| 1. |
- Andersson, Charlotte, et al.
(författare)
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Silicalite-1 membranes with small crystal size
- 2004
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Ingår i: Recent advances in the science and technology of zeolites and related materials. Part A. - Amsterdam : Elsevier. - 0444518274 ; , s. 626-631
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Konferensbidrag (refereegranskat)abstract
- Silicalite-1 membranes with small crystal size were prepared using a multiseeding method, where the support was repeatedly seeded and exposed to a short hydrothermal treatment up to five times. The film were characterized using SEM, single gas permeation, porosimetry and mixture separation experiment Films with three or four layers were of high quality i.e with minor defects according to the porosimetry experiments but showed poor separation of binary mixtures. This result may be attributed to the small crystal size and/or large amount of grain boundaries in the films.
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| 2. |
- Gualtieri, Magdalena Lassinantti, et al.
(författare)
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Crack formation in α-alumina supported MFI zeolite membranes studied by in situ high temperature synchrotron powder diffraction
- 2007
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Ingår i: Journal of Membrane Science. - : Elsevier BV. - 0376-7388 .- 1873-3123. ; 290:1-2, s. 95-104
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Tidskriftsartikel (refereegranskat)abstract
- Cracks are frequently formed in α-alumina supported MFI membranes during calcination. To better understand crack formation, in situ powder diffraction data were collected during calcination of a type of MFI membrane (ca. 1800 nm thick) which is known to crack reproducibly. In addition, data for MFI powder and a blank support were also collected. Both a synchrotron radiation facility and an in-house instrument were used. The unit cell parameters were determined with the Rietveld method, and the strain in the direction perpendicular to the film surface was calculated for the film as well as for the support. The microstrain in the support was also estimated. Based on the results obtained here, a model for crack formation in this type of MFI membrane was proposed. The lack of cracks in other types of MFI membranes (ca. 500 nm) prepared in our laboratory is also explained by the model. In thicker MFI films, the crystals are well intergrown. During heating, the MFI crystals contract and the α-alumina support expands. Consequently, a thermal stress develops in the composite which eventually leads to formation of cracks in the film and structural defects in the support. In thinner films, the crystals are less well intergrown and the thermal expansion mismatch leads to opening of grain boundaries rather than cracks.
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| 3. |
- Hedlund, Jonas, et al.
(författare)
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A masking technique for high quality MFI membranes
- 2003
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Ingår i: Journal of Membrane Science. - 0376-7388 .- 1873-3123. ; 222:1-2, s. 163-179
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Tidskriftsartikel (refereegranskat)abstract
- A procedure for the preparation of high quality zeolite membranes was developed. This procedure relies on a masking approach that fills all support pores with wax while leaving the top surface free for deposition of the zeolite film, thus, protecting the support from the synthesis mixture. Zeolite films of different thickness were grown on masked and non-masked supports using a seeded growth method. The zeolite-coated supports were calcined in order to remove the wax from the support and the template molecules from the zeolite. The membranes were characterized by SEM, XRD, single gas and multi-component permeation measurements. Support masking reduces the zeolite membrane thickness and the width of the cracks in the zeolite film. Thicker films, especially those prepared without masking, are defective. Masked membranes with a film thickness of 500 nm show no cracks or pinholes. These membranes have a H2 permeance of 220×10−7 mol/(s m2 Pa), an n-butane permeance of 9.8×10−7 mol/(s m2 Pa) and an n-butane/iso-butane separation factor of 9.0 at 25 °C. The separation factor for a mixture of n-hexane/2,2-dimethyl-butane was 227 at 400 °C and the n-hexane permeance was 5.6×10−7 mol/(s m2 Pa). The p-xylene permeance was 2.7×10−7 mol/(s m2 Pa) and the para/ortho separation factor was 17 at 400 °C for a mixture of xylenes.
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| 4. |
- Hedlund, Jonas, et al.
(författare)
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Factors affecting the performance of MFI membranes
- 2004
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Ingår i: Recent advances in the science and technology of zeolites and related materials. Part A. - Amsterdam : Elsevier. - 0444518274 ; , s. 640-646
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Konferensbidrag (refereegranskat)abstract
- Thin MFI membranes with varying morphology have been prepared using high flux alumina supports using all advanced synthesis procedure employing support masking and seeding. Evaluation of membrane quality by physical characterization and permeation measurements revealed a number of factors affecting the membrane performance. In the present work, the effects of film thickness, support type, preferred orientation and calcination rate are discussed. Some quality criteria for zeolite membranes are also debated and the porosimetry technique is discussed.
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| 5. |
- Hedlund, Jonas, et al.
(författare)
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Texture of MFI films grown from seeds
- 2005
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Ingår i: Current Opinion in Colloid & Interface Science. - : Elsevier BV. - 1359-0294 .- 1879-0399. ; 10:5-6, s. 226-232
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Tidskriftsartikel (refereegranskat)abstract
- This review describes how the texture of MFI films grown from seed crystal is developed during film preparation. Reports published during the last 5 years are in focus. Relative growth rates in various crystallographic directions, competitive growth, properties of the seed layer, defects, grain boundaries and other parameters influencing the film properties are discussed. Mathematical models describing competitive growth are also discussed. Suitable characterization methods for defects are described. The last part of the review is devoted to diffusion. Diffusion models accounting for texture in MFI films and the influence of texture on diffussion are discussed.
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| 6. |
- Jareman, Fredrik, et al.
(författare)
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Effects of aluminum content on the separation properties of MFI membranes
- 2003
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Ingår i: Separation and Purification Technology. - 1383-5866 .- 1873-3794. ; 32:1-3, s. 159-163
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Tidskriftsartikel (refereegranskat)abstract
- MFI membranes with almost identical film thickness and defect distribution but different Si/Al ratio were evaluated by separation of butane and hexane isomers. Film thickness was evaluated by SEM and defect distribution by porosimetry. When the temperature was varied, the membranes showed similar separation trends for butanes, but clear differences were observed for hexane separation. The hexane separation factor varied with temperature for the silicalite-1 membrane but was constant for the ZSM-5 membrane. It is believed that this difference may be a result of differences in adsorption properties.
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| 7. |
- Jareman, Fredrik
(författare)
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MFI-molecular sieve membranes : synthesis, characterization and modelling
- 2002
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This work concerns evaluation by permeation measurements and modeling of thin (<2µm) MFI molecular sieve membranes and, to a smaller extent, synthesis of such materials. The membranes have been synthesized on graded a-alumina microfiltration filters using The seed film method. Scanning electron microscopy and x-ray diffraction were used for characterization in addition to permeation measurements. Mathematical models describing membrane flux for real membranes and defect distributions were developed. Defect distributions were calculated from porosimetry data and were further used for prediction of single gas permeation characteristics for real membranes. The models confirm the experimental findings, with respect to ideal selectivities as a measurement of membrane quality. Membrane permeation simulations indicate increasing ideal selectivities, with increasing film thickness, for quotients containing SF6. Thereby a high quality membrane could possess low ideal selectivities. This finding was confirmed by comparing experimental data of several membranes with varying thickness. The correlation between multi component separation data and commonly used quality criteria was investigated. It was found that commonly used single gas permeation quotients (ideal selectivity) between light inorganic gases, especially those containing sulphurhexaflouride (SF6), is less appropriate for membrane quality measurement. The porosimetry experiment showed on the other hand a good agreement between experimental data and separation performance of the membranes, as expected. ZSM-5 membranes with low aluminum content and silicalite-1 membranes with similar material properties, such as defect distribution and thickness were evaluated with multi component hydrocarbon isomers permeation. The ZSM-5 membrane had lower permeances and a slightly better butane isomer separation performance than the silicalite-1 membrane. The latter membrane showed a minimum in separation selectivity between two C6 isomers whereas the ZSM-5 membrane showed an almost constant selectivity, independent of temperature, but with lower permeances. ZSM-5 membranes with a high aluminum content catalyzed the formation of diethylether and ethylen at temperatures exceeding 150°C from a water/ethanol mixture. The membrane separated a mixture of C4 isomers with good performance at elevated temperatures. However these membranes suffered from temperature instability problems.
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| 8. |
- Jareman, Fredrik, et al.
(författare)
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Modelling of single gas permeation in real MFI membranes
- 2004
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Ingår i: Journal of Membrane Science. - : Elsevier BV. - 0376-7388 .- 1873-3123. ; 236:1-2, s. 81-89
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Tidskriftsartikel (refereegranskat)abstract
- A novel permeation model for flow through defects and zeolite pores in real MFI membranes, also accounting for substrate effects has been developed. Defect distributions for two types of MFI membranes were determined from porosimetry data using the model, which incorporated the Horvath Kawazoe (micropores) or the Kelvin equation (mesopores). The narrowest (1.08 nm) and also most common defects were found to be separated with a distance of 10–40 μm according to the model. Diffusion coefficients for hydrogen, helium, nitrogen and SF6 in the zeolite were further determined from single gas permeation data using the model using the independently determined defect distribution. The coefficients are consistent with values previously reported in the literature.
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| 9. |
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| 10. |
- Jareman, Fredrik, et al.
(författare)
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Permeation of H2, N2, He and SF6 in real MFI membranes
- 2005
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 83:1-3, s. 326-332
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Tidskriftsartikel (refereegranskat)abstract
- This work shows that a previously developed model for single gas permeation in real MFI membranes is applicable to an arbitrary MFI membrane with a different film thickness and defect distribution. The model can predict the flow of H2, N2 and He resonably. Deviations in SF6 flux for thick and oriented films were observed and attributed to a lower diffusion coefficient for the narrower pores in the a-direction of the MFI crystals. By guidance from the model, variations in previously reported single gas permeance ratios for selected membranes can now be attributed to variations in feed pressure, film thickness preferred orientation and defect distribution. It was found that high feed pressures and thick oriented films resulted in large single gas permeance ratios with SF6 in the denominator, even though these membranes were more defective than thinner membranes with more randomly oriented crystals. In general, single gas permeance ratios are strongly dependent on material properties and experimental conditions. These ratios can only be used for comparison of membranes with similar morphology and the ratios must be measured under identical conditions.
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| 11. |
- Jareman, Fredrik
(författare)
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Properties and modeling of MFI membranes
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The permeation properties of thin (<2µm) film MFI molecular sieve membranes have been studied in the present work and a model has been developed. The synthesis of such materials has been studied to a smaller extent. The films have been grown on graded a-alumina microfiltration filters using a seeding method. Scanning electron microscopy and x-ray diffraction were used in addition to permeation measurements for characterization of the materials. In particular, a simple and unique model describing single component permeation was developed. The model is a combination of simple and basic equations for permeation and adsorption. The important defect distribution of the membrane and the properties of the support are measured in separate experiments. The model is unique since it is accounting for the effect of defects and support on the permeation properties. The model can adequately describe the performance of various MFI membranes. The model indicates mass transfer limitations of the supports that strongly affect, for instance, permeance ratios. It was also found that these ratios are dependent on crystallographic orientation, film thickness and experimental conditions in addition to the amount of defects. Permeance ratios can thus only be used to compare membranes with similar morphology and tested under similar conditions. It was found that defects formed in thicker films. Membranes prepared on masked substrates were of higher quality than membranes prepared on unmasked substrates. MFI membranes with low and varying aluminum content with similar material properties, such as defect distribution and thickness, were evaluated with multi-component hydrocarbon isomers permeation. The silicalite-1 membrane showed a minimum in separation selectivity between two C6 isomers whereas the ZSM5 membrane showed an almost constant selectivity, independent of temperature, but with lower permeances. The effect of the calcination rate on the membrane quality was investigated for silicalite-1 membranes. Based on a number of permeation characterization techniques, the membrane quality was independent of the calcination rate. It was found that the permeation properties of membranes comprised of small crystals in several layers were different from membranes comprised of one layer of larger crystals, although the quality of the membranes was similar. ZSM-5 membranes with high aluminum content showed catalytic conversion of ethanol into diethylether and ethylene under simultaneous separation of the ethanol / water azeotrope
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| 12. |
- Jareman, Fredrik, et al.
(författare)
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Single gas permeance ratios in MFI membranes: Effects of material properties and experimental conditions
- 2005
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 82:1-2, s. 201-207
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Tidskriftsartikel (refereegranskat)abstract
- A previously developed mathematical model with parameters fitted to experimental data was used to study effects of material properties and experimental conditions on single gas permeance ratios of MFI membranes. The model showed that single gas permeance ratios are highly dependent on substrate morphology, feed pressure, crystallographic orientation and defects in the film. It was found that the pore size and the thickness of the substrate affected permeance ratios, due to mass transfer resistance in the substrate. The applied feed pressure also had a significant effect on the permeance ratios. This is due to differences in mass transfer resistance of the substrate and adsorption characteristics with varying feed pressures. The crystallographic orientation of the zeolite film also affected permeance ratios due to changes in diffusivity with varying orientation of the crystals in the film. Finally, the effect of defects was investigated. As expected, it was found that the permeance ratios decreased when more defects were added in the model. However, if the membrane is not very defective, the permeance ratio is much more affected by the substrate and by variation in pressure drop than by defects. The results in the present work show that single gas permeance ratios cannot be used directly as a benchmark of membrane quality unless all other parameters are kept constant.
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| 13. |
- Jareman, Fredrik, et al.
(författare)
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The influence of the calcination rate on silicalite-1 membranes
- 2005
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 79:1-3, s. 1-5
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Tidskriftsartikel (refereegranskat)abstract
- Silicalite-1 films with a thickness of 500 nm on asymmetric α-alumina micro filtration filters were calcined at 500 °C with heating and cooling rates varying between 0.2 °C/min and 5.0 °C/min. The membranes were characterized with single gas permeation, porosimetry, and xylene isomer separation experiments. It was found that the quality of the prepared membranes was independent of the heating/cooling rate according to the single gas permeation and porosimetry characterization. Xylene isomer separation data was found to vary between the samples, but none of the variations could be attributed to the heating/cooling rate during calcination since the variations did not follow a trend but occurred randomly. It is thus concluded that the calcination rate does not influence the quality of these membranes.
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| 14. |
- Lassinantti-Gualtieri, Magdalena, et al.
(författare)
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Accurate measurement of the thermal expansion of MFI zeolite membranes by in situ HTXRPD
- 2004
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Ingår i: Recent advances in the science and technology of zeolites and related materials. Part A. - Amsterdam : Elsevier. - 0444518274 ; , s. 703-709
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Konferensbidrag (refereegranskat)abstract
- Template removal by calcination of MFI type membranes is often accompanied by crack formation. The thermal behavior of MFI type membranes, synthesized with and without masking, was studied to understand the mechanism. Masking prevents growth of zeolite in the interior of the Support during membrane synthesis. Rietveld refinements of powder diffraction data collected in situ at high temperature allowed to accurately determine the change in thermal expansion of the MFI film and the porous alpha-alumina support. During heating, a relatively large contraction of the cell volume during template removal occurred in the zeolite powder and in the film of the membrane prepared with masking. The much smaller decrease in the non-masked sample indicates that this membrane is under stress during heating and as a consequence, cracks are formed. The stress imposed in the membrane prepared without masking may be due to the opposite thermal behavior of the Substrate in combination with strong bonds between the membrane and the support.
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| 15. |
- Lassinantti, Magdalena, et al.
(författare)
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Preparation and evaluation of thin ZSM-5 membranes synthesized in the absence of organic template molecules
- 2001
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Ingår i: Catalysis Today. - 0920-5861 .- 1873-4308. ; 67:1-3, s. 109-119
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Tidskriftsartikel (refereegranskat)abstract
- Porous α-alumina supports with a pore size of 100 nm were seeded with colloidal TPA-silicalite-1 crystals with a size of 120 nm. The seeded supports were calcined and treated in a synthesis solution free from organic template molecules to form ZSM-5 films on the supports. According to SEM images, the films were about 2 μm thick and no defects could be found on the as-synthesized membranes. Single gas permeation data was collected and good quality membranes (defined as having a non-detectable permeance of SF6 after drying at 100°C) were further evaluated using binary/ternary gas mixtures. The selectivity for n-butane/i-butane had a maximum value of 17.8 at 220°C. Water was selectively separated from a helium-diluted vaporized water/ethanol azeotrope with a maximum selectivity of 12.4.
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| 16. |
- Rezai, Seyed Alireza Sadat, et al.
(författare)
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Water/hydrogen/hexane multicomponent selectivity of thin MFI membranes with different Si/Al ratios
- 2008
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Ingår i: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 108:1-3, s. 136-142
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Tidskriftsartikel (refereegranskat)abstract
- MFI films with a thickness of about 550 nm were prepared on α-alumina substrates. The surface Si/Al ratios (XPS) were 157 and 62 for silicalite-1 and ZSM-5 films, respectively, and in accordance, XRD data indicated lower ratios for ZSM-5 films. Higher ratios were observed by ICP-AES for crystals grown in the bulk of the synthesis mixtures. Six membranes of each type were prepared. Porosimetry measurements showed that all membranes were of high and similar quality. Single gas permeances for H2, N2, He, CO2 and SF6 at 25 °C were very similar within each type of membranes. However, the average hydrogen permeance was 27% lower and the average H2/SF6 single gas permeance ratio was 67% higher for ZSM-5 membranes. These differences are attributed to a narrower effective pore diameter for the ZSM-5 membranes due to the sodium counter ions. Separation of mixtures of H2O, H2 and n-hexane (helium balance) was investigated in the temperature range 25-350 °C. The highest separation factors α-H2O/H2 were observed at 25 °C and were 14.3 and 19.7 for silicalite-1 and ZSM-5, respectively. The membranes were selective also at 100 °C and the separation factors were about 3.2 and 6 for silicalite-1 and ZSM-5, respectively. However, the selectivity decreased at elevated temperatures and the separation factor approached 1 at temperatures above 180 °C for both membrane types. The observed water selectivity was attributed to weak adsorption of water on polar sites. A low (1.5-3) α-H2O/n-C6 separation factor was observed for both membrane types for the entire investigated temperature range.
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| 17. |
- Sterte, Johan, et al.
(författare)
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Application of the seed-film method for the preparation of structured molecular sieve catalysts
- 2001
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Ingår i: Catalysis Today. - 0920-5861 .- 1873-4308. ; 69:1-4, s. 323-329
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Tidskriftsartikel (refereegranskat)abstract
- The seed-film method has been applied for the preparation of various materials of potential interest as structured molecular sieve catalysts. The method has proven to be very flexible and allows for the reproducible preparation of a number of molecular sieve–substrate combinations as well as the control of the materials’ properties of importance in catalytic applications such as zeolite loading, film thickness, film density and crystal orientation. The preparation of thin molecular sieve films on ceramic foams, α-alumina pellets and porous alumina supports as well as various metal surfaces is described. The preparation of zoned coatings with a compositional gradient is also discussed.
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