You are on page 1of 38

Chapter 9: Sol-gel and other processes for ceramic synthesis

9.1 9.2 9.3 9.4 9.5 Introduction Solid state reactions for ceramic synthesis Precipitation methodforced hydrolysis Sol-gel process Pechini method

Ceramic Materials
A long history and a great future

Universiteit Twente

Ceramics

Ceramics are inorganic (non-metallic) materials, which are able to withstand elevated temperatures (in excess of 500 C) They are availabe as bulk or as coating For bulk ceramics (in most cases also for coatings) a powder is brough into a form and subsequently a temperature treatment is given (< Tmelt): The Ceramic Fabrication Process

9.1 Solid State Reactions


Direct reaction of solids to form the final product. In principle no decomposition is involved. Solids do not react with solids at room temperature even of thermodynamics is favorable. High temperature must be used. Solid-solid reactions are simple to perform, starting materials are often readily available at low cost and reactions are clean i.e. do not involve other chemical elements. Disadvantages include the need for high temperatures, the possibility of non-homogeneity, contamination from containers etc.

Solid State Reactions: example


Synthesis of YBCO, YBa2Cu3O7-x Direct reaction between Y2O3, BaO2, CuO (Reaction between three solid components) Grind to obtain large surface area Press into pellets (contact) Heat in alumina boat, temperature profile:

Other precursors may be used, e.g. BaCO3, which may be decomposed to fine grained BaO during the reaction.( + nitrates etc.) Decomposition must be performed in a controlled manner in order to avoid violent decomposition (i.e. choosing an appropriate temperature)

Solid State Reactions: general aspects

x 2 = kt

Solid State Reactions: general aspects

Solid State Reactions: general aspects


Ions in solids are not mobile at low temperatures. High temperatures, as a rule of thumb, at 2/3 of the melting temperature (of one component) the diffusion is sufficient to achieve solid state reactions. Formation of BaTiO3 by reacting BaCO3 and TiO2 is an example of a seemingly simple reaction is more complex than expected. BaCO3 is decomposed to reactive BaO: (Rock salt, ccp of the oxide anions, Ba2+ in octahedral sites), TiO2 (Rutile, hcp of oxide ions, Ti4+ in half of the octahedral sites) At least three stages are involved in formation of BaTiO3 from BaO and TiO2. BaO react with the surface of TiO2, forming nuclei and a surface layer of BaTiO3. Reaction between BaO and BaTiO3 to form Ba2TiO4. This is a necessary phase for increasing migration of Ba2+ ions. Ba2+ ions from the Ba-rich phase migrate into the TiO2 phase and form BaTiO3.

Solid State Reactions: general aspects


Reaction rates depends on: Area of contact between the reacting solids, i.e. surface area and density (How to increase surface area?) The rate of nucleation (How to increase rate of nucleation?) Rates of diffusion of ions (and other species) (How to increase?) Disadvantages, e.g.: Nucleation and diffusion related problems (high temperature) Formation of undesired phases (reaction paths) (e.g. BaTi2O5) Homogeneous distribution, especially for dopants, is difficult Difficult to monitor the reaction directly, in-situ?? Separation of phases after synthesis is difficult Reaction with containers/crucibles Volatility of one or more of the components

Solid State Reactions: general aspects

Solid State Reactions: general aspects

Solid State Reactions: general aspects


Nucleation may be facilitated by structural similarity between the reacting solids, or products. In the reaction between MgO and Al2O3, MgO and spinel have similar oxide ion arrangements. Spinel nuclei may then easily form at the MgO surfaces. There is often a structural orientational relationship between the reactant, nuclei and product. The lattice spacing (e.g. distance between oxide ions) should not not be too different for oriented nucleation. The ease of nucleation depends also on the actual surface structure of the reactants.

Solid State Reactions: general aspects


Increase diffusion rates (decrease diffusion lengths)
Small particles by grinding, ball milling, spray drying, freeze drying, spray pyrolysis etc. Cooling and regrinding may be necessary Intimate mixture of reactants by coprecipitation, sol-gel processes, spray pyrolysis etc. Reduction of diffusion distances by incorporating the cations in the same solid precursor. Solid state reactions involving melts, molten fluxes or high temperature solvents.

9.2 Synthesis of monodispersed colloids


precipitation
AgBr particles from precipitation

J.E. Maskasky, J . Imaging Sci. 1986,30,247.

Synthesis of monodispersed colloids


precipitation domains diagram
CuSO4 particles from precipitation
Regions: I: homogeneous solution; II: blue precipitate (brochantite); III: red-brown precipitate (tenorite).

Egon Matijevic, Chem. Mater. 5 (1993) 412.

Synthesis of monodispersed colloids spherical particles


Al2O3xH2O via 2mM Al(NO3)3 + 3 mM (NH4)2SO4 105C/24h Cr2O3xH2O via 4mM CrK(SO4)2 12H2O 75C/24h

CeO2xH2O via 1.2mM Ce(SO4)2 + 80 mM H2SO4 90C/48h

-Fe2O3 via 32mM FeCl3 + 5 mM HCl 100C/240h

Egon Matijevic, Chem. Mater. 5 (1993) 412.

Synthesis of monodispersed colloids TEM micrographs of Fe-related oxides


-FeOOH via 4.5mM FeCl3 + 0.1 M HCl 100C/24h -Fe2O3 via 19mM FeCl3 + 1.2 mM HCl +40 vol% ethanol 100C/16h -Fe2O3 via 20mM FeCl3 + 0.3 mM NaH2PO4 100C/48h -FeOOH + -Fe2O3 via 18mM FeCl3 + 30 mM HCl + 20 vol% EG 100C/48h

Egon Matijevic, Chem. Mater. 5 (1993) 412.

Synthesis of monodispersed colloids TEM micrograph and replica of ferric basic sulfate

-Fe3(SO4)2(OH)52H2O via 88mM Fe2(SO4)3 98C/2.8h

Egon Matijevic, Chem. Mater. 5 (1993) 412.

Synthesis of monodispersed colloids ZnO particles


ZnO via 5mM Zn(NO3)2 + 19 mM NH4OH PH=8.8 90C/3h
1 bar = 1m (a and b) and 10 m (c and d)

ZnO via 0.1mM Zn(NO3)2 + 0.32 mM NH4OH PH=7.7 90C/1h

ZnO via 3.2mM Zn(NO3)2 + 0.1 M TEA (triethanolamine) PH=8.9 90C/1h

ZnO via 40mM Zn(NO3)2 + 0.2 M TEA + 1.2M NaOH PH=12.1 150C/2h

Egon Matijevic, Chem. Mater. 5 (1993) 412.

Synthesis of monodispersed colloids CuO particles


CuO via 2mM CuCl2 + 0.4M urea 90C/120min CuO via 8mM Cu(NO3)2 + 0.2M urea 90C/100min

CuO via 6mM CuSO4 + 20mM urea 90C/100min

CuO via 1.2mM CuSO4 + 0.3M urea 90C/60min

Egon Matijevic, Chem. Mater. 5 (1993) 412.

10

Synthesis of monodispersed colloids Y(OH)CO3 particles

Y(OH)CO3 via 16mM Y(NO3)3 + 0.33M urea 85C/3h

Y(OH)CO3 via 30mM YCl3 + 3.3M urea 110C/20h

Egon Matijevic, Chem. Mater. 5 (1993) 412.

Synthesis of monodispersed colloids hematite and Co3O4 particles


HEDTA = N-(2-hydroxyethyl) ethylenediaminetriacetate

hematite (-Fe2O3) via 40mM Fe(NO3)3 + 0.2M TEA +1.2M NaOH + 0.5M H2O2 250C/1h

Co3O4 via 40mM Co(NO3)2 + 0.2M HEDTA +1.2M NaOH + 0.5M H2O2 250C/3h

Egon Matijevic, Chem. Mater. 5 (1993) 412.

11

Synthesis of monodispersed colloids spherical and prismatic particles


ZnS via 20mM Zn(NO3)2 + 60mM HNO3 + 0.11M thioacetamide (TAA) 26C/5h + 60C/6h Mn3(PO4)2 via 5mM MnSO4 + 5mM NaH2PO4 + 1M urea + 10mM SDS 80C/3h
SDS= sodium dodecyl sulfate

PbS via 1.2mM Pb(NO3)2 + 0.24M HNO3 + 5 mM TAA + 1.2mM TAA 26C/21h + 26C/1h CdCO3 via 10M urea (preheated 80C/24h ) + 2mM CdCl2 (1:1 v/v)

TAA= Egon Matijevic, Chem. Mater. 5 (1993) 412.

Synthesis of monodispersed colloids hybrid spherical + prismatic particles

1 m

PbSxCdS via (1) 1.2mM Pb(NO3)2+ 2.4mM HNO3+ 5 mM TAA @26C/21h => PbS seed sol A (2) 20ml A + 0.5ml 4.3 mM Cd(NO3)2 + 1ml 21 mM Pb(NO3)2 @80C/30min

Egon Matijevic, Chem. Mater. 5 (1993) 412.

12

Synthesis of monodispersed colloids functional ceramic particles

BaTiO3 via 5mM Ti(i-Opr)4 + 10mM Na2H2EDTA + 5mM BaCl2 + 0.38 M H2O2 60C/2h (PH=9.9 by NH3) NiFe2O4 via [Ni(OH)2]/[Fe(OH)2] =0.5 + 60mM FeSO4 + 0.2M NaNO3 90C/4h

PbNb2O6 via 8mM Pb(NO3)2 + 2mM NbCl5 + 10 mM Na2HNTA (+ H2O2 present) 50C/4h

BaFe12O19 via 0.125M FeCl2 + 0.1M KOH + 0.2M KNO3 + 0.01M Ba(NO3)2 90 C

Egon Matijevic, Chem. Mater. 5 (1993) 412.

Synthesis of monodispersed colloids scheme of the apparatus for continuous precipitation flow

Egon Matijevic, Chem. Mater. 5 (1993) 412.

13

Powder preparation

Precursor solution

Immobilisation step

Chemical

Physical

Gelation

Complexation

Co-Precipitation

Dispersion

Sol-Gel

- Precipitation - Pyrolyis (Citrate, EDTA Pechini, Bilcher)

Direct Emulsion

Spraying techniques - Spray drying - Freeze drying

Drying, Calcining Powder

9.3 Sol - gel


Powder/ Coating
Metal salt or metalorganic precursor Colloidal route Polymeric route

media

(Green forming)

Sol
(colloidal)

Sol
(polymeric)

membrane coating

Sintering

Colloidal gel

Polymeric gel

Drying

Post treatment

(hybrid organic-inorganic membrane)

Sintering
(pure inorganic membrane)

14

SolSol-gel chemistry for synthesis of micro and meso porous membrane systems
Multi-layer ceramic membrane is schematically build up from; Macroporous support
Colloidal processing (Ch. 6)

Meso porous intermediate layer (= sometimes the final separation layer) Micro-porous top layer (separation layer
Sol- gel Chemistry Microporous dp < 2 nm

macro Mesoporous 2 nm < dp < 50 nm


Macroporous dp > 50 nm porous ceramic membranes

meso

micro

Al2O3

TiO2

SiO2

Sol - gel
Sol-gel*:
preparation of ceramic materials by preparation of a sol, gelation of the sol, and removal of the solvent solvent

Sol*:
A sol is a colloidal suspension of solid particles dispersed in a liquid liquid (dispersed phase is small: ~1 1000 nm)

Gel*:
If one molecule reaches macroscopic dimensions, so it extends throughout the solution solution
* Brinker & Sherer, Sherer, SolSol-gel Science

15

Two routes Colloidal and polymeric

Sol - Gel
Metal salt or metalorganic precursor Colloidal route Polymeric route

Process parameters: Colloidal


water/precursor ratio temperature pH Reaction time

media

particle
Sol
(colloidal)

polymer network
Sol
(polymeric)

membrane coating

Much is known on SiO2 Al2O3 and TiO2

Colloidal gel

Polymeric gel

Drying
(hybrid organic-inorganic membrane)

Sintering
(pure inorganic membrane)

Colloidal vs. polymeric route


Colloidal Polymeric
Metal alkoxide Metal alkoxide (or Metal salt) Solvent = alcohol (or water) Solvent = alcohol Precipitation: Precipitation: Precipitation/peptisation [alkoxide]<<[water] [water]/[alkoxide ] =1alkoxide]<<[water] [water]/[alkoxide] =1-4 Inorganic polymer is formed Colloids in aqueous medium Agglomeration prevented by Agglomeration prevented by small size particle repulsion (DLVO, etc.) Gel as a result of electrostatic Gel as a result of further polymerization effects
In most cases crystalline particles Amorphous structures can be formed Micro porous systems are formed after temp. treatment

16

Alumina particle sol-gel synthesis


Al-tri-secbutoxide Hydrolysis (90 oC) Polycondensation Heating at Tb to remove alcohol Nitric acid Stabilisation Peptisation at 80 oC Water

- AlOOH (=boehmite) precipitate

STABLE SOL Gelation Calcining

Meso porous (<50 nm, >2 nm)


Pore diameter 400 oC: 3 nm (Al2O3) 800 oC: 5 nm (Al2O3)

Titania particle sol-gel synthesis


Ti-isopropoxide in isopropanol Hydrolysis Polycondensation Filtration and washing to remove alcohol Nitric acid Stabilisation Peptisation at 80 oC Solution of water and isopropanol Titanium oxyhydroxide

STABLE SOL Gelation Calcining Particle size: 300 oC: 20 nm (anatase) 600 oC: 50 nm (rutile)

17

Colloidal vs. polymeric route


Polymeric route Control of hydrolysis/condensation Hydrolysis M-(OR)4 + H2O (HO)(HO)-M-(OR)3 M-(OR)4 + 4 H2O M-(OH)4
OC2H5 OC H Methoxy 2 5 Si Ethoxy Condensation OC H OC2H5 2 5 Alcoxolation Propoxy M-OH + MOR M O M + ROH M R TEOS Butoxy Oxolation M-OH + MM-OH M-O-M + H2O Olation M-OH + H2O:MO:M-OH (M)2-O-H + H2O M-OH + ROH:MROH:M-OR (M)2-O-H + ROH

Polymeric route

Summery of reactions
Ratio hydrolysis/condensation and the associated polymerization reactions determine the properties of the gel AND the material resulting from that gel
water, H+ -C2H5OH OR Si OR OC2H5 OH water, H+ -C2H5OH OR Si OR OH OH etc.

Hydrolysis
OR Si OR OC2H5 OR

R = OC2H5

Condensation
OR Si OR OH OH HO OR OR - water OR

OH OH Si OR HO OR O OR Si OR - water Si O OR Si O OR Si OR OR OR

OR

HO

Si

Hydrolysis reactions replace an alkoxy group (OR) with hydroxyl (OH) group Condensation reactions involve the silanol groups to produce siloxane bonds (Si-O-Si) plus by-products: alcohol (ROH) or water

18

Polymeric route

Sol - gel

Adjustable process parameters


Internal parameters
nature of the metal atom and alkyl/alkoxide alkyl/alkoxide groups structure of metal precursor

External parameters

Hydrolysis-Condensation

of silica alkoxides under water/alkoxide water/alkoxide ratio acidic or basic conditions catalyst (acid or base) concentration solvent/precursor solvent temperature

Polymeric route

Mechanism of hydrolysis and condensation


hydrolysis acid
RO RO RO Si OH3+ RO OR RO RO RO Si O R H OH2
+

Hydrolysis

condensation acid
RO RO RO Si

Condensation
H+ OH + HO Si OR OR OR RO RO RO Si O Si OR OR + H3O+ OR

acid
HOR + H+

acid

RO RO

Si

OH

base
RO H2O RO Si OR OR H+ RO RO OR Si O OH2 R H
+

RO RO RO RO Si

base
OH + OH-

RO RO RO OR RO RO RO Si O + OHSi OR OR OR Si O- + H2O

base base
RO HORO Si OR OR ROOR HO RO

OR Si O OH OR 2

RO R RO

Si

O- + HO

Si

OR OR

Hydrolysis-Condensation of silica alkoxides under acidic or basic conditions

HO

Si

OR OR

and RO- + H2O

ROH + OH-

19

acid

Hydrolysis of alkoxides under acidic conditions

pH<2.2
Takes place via fast protonation of the alkoxyde Silicon becomes more electrophilic (therefore more susceptible to attack by water) Protonation becomes slower when more hydroxylhydroxyl-groups are present Hydrolysis rate decrease with extent of OH substitution

base

Hydrolysis of alkoxides under basic conditions

pH >2.2
Takes place via dissociation of water in hydroxyl anions Attack of these hydroxylhydroxyl-ions on the silicon atom Hydrolysis rate increases with the extent of OR substitution

20

acid

Condensation of alkoxides under acidic conditions

Via protonated silanol species SiSi-HOR+ Results in linear polymers

base

Condensation of alkoxides under basic conditions

Takes place by attack of a nucleophilic deprotonated silanol (SiSi-O-) on a neutral silicate species Results in more branched polymers

21

Hydrolysis and condensation of TEOS=f(pH)


An acid enhances hydrolysis more than condensation A base catalyst (NH4OH) increases condensation rates more than hydrolysis rate

Condensation

base

pH < 2 condensation rate [H+]. Developing gel networks are composed of exceedingly small primary particles. ph = 22-6 condensation rate [OH-]; (i.e., growth of a network) contributes little to growth after particles exceed 2nm in diameter. Thus, developing gel networks are composed of exceedingly small primary particles.

22

Polymeric route: summary

Morphologies of silica sols and gels made under acid or base conditions
Sol-gel derived silicon oxide networks, under acid-catalyzed conditions, yield primarily linear or randomly branched polymers which entangle and form additional branches resulting in gelation. On the other hand, silicon oxide networks derived under base-catalyzed conditions yield more highly branched clusters which do not interpenetrate prior to gelation and thus behave as discrete clusters

a)

b)

Acid catalyzed
Porous silica membrane formation

acid

H+
FAST SLOW

20 More acid

Less acid

Fractals as Building bricks

1.4

Df<1.5: Interpenetration Small pores

Micro porous (< 2 nm)

23

Acid catalyzed
micro porous silica membrane formation

acid

macro

meso

micro

Al2O3

TiO2

SiO2

Meso an micro porous layers applied on a macro porous substrate by dip coating

Amorphous TiO2

micro
- Al2O3 or anatase TiO2

meso

macro

24

Base catalyzed
Particles or cluster formation

base

O O i O S O i O O S O O S i O O

Inductive effects of substitutions attached to Si

The rate and extent of hydrolysis is influenced by the strength and concentration of the acidic or basic catalyst Temp. and solvent of secondary importance Substitution of alkyl groups for alkoxy groups increases the electron density of Si Hydrolysis (subst . OH for OR) or (subst. condensation (subst . OSi for OR or (subst. OH) decreases electron density on Si

25

Advantages and disadvantages of the sol-gel technique


The product morphology (porosity, connectivity, primary particle size) can be controlled through process conditions during synthesis synthesis Low operating temperatures Shaping is simple Homogeneous compounds can be achieved Very small primary particle sizes can be achieved (2(2-20 nm) A relative complex method

Sol-Gel

A particulate alcosol
- Coating on glass

tetraisopropyl titanate TIPT: {(CH3)2CHO}4Ti J. Am. Ceram. Soc.84 [12] 2969-74(2001) [486]

26

Gel precipitation process

Sol-Gel
Polymeer netwerk van SiO2 Makkelijk substitutie van Ca2+

Bio active glas / coating

27

Applications of Sol - gel

Colloidal route
A sol consists of a liquid with colloidal particles which are not dissolved, but do not agglomerate or sediment. Agglomeration of small particles are due to van der Waals forces and a tendency to decrease the total surface energy. Van der Waals forces are weak, and extend only for a few nanometers. In order to counter the van der Waals interactions, repulsive forces must be established. May be accomplished by: Electrostatic repulsion. By adsorption of charged species onto the surface of the particles, repulsion between the particles will increase and agglomeration will be prevented. Most important for colloidal systems. Steric hindrance. By adsorbing a thick layer of organic molecules, the particles are prevented from approaching each other reducing the role of the van der Waals forces. Works best in concentrated dispersions. Branched adsorbates works best. Usual for nanomaterials.

Particle

Organic layer

28

PZC, Point of zero charge


Stabilization due to electrostatic repulsion are due to formation formation of a double layer at the particle. The surface of a particle is covered by ionic groups, which determines determines the surface potential. Counter ions in the solution will cover this layer, shielding shielding the rest of the solution from the surface charges. For hydroxides the surface potential will be determined by reactions reactions with the ions H+ and OH-. Thus, the surface potential is pH dependent. M-OH + H+ M-OH2+ M-OH + OH- M-O- + H2O The pH where the particle is neutral is called PZC, point of zero zero charge. For pH > PZC the surface is negatively charged For pH < PZC the surface is positively charged. Typical values: MgO 12, Al2O3 9.0, TiO2 6.0, SnO2 4.5, SiO2 2.5 Depends somewhat on the size of the particle and the degree of condensation condensation The size of the surface potential 0 depends on the difference between pH and PZC.

Ostwald ripening
Small particles dissolve faster than larger particles. As the process is dynamic and reversible, smaller particles may be dissolved to feed growth of the larger particles. The growth stops when the difference in solubility between the largest and smallest particle is a few ppm. It is therefore possible to prepare monodisperse silica particles from a gel.

29

Sol-gel processes for La1-xSrxCoO3-


La1-xSrxCoO3- fine powder

Aqueous sol-gel

Polymeric sol-gel
La1-xSrxCoO3- porous layer

Mater. Sci. Eng. B 39 (2) (1996) 129-132.

J. Mater. Chem. 6(5) (1996) 815-819.

Sol-gel processes for PZT, PbZr1-xTixO3


The method may provide good control over stoichiometry and reduced sintering temperature. This is especially important if one of the components are volatile. May also enable production of low temperature phases. The largest piezoelectric response of PZT: x = 0.47. The stoichiometry is difficult to control by the ceramic method, where heating at 1100C for several hours is needed.

Louis: TIPT

30

9.4 Pechini method for powder preparation


Modified resinintermediate processing of perovskite powders:Part I. Optimization of polymeric precursors Lone-Wen Tai, Paul A. Lessing The formation of a polyester between citric acid (CA) and ethylene glycol (EG) was found to be a decisive factor for the foaming of resin intermediates in a Pechini-type powder process. This process was modified by changing the organic mass ratio of CA/EG which results in ceramic powders with different morphologies. The most porous resin intermediate (with or without chelated cations) was prepared using a polymeric gel made of equimolar citric acid and ethylene glycol. It was also found that a premixing of organic components, prior to adding constituent nitrate solutions, makes the whole process more controllable. Keywords: Ceramics; Chemical synthesis; Powder Materials: La0.85Sr0.15CrO3 J. Mater. Res., Vol. 7, No. 2, 1992, p. 502.

Pechnis method related patents and papers


1) M. Pechini, Method of Preparing Lead and Alkaline Earth Titanates and Niobates and Coating Method Using the Same to Form a Capacitor, U.S. Pat. No. 3 330 697, July 11, 1967. 2) N. G. Eror and H. U. Anderson, Polymeric Precursor Synthesis of Ceramic Materials, Mater. Res. Soc. Symp. Proc., 73, 57177 (1986). 3) P. A. Lessing, Mixed-Cation Oxide Powders via Polymeric Precursors, Am. Ceram. Soc. Bull., 68 [5] 10021007 (1989). 4) (a)L.-W. Tai and P. A. Lessing, Modified Resin-Intermediate Processing of Perovskite Powders: Part I. Optimization of Polymeric Precursors, J. Mater. Res., 7, 50219 (1992). (b)L.-W. Tai and P. A. Lessing, Modified Resin-Intermediate Processing of Perovskite Powders: Part II. Processing for Fine, Nonagglomerated Sr-Doped Lanthanum Chromite Powders, J. Mater. Res., 7, 50219 (1992). 5) H. U. Anderson, Review of p-type Perovskite Materials for SOFC and Other Applications, Solid State Ionics, 52, 3341 (1992). 6) L .-W. Tai, H. U. Anderson, and P. A. Lessing, Mixed-Cation Oxide Powders via Resin Intermediates Derived from a Water-Soluble Polymer, J. Am. Ceram. Soc., 75 [12] 349094 (1992).

31

Pechnis method
In this powder-synthesis route, citric acid forms poly(basic acid) chelates with the metal cations. These chelates undergo polyesterification, when heated with a poly(hydroxy alcohol), such as ethylene glycol, at a temperature of ~150C to form a polymeric precursor resin. The cations are expected to be dispersed uniformly throughout the polymeric resin. Additional heating of the resin in air (at ~400C) results in the removal of organics and the formation of a char with a controlled cation stoichiometry, with little cation segregation. Then, the char is heated to higher temperatures and oxidized to form the oxide ceramics.

Ethylene glycol

Nitrates solution + citric acid + ethylene glycol heat and evaporation resin (xerogel) calcine grinding sintering

Example: Preparation of strontium- and/or magnesium-doped lanthanum gallate (LSGM) Powders


Precursors: La(NO3)39H2O, Ga(NO3)3 xH2O, Sr(NO3)2, Mg(NO3)26H2O Citric acid monohydrate (C6H8O7), ethylene glycol (C2H6O2) CA:EG = 60:40 (w/w) CA:Mtot = 1.88 This solution was homogenized by stirring at room temperature for 1 h. Then, the resulting clear solution was evaporated (in a period of 3 h) on a hot plate until first a clear yellow gel and then a dark brown resin formed. The obtained resins (following overnight drying in an oven at 100C) were scraped off the beakers with a spatula, then ground by hand using an agate mortar and pestle, and finally calcined isothermally in a stagnant-air-atmosphere box furnace over a temperature range of 2001400C. Each calcination batch of powders was heated to the specified temperature at a rate of 5C/min, annealed at this temperature for 6 h, and then furnace-cooled to room temperature.

Tas et al., J. Am. Ceram. Soc. 83[12](2000) 2954.

32

Analyses of LSGM precursors at different temperatures

Fig. 3. XRD spectra of La0.8Sr0.2Ga0.83Mg0.17O2.815 precursor powders calcined at different temperatures. Secondary phases observed are indicated (1,LaSrGa3O7 peak, 2, LaOOH peak, 3, La2O3 peak, and 4, LaSrGaO4 peak).

Table I. Results of residual carbon analyses (wt%) _________________________________________________________________ Temp. (C) LaGaO3 La0.9Sr0.1GaO2.95 La0.8Sr0.2Ga0.83Mg0.17O2.815 _________________________________________________________________ 100 31.7 (3) 33.3 (2) 32.7 (6) 350 10.3 (3) 10.4 (1) 13.8 (2) 700 0.530 (3) 0.550 (5) 0.280 (4) 850 0.059 (1) 0.143 (9) 0.168 (3) 1000 0.042 (2) 0.050 (3) 0.060 (2) 1340 0.010 0.0124 (2) 0.0143 (4) _________________________________________________________________

33

Microstructures of LSGM precursors at different temperatures

100C

500C

700C

1000C

1400C (pellets)

Microstructures of LSGM pellets (1400C)

34

9.4 YBCO

Glycine-nitrate pyrolysis (GNP) method


Ce(NO3) solution Sm(NO3)3 solution blended in a certain ratio
Heated under stirring 750/2h 2/min

Sm-doped CeO2

Glycine was added G:M=0.7 to 3.4

Viscous solution
Evaporation,and ignited to flame

Pale-yellow ash

Flow chart for preparing SDC powder

35

Doped CeO2 prepared with glycine-nitrate method


Glycine-Nitrate Process (GNP) is a self-sustaining combustion synthesis technique, containing metal nitrates as oxidizers and glycine as a fuel.
NH2CH2COOH

Forms complexes with metal ions


Preventing selective precipitation Making the metals mixed at atomic level

Fuel for combustion


Ce4+

NH2CH2COOH Sm3+

Doped CeO2 prepared with glycine-nitrate method


Ce(NO3)3 + NH2CH2COOH CeO2 + CO2 + H2O + N2 (glycine /metal=14/91.56) Sm(NO3)3 + NH2CH2COOH Sm2O3 + CO2 + H2O + 4N2 (glycine/metal=15/91.67) For SDC: the glycine/metal1.58

Assumption: all glycine were oxidized by nitrate (no air ),the gaseous products of combustion were CO2 H2O and N2(no CO) The powders morphology and sinterablity is influenced by the ratio of glycine/metal.
26 Sm(NO3)3 + 30 NH2CH2COOH = 13 Sm2O3 + 60 CO2 + 75 H2O + 54 N2

36

111

220

311

1450 C

600 C

ash
30 40 50 60 70 80 90

X-ray diffraction patterns of the ash as synthesized by a glycine-nitrate process, the SDC powder calcined at 600oC, and a SDC pellet sintered at 1450oC.

Characterization(TEM)
a b c

100nm

250nm

222

400

100nm

TEM photographs of SDC powders heated at 750oC. The powders were prepared with glycine-to-metal ratio of (a) 0.7, (b) 1.0-2.5, and (c) 3.4

331 420

200

422

37

Characterization(SEM)

SEM images of Sm0.2Ce0.8O1.9 pellets fracture at different ratio sintered at 1500 o C for 5h a) the glycine /metal ratio of 0.7 or 3.4 b) the glycine /metal ratio of 1.7

Pechini method to CeO2-SnO2 and CeO2-TiO2 coatings

Thin Solid Films 410 (2002) 1-7.

38

You might also like