface area was evaluated using the multipoint BET method and the pore size distribution was obtained using the BJH model.17

Fig. 1. Phase diagram for spray drying and spray freeze drying paths.

Fig. 2. Zeta potential for nanosuspension with and without dispersant and tetra-methyl ammonium hydroxide.


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Fig. 3. Viscosity curves for the suspensions at different solids content. For comparison, the viscosity for the 14.3 vol% ZrO2 supsension without dispersant was B0.5 Pa s at 100 s1.

III. Results and Discussion

Table I gives a list of the powders that were analyzed in this study with their preparation conditions. Figure 2 shows the zeta potential of the nanosuspension before and after the addition of Dispex A40. The IEP may be seen to have shifted toward a lower pH with the addition of the anionic dispersant, as observed by Fengqiu et al.,18 indicating that the suspension with dispersant was more stable at basic pH as expected. Figure 3 shows a comparison of the viscosity of the suspensions at the two different solids contents. The viscosity of the 5.5 vol% suspension without dispersant was measured at pH 5 2.470.1 while that with 14.3 vol% solids content, both with and without dispersant, was measured at pH 5 1070.1, i.e. at their respective useable values. Although the increase in viscosity with the increase in solids content was expected, the viscosity of the more concentrated suspension without dispersant was higher than 0.5 Pa s (at 100 s1) and hence could not be sprayed. Figure 4 shows the loss on ignition for the SFD14 powders; a peak may be observed at B2701C that corresponds to the decomposition of Dispex A40 and TMAH. Micrographs of the different powders are shown in Fig. 5. As expected, both SD and SFD yielded spherical granules while the OD powder was in the form of irregular agglomerates. Some of the SD granules from the as-received suspension had a crater, while hollow donutshaped granules were formed from the higher solid content suspension containing the dispersant. These observations are

Fig. 5. (a) Spray drying (SD) granules from 5.5 vol% suspension at low and high magnications showing spherical agglomerates, some with drying craters, (b) SD granules from 14.3 vol% suspension with dispersant at low and high magnications showing hollow and donutshaped agglomerates, (c) spray freeze drying (SFD) granules from 5.5 vol% ZrO2 suspension at low and high magnication showing the porous structure, (d) SFD granules from 14.3 vol% solids suspension at low and high magnications showing the closer packing density of the primary particles, (e) OD5 powder from 5.5 vol% suspension at low and high magnication showing irregularly shaped agglomerates, and (f) Benchmark powder from Tosoh.

Fig. 4. TGA of SFD14 powder showing weight loss due to organic burnout.

similar to those observed by previous researchers1922 in other ceramic systems and is caused by the inward collapse of the granules during drying.23 SFD on the other hand, always resulted in spherical granules. It can be seen that the SFD granules were larger than the SD granules. This can be attributed to two

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Spray Granulation of Nanometric Zirconia Particles


Fig. 6. Spray freeze drying granule from 5.5 vol% solids suspension at a very high magnication showing the nanosized primary particles.

reasons: (i) there is no shrinkage of the granules during the SFD process as the moisture is removed through sublimation; (ii) the type of atomization used is different for the two processes. It can also be seen that the primary particles were packed closer in the SD powders while loose packing and ake like structures may be seen in the SFD powders. During SD, the moisture was removed from the droplets by a stream of hot air. As a result, the central core of the droplet will have retained more moisture, aiding in shrinkage due to capillary forces and resulting in closer particle packing within the granule. On the other hand, the granule density in SFD powders was directly proportional to the solid content of the starting suspension; hence, the particle packing was tighter in the granules formed from the 14.3 vol% suspension than from that containing 5.5 vol% solids. The higher magnication image in Fig. 6 shows that these granules were made of the primary particles, which were typically B16 nm in size. The granule distribution for the SD, SFD, and OD powders are shown in Fig. 7. While the SD5 powder had a wide and complex granule size distribution (Fig. 7(a)), the SD14 had a large and clear bimodal distribution (Fig. 7(b)). Based on the SEM micrographs, this is probably because of the different particle shapes, i.e. spherical and donut-shaped SD14 granules. Interestingly, the SFD5 powder displayed a quaternary distribution as for the SD5 powder, although the proportions of the different size distributions was different. The presence of a large proportion of nes in the SFD5 may be attributed to a weaker granule strength. In contrast, the SFD14 powder exhibited a single granule size distribution with an absence of granules larger than B200 mm. There was good correlation between the SEM images and the particle size distribution obtained from laser scattering for almost all of the powders. This showed that the technique measured the granule size distribution rather than the primary particle size distribution. However, the correlation was not true for SD14 powders (Figs. 5(b) and 7(b)). This may be due to the granules having a donut shape (Fig. 5(b)). It is known that when the particle or granule shape deviates from a sphere, then the size as reported by a Malvern Mastersizer is often larger than the actual value.24 In addition, anomalous scattering can also occur if the light can penetrate through the particle, as for donut-shaped granules.25 The agglomerate size distribution for OD5 powders is shown in Fig. 7(e) and reects the broad size distribution seen in the micrographs. The benchmark Tosoh powders had a unimodal granule size distribution. Table II shows the results of the ll and tap density and owability. The SD5 powder had the highest ll and tap densities, even higher than those of the benchmark powder. The reason for it being so high is probably due to the lack of organics (dispersant and pH modier), while the wide granule size distribution will have aided in achieving closer particle packing

Fig. 7. Granule size distribution: (a) spray dried (SD) from 5.5 vol% solids suspension, (b) SD from 14.3 vol% solids suspension, (c) spray freeze dried (SFD) from 5.5 vol% solids suspension, (d) SFD from 14.3 vol% solids suspension, (e) agglomerate size distribution: oven dried from 5.5 vol% solids suspension.

with the ner granules lling the interstices between the larger granules. In contrast, the lower densities of the SD14 powder would have been because of the donut shape of the particles, which would have left more voids, and the presence of organics reducing the absolute density. In contrast, the densities of the SFD granules were very much lower because no granule shrinkage occurred during sublimation of the frozen granules. As expected, the ll density increased with the increase in the solid content of the starting suspension, the SFD14 powder having values approximately half of those of the benchmark powder. Interestingly, the oven-dried powder had a tap density comparable with those of the SD powders. This is due to the very similar primary particle packing of these


Journal of the American Ceramic SocietyRaghupathy and Binner

Vol. 94, No. 1

Table II. Flowability of the Different Powders Investigated

Powder Fill density (g/cm3) Tap density (g/cm3) Hausner ratio Carr index


1.27 1.19 0.23 0.65 0.95 1.24

1.65 1.46 0.36 0.715 1.62 1.52

1.30 1.22 1.56 1.1 1.70 1.22

23.03 22.22 36.11 9.09 41.18 18.51

powders. The ll density was lower because of the irregular shape of the granules (Fig. 5(e)). The Carr index and Hausner ratio were used to characterize the owability and ease of die lling15,26; a lower value for these indices means that the powders have better owability. The oven-dried powders had the highest values and hence the worst owability owing to the irregular particle shape and the presence of a large number of nes. Although both SD and SFD nanopowders have, in general, improved owability compared with OD powders, the SFD5 powder had a poor owability due to the aky external surface morphology and low density of the granules. In addition, these granules were so weak that some of them could not withstand handling and hence crushed down to form nes even during the ow rate measurements. The SFD14 granules, in contrast, had near perfect spherical shape, lower amounts of nes, and smoother surfaces resulting in better owability than all the other powders, including the benchmark, when assessed using these techniques. Compaction curves were used to nd the apparent granule strength and to determine the optimal pressing pressure to achieve the highest possible green density compacts. The results for the different powders are shown in Fig. 8. The rst observation is that the density values at the lowest applied pressure, effectively the ll density values, follow the trend seen in Table II. As the pressure is increased, the benchmark and SFD5 granules show a clear knee point, which corresponds to the granule strength. The other granules do not have such clear break points, and this may be because of the presence of organics leading to more plastically deformable granules, which means that a sharp change in gradient is not observed. Nevertheless, all the curves show a change in gradient at below 10 MPa, which shows that the granules are crushed or rearranged during the rst stages of uniaxial pressing. Interestingly, the nal densities at the maximum stress used, 380 MPa, were not dissimilar. The green density of the nanopowder compacts from various powders was B54.571% of the theoretical value (6 g/cm3) while it was B5771% for TOSOH-based powder.

Fig. 9. Fracture surface of the die-pressed compact at low and high magnications for (a) SD5, (b) SD14, (c) SFD5, (d) SFD14, (e) OD5, and (f) Tosoh powder compacts.

Fig. 8. Compaction curves for the different powders showing the granule deformation characteristics.

The cylindrical disks made by uniaxially die pressing the nanopowders at 380 MPa were fractured and the surfaces were analyzed using SEM (Fig. 9). Figures 9(a) and (b) demonstrate very clearly that the SD granules were not completely crushed into their primary particles, while the SFD powders, being softer, crushed completely yielding much more homogeneous microstructures (Figs. 9(c) and (d)). Uncrushed agglomerates are seen in Fig. 9(e) for the OD powders. The benchmark Tosoh powders have crushed down completely and hence a homogeneous microstructure is evident in Fig. 9(f). As a result of the different granule strengths, the different powder compacts

January 2011

Spray Granulation of Nanometric Zirconia Particles


Fig. 10. Pore size distribution in a die-pressed compact made from SD5 powder using 380 MPa.

Fig. 12. Pore size distribution in a die-pressed compact made from benchmark Tosoh powder using 380 MPa.

had different pore size distributions (Figs. 1014), although they were all produced at the same pressure. The bimodal pore size distribution for the SD5 powder (Fig. 10), is a result of the remnant uncrushed granules within the green compact. The larger pores correspond to the interagglomerate porosity16 while the ner pores correspond to those within the agglomerate, or the intraagglomerate pores. This situation was much worse for the SD14 powder (not shown). In contrast, all of the green compacts made from SFD powders, both SFD5 (not shown) and SFD14, Fig. 11, had a unimodal pore size distribution. The pores were small and corresponded to those between the primary particles, i.e. intraagglomerate porosity. This supports, and indeed enhances, the results shown in Figs. 9(c) and (d), that the SFD granules were softer and crushed completely. The benchmark powder compacts also showed a more or less unimodal pore size distribution, although the mean pore size was larger and corresponded to the pores existing between submicrometer particles (Fig. 12). The nitrogen adsorption isotherms yielded more data about the nest porosity, that between about 2 and 100 nm. Above this range, nitrogen reaches its saturation pressure at liquid nitrogen temperatures. The pore size distribution for the granules and compacts (Figs. 13 and 14) for the SD and SFD powders, respectively, shows that the pore volume and average pore diameter for the nest pores were both reduced by die pressing at 380 MPa, demonstrating that the granules were being disrupted to some extent with both granulation techniques.

Unfortunately, this technique could not be used to generate further data about the larger, interagglomerate porosity because these were 4100 nm in diameter. Legros et al.27 deduced the volume of interagglomerate porosity in nanopowder compacts by subtracting the porosity detected by nitrogen adsorption from the total porosity calculated from geometrical measurement. Table III follows this approach and summarizes the total volume of interagglomerate pores in the green compacts. It can be seen that the relatively hard SD and OD granules had a higher percentage of pores with a size 4100 nm while the softer SFD powders yielded a more homogeneous nanostructure with very ne porosity. This is key for obtaining small grain size during sintering. The pores in the benchmark submicrometer powder compacts were generally larger than 100 nm and hence very little porosity was detected by the nitrogen adsorption technique.

IV. Conclusions
The long-term goal of achieving a granulated nanopowder that ows as well as current commercial submicrometer powders so that existing presses can be used by industry, while also crushing to yield a green nanostructure without any granule relics has been at least partially achieved. While spray-dried powders with good owability have been produced from zirconia nanosus-

Fig. 11. Pore size distribution in a die-pressed compact made from SFD14 powder using 380 MPa.

Fig. 13. Pore size distribution in spray-dried granules and their compacts.


Journal of the American Ceramic SocietyRaghupathy and Binner

Vol. 94, No. 1

Table III. Interagglomerate Porosity in Die-Pressed Green Compacts

% Compaction pressure Theoretical density (MPa) Actual pore volume (cm3/g) Cumulative % of pores pore volume undetected (from N2 (by N2 adsorption) adsorption)

initial help with spray drying, and EPSRC and PowdermatriX for the research grant (GR/S70920/01).

J. R. Groza, Sintering of Nanocrystalline Powder, Int. J. Powder Metall., 35 [7] 5966 (1999). 2 D. Liu, Densication of Zirconia from Submicron-Sized to Nano-Sized Powder Particles, J. Mater. Sci. Lett., 17, 4679 (1998). 3 J. G. P. Binner and B. Vaidhyanathan, Processing of Bulk Nanostructured Ceramics, J. Eur. Ceram. Soc., 28, 13293 (2008). 4 R. W. Rice, Forming and Pressureless Sintering of Powder Derived Bodies; pp. 99141 in Ceramic Fabrication Technology. Marcel Dekker, New York, 1992. 5 J. R. G. Song and J. Evans, A Die Pressing Test for the Estimation of Agglomerate Strength, J. Am. Ceram. Soc., 77 [3] 80614 (1994). 6 S. J. Lukasiewicz, SprayDrying Ceramic Powders, J. Am. Ceram. Soc., 72 [4] 61724 (1989). 7 S. Balasubramanian, D. E. Shaneeld, and D. J. Niesz, Effect of Externally Applied Plasticizer on Compaction Behavior of Spray Dried Powders, J. Am. Ceram. Soc., 85 [4] 74954 (2002). 8 S. Tanaka, Y. Togashi, Z. Kato, C. P. Chiu, N. Uchida, and K. Uematsu, Internal Structure of Zirconia Nano-Powder Compact Evaluated by an Infrared Microscope, Adv. Technol. Mater. Mater. Processing, 6 [2] 1803 (2004). 9 D. Liu, W. H. Lin, and J. Tuan, Interdependance Between Green Compact Property and Powder Agglomeration and Their Relation to the Sintering Behaviour of Zirconia Powder, Ceram. Int., 25, 5519 (1999). 10 A. Moritz and T. Nagy, Preparation of Super Soft Granules from Nanosized Ceramic Powders by Spray Freezing, J. Nanoparticle Res., 4, 43948 (2002). 11 N. Uchida, T. Hiranami, K. Tanaka, and S. Uematsu, Spray Freeze Dried Granules for Ceramics Fabrication, Am. Ceram. Soc. Bull., 81 [2] 5760 (2002). 12 R. L. K. Matsumoto, Generation of Powder Compaction Response Diagrams, J. Am. Ceram. Soc., 69 [10] C2467 (1986). 13 M. I. Santacruz, J. G. P. Annapoorani, and K. Binner, Preparation of High Solids Content Nano Zirconia Suspensions, J. Am. Ceram. Soc., 91 [2] 398405 (2008). 14 J. G. P. Binner, K. Annapoorani, and I. Santacruz, Method for Concentrating Nanosuspensions; Patent No. WO 2006/136780 A2, December 28, 2006. 15 British Standards Institution, BS EN ISO 787-11:1995, General Methods of Test for Pigments and Extenders Part 11: Determination of Tamped Volume and Apparent Density After Tamping. BSI, London, 1996. 16 J. L. Shi, Z. X. Lin, T. S. Qian, and W. J. Yen, Characterisation of Agglomerate Strength of Coprecipitated Superne Zirconia Powders, J. Eur. Ceram. Soc., 13, 26573 (1994). 17 E. P. Barrett, P. P. Joyner, and L. G. Halenda, The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms, J. Am. Chem. Soc., 73 [1] 37380 (1951). 18 T. Fengqiu, H. Xiaoxian, G. Yufeng, and Z. Jingkun, Effect of Dispersants on the Surface Chemical Properties of Nano-Zirconia Suspensions, Ceram. Int., 26, 937 (2000). 19 G. Bertrand, C. Filiatre, H. Mahdjoub, C. Foissy, and A. Coddet, Inuence of Slurry Characteristics on the Morphology of Spray Dried Alumina Powders, J. Eur. Ceram. Soc., 23, 26371 (2003). 20 A. Tsetsekou, C. Agraotis, A. Leon, and I. Milias, Optimisation of the Rhelogical Properties of Alumina Slurries for Ceramic Processing Applications, Part II: Spray Drying, J. Eur. Ceram. Soc., 21, 493506 (2001). 21 H. Mahdjoub, P. Roy, C. Filiatre, C. Betrand, and G. Coddet, The Effect of the Slurry Formulation Upon the Morphology of Spray-Dried Yttria Stabilised Zirconia Particles, J. Eur. Ceram. Soc., 23, 163748 (2003). 22 G. Bertrand, P. Roy, C. Filiatre, and C. Coddet, Spray-Dried Ceramic Powders: A Quantitative Correlation Between Slurry Characteristics and Shapes of the Granules, Chem. Eng. Sci., 60, 95102 (2005). 23 J. S. Walker Jr. and W. J. Reed, Inuence of Slurry Parameters on the Characteristics of Spray Dried Granules, J. Am. Ceram. Soc., 82 [7] 17119 (1999). 24 R. Xu and O. A. Di Guida, Comparison of Sizing Small Particles Using Different Technologies, Powder Technol., 132, 14553 (2003). 25 C. Washington, Particle Size Analysis in Pharmaceutics and Other Industries Theory and Practice. Ellis Horwood Limited, 1992, 114pp. 26 C. D. Sagel-Ransijn, A. J. A. Winnubst, B. Kerkwijk, H. Burggraaf, and A. J. Verweij, Production of Defect Poor Nanostructured Ceramics of Yttria-Zirconia, J. Eur. Ceram. Soc., 17, 8314 (1997). 27 C. Legros, C. Carry, H. Bowen, and P. Hofmann, Sintering of a Transition Alumina: Effects of Phase Transformation, Powder Characteristics and Thermal Cycle, J. Eur. Ceram. Soc., 19, 196778 (1999). &


OD SD5 SD14 SFD5 SFD14 Benchmark

380 380 380 380 380 380

53.4 55.3 54.9 55.1 55.1 56.3

0.14 0.13 0.14 0.14 0.14 0.13

0.11 0.11 0.10 0.13 0.13 0.01

21 15 28 7 7 92

Fig. 14. Pore size distribution in spray freeze-dried granules and their compacts.

pensions, the granules were not weak enough to be crushed during die pressing, even when using pressures as high as 380 MPa (existing presses in the ceramics industry typically use pressures of up to 250 MPa). In contrast, SFD yielded owable and crushable granules, although the owability and ll density were reduced, especially from the low solid content suspension. The analysis of the green nanostructures using electron microscopy, mercury porosimetry, and nitrogen adsorption isotherms showed that an homogeneous nanostructure was obtained from pressing the spray-freeze-dried granules. Optimization of the SFD parameters, including the solids content and organic content of the suspension to be sprayed, might yield granulated powders that have both improved owability and ll/tap density characteristics without sacricing the crushability of the granules.

The authors would like to thanks MEL Chemicals Ltd, U.K., for the provision of the precursor nanosuspension free of charge, CERAM Research, U.K., for