| 1. |
- Björk, Emma M., 1981-
(author)
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Mesoporous Building Blocks : Synthesis and Characterization of Mesoporous Silica Particles and Films
- 2013
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Doctoral thesis (other academic/artistic)abstract
- Catalyst supports, drug delivery systems, hosts for nanoparticles, and solar cells are just some examples of the wide range of exciting applications for mesoporous silica. In order to optimize the performance of a specific application, controlling the material’s morphology and pore size is crucial. For example, short and separated particles are beneficial for drug delivery systems, while for molecular sieves, the pore size is the key parameter.In this thesis, mesoporous silica building blocks, crystallites, with hexagonally ordered cylindrical pores were synthesized, with the aim to understand how the synthesis parameters affect the particle morphology and pore size. The synthesis of the particles is performed using a sol-gel process, and in order to increase the pore size, a combination of low temperature, and additions of heptane and NH4F was used. By variations in the amounts of reagents, as well as other synthesis conditions, the particle morphology and pore size could be altered. Separated particles were also grown on or attached to substrates to form films. Also, a material with spherical pore structure was synthesized, for the first time using this method.It was found that a variation in the heptane concentration, in combination with a long stirring time, yields a transition between fiber and sheet morphologies. Both morphologies consist of crystallites, which for the fibers are joined end to end, while for the sheets they are attached side by side such that the pores are accessible from the sheet surface. The crystallites can be separated to a rod morphology by decreasing the stirring time and tuning the HCl concentration, and it was seen that these rods are formed within 5 min of static time, even though the pore size and unit cell parameters were evolving for another 30 min. Further studies of the effects of heptane showed that the shape and mesoscopic parameters of the rods are affected by the heptane concentration, up to a value where the micelles are fully saturated with heptane. It was also observed that the particle width increases with decreasing NH4F concentration, independent of heptane amount, and a platelet morphology can be formed. The formation time of the particles decrease with decreasing NH4F, and the growth mechanism for platelets was further studied. The pore sizes for various morphologies were altered by e.g. variations in the hydrothermal treatment conditions, or the method for removing the surfactants.The separated particles can be attached to substrates, either during the particle synthesis or by post grafting prior to calcination. The film formation during the one-pot-synthesis was studied and a formation mechanism including nucleation of elongated micelles on the substrate was suggested. During the post grafting film synthesis, the medium in which the particles are dispersed, as well as functionalization of both particle and substrate are crucial for the post grafting process. The pores are easily accessible independent of the method, even though they are aligned parallel to the substrate when the one-pot-method is used, while post grafting gives a perpendicular pore orientation.In summary, this work aims to give an understanding for the formation of the synthesized material, and how to tune the material properties by alterations in parameter space. Successful syntheses of four different particle morphologies and two new types of films were performed, and the pore size could easily be tuned by various methods.
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| 2. |
- Abrikosov, Igor, et al.
(author)
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Phase Stability and Elasticity of TiAlN
- 2011
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In: Materials. - : MDPI. - 1996-1944 .- 1996-1944. ; 4:9, s. 1599-1618
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Journal article (peer-reviewed)abstract
- We review results of recent combined theoretical and experimental studies of Ti1−xAlxN, an archetypical alloy system material for hard-coating applications. Theoretical simulations of lattice parameters, mixing enthalpies, and elastic properties are presented. Calculated phase diagrams at ambient pressure, as well as at pressure of 10 GPa, show a wide miscibility gap and broad region of compositions and temperatures where the spinodal decomposition takes place. The strong dependence of the elastic properties and sound wave anisotropy on the Al-content offers detailed understanding of the spinodal decomposition and age hardening in Ti1−xAlxN alloy films and multilayers. TiAlN/TiN multilayers can further improve the hardness and thermal stability compared to TiAlN since they offer means to influence the kinetics of the favorable spinodal decomposition and suppress the detrimental transformation to w-AlN. Here, we show that a 100 degree improvement in terms of w-AlN suppression can be achieved, which is of importance when the coating is used as a protective coating on metal cutting inserts.
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| 3. |
- Ballem, Mohamed Ali, et al.
(author)
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Growth of Gd2O3 nanoparticles inside mesoporous silica frameworks
- 2013
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In: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 168, s. 221-224
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Journal article (peer-reviewed)abstract
- Gadolinium oxide (Gd2O3) nanoparticles with very small size and narrow size distribution were synthesized by infiltration of Gd(NO3)(3)center dot 6H(2)O as an oxide precursor into the pores of SBA-15 mesoporous silica using a wet-impregnation technique. High resolution transmission electron microscopy and X-ray diffraction show that during the hydrothermal treatment of the precursor at 550 degrees C, gadolinium oxide nanoparticles inside the silica pores are formed. Subsequent dissolution of the silica framework in aqueous NaOH resulted in well dispersed nanoparticles with an average diameter of 3.6 +/- 0.9 nm. If GdCl3 center dot 6H(2)O is used as precursor, GdOCl is formed instead of Gd2O3. The Gd2O3 nanoparticles showed a weak antiferromagnetic behavior, as expected.
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| 4. |
- Ballem, Mohamed A., et al.
(author)
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Influence of synthesis temperature on morphology of SBA-16 mesoporous materials with a three-dimensional pore system
- 2010
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In: Microporous and Mesoporous Materials. - : Elsevier BV. - 1387-1811 .- 1873-3093. ; 129, s. 106-111
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Journal article (peer-reviewed)abstract
- Spherical particles of mesoporous silica SBA-16 with cubic Im3m structure were synthesized at low pH using Pluronic F127 as template and TEOS as silica source. The diameter of the spherical particles can be controlled in the range of 0.5–8 μm by varying synthesis temperature from 1 °C up to 40 °C. A sharp transition from large particle sizes at approximately 20 °C to smaller ones is observed when the temperature is increased. It is suggested that this morphology transition is due to a change in hydrolysis and condensation rate of the silica source and as a result the assembly of F127 micelles will differ. The SBA-16 samples were characterized using powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption techniques.
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| 5. |
- Ballem, Mohamed A., et al.
(author)
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Low Temperature Nanocasting of Ultrafine Hematite Nanoparticles using Mesoporous Silica Molds
- 2012
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In: Powder Technology. - : Elsevier. - 0032-5910 .- 1873-328X. ; 217, s. 269-273
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Journal article (peer-reviewed)abstract
- Iron oxide (α-Fe2O3) nanoparticles with very small size, high crystallinity, and narrow size distribution were synthesized by infiltration of Fe(NO3)3.9H2O as an oxide precursor into mesoporous silica (SBA-15 and SBA-16) molds using a wetimpregnation technique. High resolution transmission electron microscopy shows that during the hydrothermal treatment of the precursor at 140 °C for 2 days, stable α-Fe2O3 nanoparticles inside the silica pores are formed. Subsequent leaching out of the silica template by NaOH resulted in well dispersed nanoparticles with an average diameter of ~ 4 nm.
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| 6. |
- Ballem, Mohamed A., et al.
(author)
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Mesoporous silica templated zirconia nanoparticles
- 2011
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In: Journal of nanoparticle research. - : SpringerLink. - 1388-0764 .- 1572-896X. ; 13:7, s. 2743-2748
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Journal article (peer-reviewed)abstract
- Nanoparticles of zirconium oxide (ZrO2)were synthesized by infiltration of a zirconia precursor(ZrOCl28H2O) into a SBA-15 mesoporous silicamold using a wet-impregnation technique. X-raydiffractometry and high-resolution transmission electronmicroscopy show formation of stable ZrO2nanoparticles inside the silica pores after a thermaltreatment at 550 C. Subsequent leaching out of thesilica template by NaOH resulted in well-dispersedZrO2 nanoparticles with an average diameter of*4 nm. The formed single crystal nanoparticles arefaceted with 110 surfaces termination suggesting it tobe the preferred growth orientation. A growth modelof these nanoparticles is also suggested.
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| 7. |
- Ballem, Mohamed A.
(author)
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Synthesis of Mesoporous Silica and their Use as Templates for Metal and Metal Oxide Nanoparticles
- 2011
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Doctoral thesis (other academic/artistic)abstract
- This thesis covers the synthesis and characterization of two types of mesoporous silica, SBA-15 silica with two-dimensional hexagonal arrangement, and SBA-16 silica with three-dimensional cubic arrangement. The obtained mesoporous materials were then used as hard templates for synthesizing of different types of nanostructures. In the first part, the effects of some synthesis parameters on the morphology and texture properties of the mesoporous silica have been studied. By varying the synthesis temperature solid spheres of SBA-16 with different sizes were synthesized and by additions of heptane as a swelling agent, SBA-16 in a hollow-sphere morphology with a large pore size was obtained. In the case of SBA-15, dispersed rods were synthesized in the presence of heptane and NH4F in a low-temperature synthesis. The length of the rods was varied by changing the concentration of HCl, and the pore size was tuned by changing the hydrothermal treatment time and temperature. Furthermore, the reaction time was decreased with a well-retained pore size and morphology. This work has resulted in SBA-15 rods with large pore sizes for this morphology. In the second part, SBA-15 and SBA-16 silica were used to synthesize different nanostructured materials such as metal and metal oxide nanoparticles. In fact, most of the work in this part is focused on the use of mesoporous silica as hard templates for synthesis of different types of nanoparticles. The synthesis of these nanoparticles was carried out by infiltration of a suitable precursor in the pores of the silica template. The mesoporous frameworks act as molds controlling the size and the final shape of the formed nanostructures. Subsequent dissolution of the silica templates by NaOH resulted in e.g., monodispersed zirconia, hematite, and cobalt nanoparticles with narrow size distributions. Functionalization of the SBA-15 surfaces was carried out in the synthesis of cobalt nanoparticles. This functionalization plays a crucial role on the infiltration and reaction of the reagents in the pores of the silica. By functionalization of the external surface, a highly hydrophobic surface was achieved, which proved to be sufficient to avoid formation of large cobalt particles outside the silica channels, while the internal functionalization enhances the attraction of cobalt ions to the silica pores, and as a result the nanoparticles grew inside these pores.
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| 8. |
- Ballem, Mohamed, et al.
(author)
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Synthesis of hollow silica spheres SBA-16 with large-pore diameter
- 2011
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In: Materials letters (General ed.). - : Elsevier Science B.V., Amsterdam.. - 0167-577X .- 1873-4979. ; 65:7, s. 1066-1068
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Journal article (peer-reviewed)abstract
- Hollow silica SBA-16 spheres with cubic ordered mesoporous shells were synthesized by an emulsion-templating method, using Pluronic F127 as a structure-directing agent. tetraethyl orthosilicateas as a silica source and heptane as a cosolvent in the presence of NH4F. The size of these spheres is in the range of 10 to 30 mu m. The shell is about 700 nm thick and consists of large pores, similar to 9 nm in diameter, arranged in a cubic order. After calcination, the spheres maintain their mesoporosity and show a high surface area of 822 m(2)/g. The formation mechanism of the silica hollow spheres is discussed.
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| 9. |
- Björk, Emma M., et al.
(author)
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Grafting mesoporous silica particles to substrates : a method for synthesizing mesoporous films with cylindrical pores perpendicular to the substrate
- 2013
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Other publication (other academic/artistic)abstract
- A method for synthesizing mesoporous silica films with cylindrical pores perpendicular to the substrate has been developed. The films consist of SBA-15 platelets that are grafted on glass substrates. The grafting is studied in terms of parameters such as pH, substrate functionalization, salt additions, time for TEOS prehydrolysis, and calcination. The best coverage of particles on the substrate was achieved for a low pH in combination with OTS-treated glass substrate. Furthermore, the prehydrolysis time of the TEOS was found to be a key parameter in order to bind the particles to the substrate. These porous films have potential in applications such as catalysis, drug delivery, and as a template for nanoparticle or nanorod, growth.
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| 10. |
- Björk, Emma M., et al.
(author)
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Tuning the shape of mesoporous silica particles by alterations in parameter space : from rods to platelets
- 2013
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In: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 29:44, s. 13551-13561
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Journal article (peer-reviewed)abstract
- The knowledge of how to control the pore size and morphology of separated mesoporous silica particles is crucial for optimizing their performance in applications, such as molecular sieves and drug delivery systems. In this work, we have systematically studied the effects of various synthesis parameters to gain a deeper understanding of how particle morphologies can be altered. It was found that the morphology for isolated particles of SBA-15 type, with unusually short and wide pores, could be altered from rods to platelets by variations in the NH4F concentration. The pore length is nearly constant (similar to 300 nm) for the different morphologies, but the particle width is increasing from 200 nm to >3 mu m when decreasing the amount of NH4F, and the pore size can be tuned between 10 and 13 nm. Furthermore, other synthesis parameters such as heptane concentration, pH, silica precursor, and additions of ions have also been studied. The trend regarding particle width is independent of heptane concentration, at the same time as heptane increases the particle length up to a plateau value of similar to 500 nm. In all, parameters controlling particle width, length, and pore size have been separated in order to evaluate their function in the particle formation. Additionally, it was found that the formation time of the particles is strongly affected by the fluoride ion concentration, and a mechanism for particle formation for this system, where micelles transform from a foam, to multilamellar vesicles, and finally to cylindrical micelles, is suggested.
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