Jennifer Hanson Student Number: 0631824 12/16/2011 MSE 502: Sol-Gel Processing 1.

Electrophoretic deposition is often used to combine with sol-gel processing to make thicker films to overcome the limitation of dip or spin coating methods, which are commonly used for thin film fabrication. Please explain: (1) Why sol-gel film thickness is limited when fabricated by dip or spin coating? Spin coating applies a uniform thin film to flat substrate. An excess amount of a solution is placed on the substrate, then the system (substrate + excess solution) is rotated at high speed to spread the fluid by centrifugal force. The excess solution spins off the edges of the substrate during rotation, and rotation is stopped once the desired thickness has been reached. Viscosity and spin speed (angular velocity) are the main parameters affecting film thickness. The range of film thicknesses easily achieved by spin coating is 1-200mm. For thicker films, high viscosity, low spin speed, and a short spin time are needed. Beyond this limit several problems arise including skin formation (differences in the properties of the spinning material near the air interface and the properties of the bulk fluid), cracking, uneven film distribution. The film can be modeled as a Newtonian liquid or non-volatile liquid, providing us with the following equation for thickness h: = 1
! ! !

3 ! 2 ! ! !

h = thickness rA = mass of volatile solvent per unit volume rAo = initial mass of volatile solvent per unit volume wA = angular velocity n = viscocity e = evaporation rate In dip coating, the substrate is immersed in the coating material solution, allowed to rest in it for a while, and then carefully pulled out/up from the solution. The thin layer deposits itself on the substrate while it is pulled up. The speed determines the thickness of the coating (thicker coating material requires faster withdrawal). Excess liquid will drain from the surface and the solvent evaporates from the liquid to form the thin layer. Dip coating forms a gel network with weak structure and removal of the solvent causes a stress gradient that can lead to easier cracking of the film. For dip coating, the liquid coating material is assumed to be a Newtonian liquid. The sol isnt Newtonian so it has

added surface tensions and stressors that cause the stress gradient and the cracking. Thus we can find its critical hardness: ! = !"
!

hc = critical thickness klc = hardness = tensile strength = ratio of elastic mod. of substrate to film Cracks will form for any thickness h such that h > hc. Thus we have a limiting factor on the thickness (typically ~500nm or less). (2) What is the mechanism of electrophoretic deposition? Colloidal particles suspended in a solution often carry a net charge. Under the influence of an electric field, these charged particles move towards the oppositely charged electrode and get deposited as film on the electrode. The particles themselves carry an electric charge and the direction that each particle travels is dictated by its charge. Positively charged particles will migrate towards the negatively charged electrode (catophoresis) and negatively charged particles will move towards the anode (anophoresis). (3) What are the major differences between electrophoretic deposition and electrochemical deposition? Electrochemical deposition (electroplating) is a process in which metal ions in a solution are moved by an electric field to coat an electrode. Electrical current is used to reduce cations of the desired material from a solution and coat a conductive object with a thin layer. In electrophoresis solid particles are moving with no cumulative/total charge transfer. The required conductance of the liquid medium is low. The preferred liquid is organic and the typical deposition rate is on the order of 1000 m/min. In electroplating ions are the moving species. The charge transfer is ion reduction. The required conductance of the liquid medium is high. The preferred liquid/solvent is water. The typical deposition rate is order of 0.1 m/min. Electrophoretics is used for both organics and metals while electroplating is for metals. Electrophoretics deposits the material without having it dissolve into ions. (4) What are the parameters determining the mobility of a particle in a sol?

Ultimately the Gibbs free energy controls the mobility and reactivity of particles in the sol. Reactions and transitions that reduce this energy are favorable. The Gibbs free energy is high for solutions with solute exceeding the solubility or supersaturated possesses. To reduce the overall system energy the solute is segregated from the solution. This is the driving force for both nucleation and growth of particles. However, it is counter-balanced by the introduction of surface energy of these segregated particles. The newly formed nucleus (eg segregated particle) is stable only if its radius exceeds a critical size with radius r*(sizes larger than r* result in continued growth and lower than r* in dissolution). This critical size can be modified through reducing the surface energy, using different solvents/additives, or incorporating impurities into the solid phase. Thus the Gibbs free energy and the surface energy are the driving parameters for the particle mobility (eg the particle will either be above the critical combination of these parameters and continue to grow larger or it will dissolve). Total change of chemical potential for the formation of the nucleus G as well as the critical radius and energy for nucleation are: G = v + s = (4/3)r3Gv + 4r2 r* = -2/Gv G* = 16/3(Gv)2 Gv = change of Gibbs free energy per unit volume of the solid phase = surface energy per unit area v = change of Gibbs free energy or volume energy r = radius of spherical nucleus formed s = surface energy of the system r* = critical radius G* = critical energy, the energy barrier that a nucleation process 2. For the fabrication of complex oxides or organic-inorganic hybrids, multiple precursors are used. Different precursors possess different chemical reactivity; some are more reactive than others. Please briefly describe and explain: (1) What affects the chemical reactivity of a family of given element precursors, for example, titanium alkoxides? The chemical reactivity of a family of given element precursors can be affected by chemical reactions within the family itself due to pH dependence and polar functional groups such as -OH. Precursors with multiple polar oxide bonds can take on different pH dependent forms (eg in extremely acidic environments the full protonated hydroxide M-OH is preferred while in extremely basic environments the deprotonated form M-O- is preferred) as can be seen

for titanium alkoxides. These different forms can go on to react with one another forming dimers (~M-O-M~) and even more complicated network structures. Titanium alkoxides are polar and can be easily reacted with water to produce hydroxides or hydrated oxides: Ti(OR)n + H20 Ti(OH)n + nR(OH) However, the hydrolysis of titanium alkoxides is very complex as these reactions produce polycondensates whose chemical compositions are a function physical size and polymeric morphology. During the hydrolytic condensation an inorganic network can be formed by a chain of hydrolysis and polymerization reactions: ~Ti-OR + H2O ~Ti-OH + R(OH) ~Ti-OH + RO-Ti ~ ~Ti-O-Ti~ + R(OH) (2) What are the typical approaches to manipulate and modify the chemical reactivity of precursors? In a general sense, any chemical reaction that does not set off the polymerization of the sol (eg start the whole sol-to-gel process) will give us a slightly different set of precursors with correspondingly different chemical reactivities. Inorganic salts are highly reactive. They can be converted (or partially converted) to alkoxides via acid-base reactions to reduce the chemical reactivity. Organometallic precursors can be modified via ligand substitution reactions in which one or more organic ligand groups are removed from the metal center and replaced with different groups. This can either increase or decrease the chemical activity of the organometallic precursor. Simple, small ligands often increase reactivity as they can be easily removed/replaced or temporarily shifted into higher-energy complex configurations during a reaction. Chelating ligands can sterically affect the precursor. Nucleophilic substitution is the reaction of an electron pair donor (nucleophile) with an electron pair acceptor (electrophile). The nucleophile selectively bonds with or attacks the positive charge of the leaving group electrophile. This can either occur via SN1 or SN2 and is a very common organic reaction changes the chemical reactivity of organic precursors. Hydrolysis replaces ligands of the precursor with OH groups in an exothermic reaction. Condensation is the reverse of hydrolysis and forms larger molecular oxides. Last, we can always consider changes in pH affect the reactivity of most precursors and affect all the reactions mentioned above.

3. Sol-gel processing is widely used to synthesize and fabricate dense or porous films, nano- to miscrosized particles or fibers. Please briefly describe: (1) What are the fundamental considerations for the synthesis and fabrication of dense or porous structures? In a typical sol-gel process, the precursor is subjected to a series of hydrolysis and polymerization reactions to form a colloidal suspension, or a sol. If these hydrolysis/condensation reactions are not diffusion-limited, dense materials are formed. While more porous structures are diffusion controlled. The initial pore size is largely dependent on the size of nanoclusters formed in the sol and how well they are packed. Take silica for example, when silicon alkoxide precursors are hydrolyzed/condensed with an acid catalyst, a linear silica chain forms. This linear chain easily collapses upon solvent removal, providing a dense material. When a catalyst base is used, highly branched nanocluster structures form, giving highly porous materials. Further processing of the sol makes it possible to make materials in different forms. When the sol is cast into a mold, a wet gel forms. With further drying and heat treatment, the gel is converted into dense materials. If the liquid in a wet gel is extracted under a supercritical condition, a highly porous and extremely low-density material called aerogel is obtained. After the initial drying, compaction can still be made by pressing and sintering, hot pressing, and hot isostatic pressing. Sintering/annealing at high temperatures remove porosity (the pores collapse) in the material, increasing the densification. (2) What are the considerations to ensure the formation of nanoparticles? Nanoparticles are defined as particulate dispersions or solid particles with a size in the range of 1-10 nm. Thus the primary consideration is to maintain this size limitation when forming and aging particles in the sol-gel process. The size distribution of nanoparticles is dependent on the subsequent growth process of initial nuclei. The process involves the generation of growth species, diffusion of the growth species from bulk to the growth surface, adsorption of the growth species onto the growth surface, and surface growth through irreversible incorporation of growth species onto the solid surface. This can be simplified into the process of diffusion (supplying the growth species to the growth surface) and growth (growth of adsorbed species on the growth surface in a solid structure). The growth can either be diffusion-controlled (which promotes uniformly sized particles) or surface-controlled (concentration on the surface is the same as in the bulk, gives a larger distribution) and is environment-dependent (eg add a new solvent/impurity/etc to

get different growth). Surface-controlled growth consists of both mono- and poly- nuclear growth. Ultimately to stop this growth, we need to cap the nanoparticles. This can be done with various organic ligand groups that react/attach to the outermost layer of the nanoparticle, preventing more layers from forming. (3) What are the requirements for the fabrication of sol-gel derived nano- or micrsosized fibers? Fibrous gels are drawn from the sols around room temperature, and then are converted to glass or ceramic fibers by heating at several hundred to one thousand degrees centigrade. The fibers can also be formed through low or high temperature drawing or unidirectional freezing of the gel. Controlling the viscosity of the sol is highly important, as the sol must be spinnable or drawable to form fibers. The viscosity of the gel increases with time as the hydrolysis polycondensation reactions proceed. When the solution starts to become sticky (~10 poise), it is spinnable and fibers can be drawn from the solution. Problematically, hydrolysis continues and the gel viscosity increases with time. Thus the synthesis of fibers is extremely time dependent. Overly viscous solutions produce elastic gels, which are incapable of forming fibers. During the formation of the fiber, the solvent is lost from the skin into the core. Thus the outer skin can become rigid if there is not enough water available internally for gelation and the fiber bloats (bad). By having a gel with higher water content the fiber dries more uniformly. (4) What are the other approaches to promote a dense structure or to retain porous skeletons without subject to sintering at high temperature? Incorporating organic components into an inorganic gel network can facilitate pore size and porosity. They manipulate the inbalance between the large capillary force and the small mechanical strength of the gel network, preventing collapse during solvent removal. These organic components can be introduced via physical trapping or chemical bonding. For example, alkyl chains can be incorporated into silica network to form relative dense organicsilica hybrids. The porous structures can then obtained through pyrolysis where the organic components are burnt off. Organic groups can also have catalytic effects, promoting hydrolysis and condensation reactions. Long-chained organic ligands can either be a steric diffusion barrier or increase the viscosity of the sol, resulting in a diffusion-limited process. This changes the porosity without subjecting the material to heat-treatment at elevated temperatures.

4. Sol-gel derived materials are commonly porous with pores sizes ranging from micropores (<2 nm in diameter), mesopores (2-50 nm in diameter) and macropores (>50 nm in diameter), and a variety of techniques can be applied to the characterization of such porous structure. (1) How the specific surface area is determined from the gas sorption? specific surface area: surface area per unit mass (eg m2/g) gas sorption: phenomenon of a gas being taken up by a solid, simultaneously entering the solid(absorption) or remaining on the outside attached to the surface(adsorption) Experimentally, the desired material is heated and degassed to remove adsorbed foreign molecules. Next controlled doses of an inert gas (eg nitrogen or argon) are introduced. This gas is adsorbed and desorbed in a vacuum chamber at constant, low temperature. We vary the pressures to generate desorption isotherms and determine the pressure variations due to ad/desorption of the gas molecules by the material. Applying an adsorption model to this information allows us to determine the specific surface area. The most common model is the Brunauer, Emmett, and Teller (BET) equation for a multilayer surface: 1 1 = + ! ! ! ! = exp ! !

P = adsorption pressure P0 = saturation vapor pressure c = BET contstant n = amount adsorbed (moles per gram of adsorbent) at the relative pressure P/P0 nm = monolayer capacity (moles of molecules needed to make a monolayer coverage on the surface of one gram of adsorbent) E1 = heat of adsorption for the first layer EL = heat of the adsorption for the second and higher layers = heat of liquefaction R = gas constant T = temperature The value nm can be found via the slope and intercept of a plot of P/[n(PO-P)] against (P/PO). We can then plug this into the following equation for the specific surface area: = ! ! S = specific surface area Na = Avogadros number

 = area occupied by one adsorbate molecule

(2) Why a hysteresis is observed in some sol-gel derived materials, but not in others? Hysteresis is the historical dependence such that a physical system is dependent upon both its current and past environment. Pyroelectric materials generate voltage when heated or cooled; thus exhibiting a historical dependence on temperature and showing hysteresis. A subset of these pyroelectrics, ferromagnetic materials exhibit hysteresis when an external magnetic field is applied, the atomic dipoles align themselves with it. When the field is removed, part of the alignment is retained and the material has been magnetized. Similarly ferroelectric materials exhibit hysteresis as the direction of their spontaneous polarization can be reversed via an applied electric field, giving a hysteresis loop. Thus hysteresis is observed for sol-gel derived materials with these properties. Usually the gas adsorption process is considered completely reversible, but under some conditions the isotherm may exhibit a different shape in desorption vs adsorption. This is adsorption hysteresis. While its causes are still being investigated, it has linked to differences in the nucleation and evaporation mechanisms inside the mesopores. Materials without special properties (eg pyroelectricity, ferroelectricity) or adsorption hysteresis can still be derived from sol-gel processing and they do not exhibit hysteresis. (3) With sol-gel derived membrane using Knudsen diffusion to separate nitrogen and oxygen, the separation factor is found smaller than theoretical number, what are the possible reasons? The theoretical separation factor from the Knudsen diffusion is based on the inverse square root ratio of the two molecular weights for a binary mixture. Thus separation process is limited to systems with large values for the molecular weight ratio as molecules with similar weights will have similar diffusivity and hence wont separate well. Nitrogen and oxygen have extremely similar weights (N2 = 14.01 g/mol, O2 = 16.00 g/mol), so their theoretical separation factor is fairly small (0.94 for O2/N2). The Knudsen model does not take into account relative reactivity or sorption of the species being separated with the membrane (it assumes that the molecules will hit the sides of the pore and not stick or at stick at the same rate). If the membrane adsorbs/absorbs N2 at a higher rate than O2, this will lower the separation factor. The Knudsen model only works under extremely low pressure. When the gas pressure is high, molecule-molecule collisions dominate compared to the molecule-pore wall collisions; Fickian diffusion dominates. If the experiment was performed under even moderate pressure, this would affect the separation factor.

(4) When sol-gel derived oxide membranes were used at moderately high temperature for a long period of time, gas flux (the amount of gas flow through unit area) increased, though the thickness and index of refraction of the membrane did not change at all, give a brief explanation. index of refraction n = speed of light in a vacuum / speed of light in material The oxide membrane can undergo gas sorption, namely of the atmospheric gases including O2 and N2. As the gas is pumped through the membrane, more of its particles stick adsorb and absorb into the membrane. Initially the membrane was empty in the sense that a significantly smaller amount of gas particles travelled through at previous pressure as compared to the new gas flux. Thus the membrane could absorb/adsorb the pumped in gas particles at a greater rate and the system of the membrane/pumped gas is out of equilibrium. Over a long period of time and constant pressure of gas being pumped into the membrane, the system equilibrated. At equilibrium some gas particles already are adsorbed/absorbed with the membrane, thus the new particles being pumped in cannot react as much when compared to starting the gas flux. Thus they move through the membrane more quickly and gas flow is increased. Since its just atmospheric gas particles that are absorbed, there is no change in the refractive index. Light used in measuring the index has to go through air to get to/through the membrane, so were not going to be able to measure any difference in the index. Similarly the thickness of the material is not changed as we fundamentally havent changed the material (eg no irreversible chemical reactions). Once the gas flux is removed, the membrane will re-equilibrate to the previous conditions.

Note: (1) I prefer concise answers, but you do need to make your points clear. (2) I also prefer the answers typed or printed, if your handwriting is not easy to follow. (3) Please not copy from internet, as I can find the same information online by myself.