UNIVERSITAT DE BARCELONA

DEPARTAMENT DE FÍSICA APLICADA I ÒPTICA

SILICA AEROGELS: SYNTHESIS AND CHARACTERIZATION

Magda Moner i Gerona

INSTITUT DE CIÈNCIA DE MATERIALS DE BARCELONA-CSIC

UNIVERSITAT DE BARCELONA
DEPARTAMENT DE FÍSICA APLICADA I ÒPTICA

SILICA AEROGELS: SYNTHESIS AND CHARACTERIZATION

Magda Moner i Gerona

INSTITUT DE CIÈNCIA DE MATERIALS DE BARCELONA-CSIC

Programa de doctorat: Física i Tecnologia de Materials Bienni: 1997-1999 Tutor: Joan Esteve i Pujol Directors: Elies Molins i Grau Anna Roig i Serra

Memòria presentada per optar al grau de Doctor en Ciències Físiques Barcelona, Juny 2002

ii

Aquesta tesi ha estat realitzada a l‟Institut de Ciència de Materials de Barcelona-CSIC en el departament de Cristal.lografia i Química de l‟Estat Sòlid, sota la direcció del doctor Elies Molins i la doctora Anna Roig. El treball ha esta realitzat dins el marc dels projectes d‟investigació de la CICYT MAT97-0688 i MAT2000-2016, i de varis projectes R+D entre l‟empresa Carburos Metálicos S.A i l‟Institut de Ciència de Materials de Barcelona. Durant els dos últims anys, la doctorant ha gaudit d‟una beca 2001TDOC011 de la Direcció General de Recerca de la Generalitat de Catalunya.

iii

iv

AGRAÏMENTS

He d’agrair al Dr. Elies Molins, cap del grup d’aerogels de l’ICMAB i co-director d’aquesta tesi, l‘oportunitat que em va donar d’iniciar la tesi amb un material tan sorprenent i atractiu com és l’aerogel. Per descomptat agrair-li les seves constants noves idees, la il·lusió que m’ha transmès per està obert a qualsevol proposta, i la seva accessibilitat i respecte pel meu treball. De manera especial, m’agradaria transmetre el meu agraïment a la Dra. Anna Roig, co-directora d’aquesta tesi, per oferir-me un continu i ferm suport tant científic com personal en la realització d’aquesta tesi. Agreixo la seva dedicació i interès constant per la meva feina, i sobretot pel seu tracte com a persona. La meva gratitud al Dr. Carles Miravitlles director de l’Institut de Ciència de Materials de Barcelona per posar a la meva disposició els mitjans necessaris per dur a terme aquesta tesi i al Dr. José-Luis Morenza, director del departament de Física Aplicada i Òptica pels seus consells en la logística de presentació de la memòria. Durant el temps de realització d’aquesta tesi he tingut la sort de treballar en un grup que sempre m'ha ofert la seva ajuda i amb moltes ganes per treballar en equip tant dins com fora de l'institut. A tots els companys que heu participat en la realització d'aquesta tesis gràcies pel vostre ajut i amistat: a l’Ignasi (pel seu constant ajut i per l’esforç de millorar la situació dels becaris), l’Elisenda (per la seva amistat i la seva voluntat de donar sempre un cop de mà), en Lluís (com no, per fer-nos compartir la seva passió pel món occità), el Raul (sense el seu treball constant i la seva paciència no hauria estat possible l’obtenció dels aerogels presentats en aquesta tesi), la Joana (el seu ajut ha estat imprescindible alhora d’organitzar aquesta tesi), en Martí, la Mònica, la Mihaela, l’Agnes, la Stephanie, en Fabian i en Ramon (a tots ells per haver aportat part d’aquest treball) . A molts d’altres companys de l’ICMAB, la Karina (por su original y apasionante visión de la ciencia), el Ramon, l’Oriol, l’Andrea, l’Imma, el Manu, en Jerôme, en Felip, la Sílvia, per ajudar-me a passar molt bons moments a l’Institut. I especialment en Lluís Balcells per tots els seus consells i les discussions que hem mantingut. To Sari for introducing me in the IR analysis and to share a very nice time in Gràcia.

Aquesta tesi ha estat realitzada gràcies a un conctracte d’investigació per part de Carburos Metalicos, i al suport científic de Joan Llibre, Joaquim Torras, i d’Emili de la Serna He d’agrair tot l’equip d’infrastructura de l’Institut, administració, documentació, servei informàtic i manteniment per la seva ajuda en aquella part del treball que no queda reflectit en la tesi però que és imprescindible alhora de desenvolupar-la.

v

Així mateix, el fet de treballar amb un material poc conegut i amb unes propietats tan sorprenents com les de l’aerogel ajuda a que molt sovint m’hagi trobat amb l’entusiasme d’altres investigadors per a ‘provar’ noves iniciatives i ‘jugar’ amb la seva peculiar estructura. Principalment he tingut la sort de treballar conjuntament amb l’Elena Martínez i en Joan Esteve en la caracterització mecànica dels aerogels. Ha estat una experiència molt positiva de treballar en col·laboració d'un equip que em rebien amb les portes ben obertes cada vegada que els portava noves mostres per caracteritzar. Gràcies Elena per l'ajuda i per l’afecte que sempre m’has mostrat i a en Joan per aquella energia que transmets per gaudir amb la investigació. Sense l'ajuda de Yves Maniette i Joaquim Portillo (i la visualització dels nostres ‘núvols’ per TEM), Núria Ferrer i Pau Gorostiza, tots ells dels serveis científico-tècnics de la UB, no hauria estat possible la caracterització dels aerogels. Agraeixo en Miquel-Àngel Cuevas per haver-me acollit en el seu grup i per haver-me donat suport al llarg dels anys de la realització d’aquesta tesi. I would like to kindly express my gratitude to Arlon Hunt for his guidance during the realization of the stages in his Microstructure Group at the Lawrence National Berkeley Laboratory. I have learned a lot not only about these surprising aerogels but also about the sweet manner to appreciate science. Of course to Mike Ayers, thanks a lot to teach me so many fruitful ‘tricks’ about how to handle the aerogels, for his interest and nice suggestions. And in particular, this wonderful decision to bike always to everywhere and under any kind of weather, and to repair my ‘vintage’ bike so many times …To Ian Shepherd for his interest and pleasant discussions and to try (without much results) to improve my English, and to Paul Berdahl and Gary for his valuable contributions to the development of the nephelometer set-up and analysis of the data. I nicely thank to Giovanni Dietler, Cynthia Lopez and Steven Grover to advice and help me so many times.

D’altres persones que no han col·laborat directament en la meva feina però han estat imprescindibles perquè fos complerta: l’Àlex, per la seva paciència constant durant el temps de la realització de la tesi, i per haver-me donat suport sempre que l’he necessitat. Els meus avis Núria, Antonio i Roser per encoratjar-me sempre tan dolçament i pel vostre suport incondicional. L'Alba, l'Enric, el Josep-Lluís i la Mercè per aguantar a la tipàtica força sovint. I com no, per ensenyar-me uns valors tan importants com són el respecte a la natura i la passió per la muntanya . A totes/ts les jugadores/rs i companyes del Sitari i del Bonanova que sense saber-ho hi han col·laborat ajudant-me a desconnectar totalment dels aerogels. A tot aquest cercle d’amics que m’han encoratjat i que han tingut la paciència d'escoltar el procés d'aquesta tesi: A l'Aracel.li, la Marta Pérez (per desenboirar-me a mb les correlacions i per mantenir la nostre amistat a distància), la Maria Serra, la Marta Janeras, l’Oriol, la Betlem, l’Albert, i el Fidel.

vi

INDEX

PRÒLEG ....................................................................................................................................................................... 1 GLOSSARY OF TERMS ......................................................................................................................................... 4

C h a p t e r I . AEROGELS: AN INTRODUCTION
1. GENERAL OVERVIEW ON AEROGELS .....................................................................................12 1.1. 2. COMMERCIAL SILICA AEROGEL .................................................................................. 14

SOL-GEL METHOD.............................................................................................................................15 2.1. 2.2. ANTECEDENTS OF GEL SYNTHESIS ......................................................................... 16 PREPARATION OF SILICA GELS .................................................................................... 16

3. 4.

DRYING PROCEDURE OF GELS .................................................................................................. 20 AEROGEL APPLICATIONS ............................................................................................................. 22 4.1. POROSITY AND SURFACE AREA APPLICATIONS ................................................. 22 Electrodes in capacitors ................................................................................. 22 Capacitive deionization ................................................................................. 23 Studies of superfluid transitions and phase separation of 3He-4He...................... 23 4.2. 4.3. 4.4. 4.5. 4.6. OPTICAL PROPERTY APPLICATIONS ........................................................................ 23 Çerenkov (particle detection and counters)........................................................ 23 THERMAL INSULATOR APPLICATIONS .................................................................. .24 ACOUSTICAL AND MECHANICAL APPLICATIONS ............................................. 24 Shock compression experiments ...................................................................... 25 ELECTRICAL AND ELECTRONIC APPLICATIONS .............................................. 25 SPACE APPLICATIONS........................................................................................................ 25

5.

REFERENCES....................................................................................................................................... 25

C h a p t e r I I : SYNTHESIS OF SILICA AEROGELS
1. 2. INTRODUCTION ................................................................................................................................ 32 PREPARATION OF AEROGELS .................................................................................................... 33 2.1. 2.2. 2.3. USED REACTIV ES ................................................................................................................. 33 SYNTHESIS PROCEDURE ................................................................................................. 34 DRYING PROCEDURE ........................................................................................................ 36

Index
2.3.1

ii
Supercritical drying at high temperature ................................................................ 36

2.3.2 CO2 supercritical drying................................................................................................ 38 3. SYNTHESIS ROUTES: EFFECT OF DIFFERENT ALKOXIDE PRECURSORS ........... 39 3.1. TETRAMETHOXYSILANE: TMOS AEROGELS ........................................................ 40 3.1.1 3.1.2 3.1.3 3.2. The effect of the TMOS concentration...................................................................... 45 The effect of the nature of the solvent ...................................................................... 46 The effect of the hydrolysis solution .......................................................................... 47 Water amount.............................................................................................. 47 TETRAETHOXYSILANE: T EOS AEROGELS ............................................................. 49 3.2.1 The effect of the TEOS concentration ................................................................... 53 Neutral....................................................................................................... 53 Acid catalyst ................................................................................................ 54 Base-catalyst ................................................................................................ 56 3.2.2 The effect of hydrolysis solution ............................................................................... 58 Water amount.............................................................................................. 58 Influence of the amount of the catalyst ............................................................. 61 Influence of the nature of the catalyst ............................................................... 64 3.3. ‘TWO-STEP’ SYNTHESIS .................................................................................................... 66 Effect of precursor concentration...................................................................... 67 Effect of water amount .................................................................................. 69 Influence of the amount of the catalyst ............................................................. 70 4. SUMMARY AND CONCLUSIONS...................................................................................................71 5. REFERENCES....................................................................................................................................... 72

C h a p t e r I I I : BULK SILICA AEROGEL CHARACTERIZATION
1. MONOLITHICITY, BULK SHRINKAGE, DENSITY AND POROSITY............................ 75 1.1. TMOS AEROGELS .................................................................................................................. 76 Skeletal density ............................................................................................ 76 Bulk density ................................................................................................ 76 1.1.1 1.2. 1.2.1 1.2.2 1.2.3 Supercritical drying at CO2 conditions.................................................................... 80 TEOS aerogels without presence of catalyst.......................................................... 82 Base-catalyst ................................................................................................................. 84 Acid-catalyst .................................................................................................................. 87 Fluorhydric acid ........................................................................................... 88 Citric acid.................................................................................................... 88 1.3. TWO-STEP METHOD H5 AEROGELS .......................................................................... 91 TEOS A EROGELS ................................................................................................................... 81

Index
2. 3.

iii
SURFACE AREA MEASURENTS BY BET (BRUNAUER, EMMET AND TELLER).... 94 INFRARED SPECTROPHOTOMETRY, IR ................................................................................ 99 3.1. 3.2. METHANOL SERIES .......................................................................................................... 100 ACETONE SERIES ............................................................................................................... 102

4.

ULTRA VIOLET-VISIBLE SPECTROSCOPY ............................................................................103 4.1. 4.2. AEROGEL TRANSPARENCY .......................................................................................... 103 RAYLEIGH SCATTERING................................................................................................ 107 4.2.1 A model to interpret the porous aerogel structure using Rayleigh scattering110

5.

LIGHT SCATTERING MEASUREMENTS OF AEROGELS BY A POLARIZATIONMODULATED NEPHELOMETER .............................................................................................. 113 5.1. INTRODUCTION TO LIGHT SCATTERING VERSUS ANGLE EXPERIMENTS ......................................................................................................................113 5.1.1 5.2. 5.3. Description of the polarization-modulated nephelometer ................................. 114 EXPERIMENTAL RESULTS .............................................................................................115 STRUCTURAL INFORMATION FROM THE LIGHT SCATTERING MEASUREMENTS .................................................................................................................118 5.3.1 Inhomogeneous media .............................................................................................. 118 Short range correlations: Rayleigh scattering................................................... 120 Long range correlations: departures from Rayleigh scattering ............................ 121 5.4. 5.5. COMPARATIV E STUDY BETW EEN EXPERIMENTAL M EASUREMENTS AND THEORY ....................................................................................................................... 122 CONCLUS IONS AND FUTURE W ORK ....................................................................... 125

6.

DIRECT METHODS: ELECTRON MICROSCOPY ...............................................................127 6.1. STRUCTURAL STUDIES BY SCANNING ELECTRON MICROSCOPY ........ 127 6.1.1 6.1.2 6.1.3 6.1.4 6.2. Acetone series ..............................................................................................................127 Effect of the solvent .................................................................................................... 131 Drying procedure ........................................................................................................132 TMOS aerogels in CO2 as solvent ...........................................................................133 Sample preparation..................................................................................... 134 TEM set-up .............................................................................................. 134 6.2.1 6.2.2 6.2.3 Imaging the acetone-series silica aerogels ...........................................................135 Methanol series............................................................................................................135 Replicas visualization.................................................................................................138 Replicas visualization.................................................................................. 138

TRANSMISSION ELECTRON MICROSCOPY .......................................................... 134

7.

REFERENCES...................................................................................................................................... 141

Index

iv

C h a p t e r I V : MECHANICAL CHARACTERIZATION OF SILICA AEROGELS
1. INTRODUCTION ...............................................................................................................................146 1.1. 1.2. 2. MICROINDENTER DESCRIPTION............................................................................. 147 MECHANICAL CHARACTER IZATION...................................................................... 149

MECHANICAL PROPERTIES OF SILICA AEROGELS AS A FUNCTION OF DENSITY................................................................................................................................................152 2.1. 2.2. SAMPLE PREPARATION .................................................................................................. 152 EFFECT OF THE A LKOXIDE......................................................................................... 152

3.

INFLUENCE OF SOLVENT AND SUPERCRITICAL DRYING METHOD ON THE MECHANICAL PROPERTIES .......................................................................................................156 3.1. 3.2. EFFECT OF THE DRYING PROCEDURE................................................................. 156 EFFECTS OF THE S OLVENT......................................................................................... 158

4.

MICROMECHANICAL PROPERTIES OF CARBON-SILICA AEROGEL COMPOSITES ......................................................................................................................................159 4.1. 4.2. INTRODUCTION ................................................................................................................. 159 EFFECT OF CARBON ADDITION................................................................................ 160

5.

VISCOELASTICITY OF SILICA AEROGELS AT ULTRASONIC FREQUENCIES .....169 5.1. 5.2. 5.3. 5.4. INTRODUCTION ................................................................................................................. 166 EXPERIMENTAL SET-UP: AIR-COUPLED BROAD-BAND PIEZOELECTRIC TRANS DUCERS ............................................................................. 167 DETERMINATION OF THE VISCOELASTICITY OF SILICA AEROGELS AT ULTRASONIC FREQUENCIES ..................................................................................... 169 DISCUSSION............................................................................................................................171

6. 7.

CONCLUSIONS ...................................................................................................................................173 REFERENCES......................................................................................................................................175

C h apt e r 1.

V : SILICA AEROGEL MICROPARTICLES

SOL-GEL ROUTE TO DIRECT FORMATION OF SILICA AEROGEL MICROPARTICLES USING SUPERCRITICAL ETHANOL/ACETONE........................ 181 1.1. 1.2. ‘IN SITU’ PA RTICLE PROCESSING ............................................................................. 182 AEROGEL MICROPARTICLE CHARACTERIZATION ........................................ 184 1.2.1 Scanning Electron Microscopy ................................................................................185 Independent solutions .................................................................................. 189

Index
1.2.2 1.2.3 2.

v
Transmission Electron Microscopy ........................................................................190 Atomic Force Microscopy ......................................................................................... 191

SOL-GEL ROUTE TO DIRECT FORMATION OF SILICA AEROGEL MICROPARTICLES USING SUPERCRITICAL CARBON DIOXIDE ...............................195 2.1. 2.2. ‘IN SITU LOW TEMPERATURE MICROPARTICLES : TEOS, HCOOH, AND SUPERCRITICAL CO2 AS SOLV ENT ............................................................................196 ‘PRECURSOR DIRECTLY INJECTED IN CO2 SUPERCRITICA L CONDITIONS AT LOW TEMPERATURE.................................................................. 198 2.2.1 2.2.2 2.3. 2.4. Injection of hydrolysis and precursor solution independently ..........................199 Injection of sol ............................................................................................................ 203

IN SITU’ INJECTION IN LIQUID CO2 ........................................................................ 203 INJECTION OF PREPOLYMERIZED PRECURS OR IN SUPERCRITICA L CO2 .............................................................................................................................................. 205

3. 4.

CONCLUSIONS .................................................................................................................................. 208 REFERENCES..................................................................................................................................... 208

C h a p t e r V. SILICA AEROGEL FILMS
1. APPLICATIONS OF AEROGEL FILMS.......................................................................................212 1.1. 1.2. 1.3. 1.4. 1.5. 2. ELECTRONIC ........................................................................................................................ 212 OPTICAL .................................................................................................................................. 213 THERMAL ............................................................................................................................... 214 ACOUSTIC ............................................................................................................................... 214 ENVIRONMENT AND OTHERS ................................................................................... 214

SOL-GEL COATING METHODS...................................................................................................215 2.1. 2.2. 2.3. 2.4. 2.5. DIP COATING........................................................................................................................ 215 SPIN COATING ..................................................................................................................... 216 SPRAY COATING.................................................................................................................. 217 SURFACE TENSION COATING..................................................................................... 217 SUBCRITICAL DRYING BY SURFACE DERIVATION ......................................... 217

3.

REFERENCE EXPERIMENTAL RESULTS ..............................................................................217 3.1. DIP COATING........................................................................................................................ 217 a) Low-temperature dip coating .................................................................... 218 b) High-temperature dip coating ................................................................... 219 3.2. SPIN COATING ..................................................................................................................... 221 a) Spin coating with High-Temperature drying .............................................. 222

Index
4.

vi
PROPOSED NEW METHODS: ‘IN SITU’ PREPARATION AT HIGH PRESSURE AND INJECTION AT SUPERCRITICAL CONDITIONS..................................................... 224 4.1. ‘IN SITU’ PREPA RATION AT HIGH PRESSURE.................................................... 224 4.1.2 4.1.3 4.2. ‘In situ’ high temperature......................................................................................... 225 ‘In Situ’ low-temperature coating method............................................................ 225

SPRAY COATING BY DIRECT INJECTION IN SUPERCRITICAL CO2 AT LOW TEMPERATURE........................................................................................................ 227

5. 6.

CONCLUSIONS .................................................................................................................................. 230 REFERENCES......................................................................................................................................231

CONCLUSIONS ....................................................................................................................................................233 ARTICLES PUBLISHED RELATED TO THIS THESIS........................................................................241 ANNEX I: SUPERCRITICAL FLUIDS..........................................................................................................243 ANNEX II: TECHNICAL DESCRIPTION OF THE JOIN ICMAB-CM HIGH PRESSUREHIGH TEMPERATURE LABORATORY....................................................................................................247 ANNEX III: INTRODUCTION TO ADSORPTION ANALYSIS AND THE BET MODEL ...257 REsum de la tesis. AEROGELS de sílice: SÍNTESIS i caracterització AGRAÏMENTS ............................................................................................................................................... 297 265

PRÒLEG

Durant el temps de realització d‟aquesta tesi he tingut la sort de treballar amb un material tan sorprenent i atractiu com és l‟aerogel. El resultat ha estat aquesta tesi estructurada en 5 capítols: El primer capítol („Aerogels: An Introduction’), és una introducció amb apunts històrics dels aerogels i de les seves aplicacions. El capítol està estructurat en 5 apartats: 1) mètode sol-gel, una recapitulació bàsica de la tècnica sol-gel, 2) assecat supercrític dels gels, on s‟expliquen els conceptes bàsics dels fluids supercrítics i els diferents mètodes d‟assecat supercrític, 3) tècniques de caracterització, breu introducció a les tècniques aplicades per la caracterització dels aerogels, 4) aplicacions, un resum de les aplicacions més comunes dels aerogels i, finalment 5) bibliografia, on es presenta un ampli llistat de referències. La motivació per escriure aquesta llarga introducció és el fet de que aquesta tesis doctoral és „la primera‟ del nostre grup, i probablement de l‟estat espanyol, centrada en l‟estudi, caracterització i síntesi d‟aerogels de sílice. La idea principal és que serveixi d‟ajut a futurs projectes que impliquin aquest material. El segon capítol, (Synthesis and optimization of silica aerogels: Influence of molar ratios of precursor, solvent and water) és bàsicament descriptiu i el seu objectiu es centra en fer un seguiment del procés usat per a l‟optimització de la síntesi i del cicle d‟assecat dels aerogels. En aquest capítol s‟estableix quin és el camí de síntesi més adequat per obtenir les característiques requerides per cada tipus d‟aerogel. Aquesta secció també conté una bibliografia àmplia per a que es faciliti l‟oportunitat d‟obtenir més informació d‟una determinada síntesi. En definitiva el segon capítol inclou bàsicament informació per a la reproducció de les síntesis que he seguit en el nostre laboratori. Aquesta informació la trobem esbossada en taules que contenen la majoria de paràmetres importants de la preparació de les mostres. En l‟últim apartat d‟aquest capítol s‟inclouen les conclusions on es resumeix les síntesis més adequades per a cada procés, per tant la lectura completa d‟aquest capítol serà essencialment necessària només en el cas que es vulgui reproduir algun dels resultats.

Prefaci

2

En el tercer capítol (Aerogel Characterization) s‟exposa la caracterització realitzada en les diverses sèries d‟aerogels obtingudes amb diferent transparència, densitat i porositat, com a conseqüència de la seva microestructura. Un dels aspectes més importants en la preparació d‟aerogels és la possibilitat de control de les propietats físiques del material: densitat, porositat i àrea superficial. Aquestes propietats estan directament relacionades amb l‟estructura del material: la distribució i mida de porus, la distribució i mida de partícules, la mida de „clusters‟,... Per determinar la microestructura porosa d‟aquest material s‟ha desenvolupat un model que utilitza els resultats de varies tècniques ja que l‟ús d‟una sola no permet la caracterització completa de tot el rang de porositats i de mida de partícules. Les tècniques utilitzades en aquest treball per a obtenir informació estructural dels aerogels són les tècniques de BET, microscopia electrònica (SEM, TEM) o microscopia de forces atòmiques AFM). Per a obtenir informació complementaria de la microestructura d‟aquests materials tan altament porosos -determinació de la mida de porus i partícula- és necessària la utilització d‟altres tècniques (l‟anàlisi de la dispersió de la llum). Un dels inconvenients dels aerogels és la seva fragilitat, és per aquest motiu que un dels objectius d‟aquesta tesi s‟ha centrat en la caracterització mecànica d‟aquests materials mitjançant una tècnica no destructiva: la microindentació. El quart capítol („Mechanical properties of silica aerogels’) mostra els resultats obtinguts explicant els resultats publicats en una sèrie de quatre articles, el primer relaciona la dependència de les propietats mecàniques dels aerogels de sílice amb la seva densitat, el segon article analitza l‟influencia de varis paràmetres de síntesi (solvent utilitzat i procediment de assecat supercrític) amb les propietats mecàniques dels aerogels de sílice, finalment el tercer article descriu com, amb la finalitat de millorar les propietats mecàniques dels aerogels es varen sintetitzar nous aerogels compostos amb carbó actiu. Aquests composites presenten un augment molt accentuat de l‟elasticitat de l‟aerogel de sílice. En l‟últim article es caracteritzen les propietats viscoelàstiques dels aerogels de sílice. En el cinquè capítol (Aerogel Microparticles) es descriu el procés d‟obtenció de micropartícules d‟aerogels mitjançant una nova tècnica. També s‟hi descriu la caracterització de les diferents micropartícules obtingudes.

Prefaci

3

En el sisè capítol (Aerogel Films) es desenvolupa un estudi d‟obtenció de capes d‟aerogels mitjançant una nova tècnica. També es porta a terme la caracterització de les diferents capes obtingudes.

GLOSSARY OF TERMS1:

Aerogel Defined as a group of extremely light and porous solid materials; the lightest is less than four times as dense as dry air. Aerogels are derived via a sol-gel process in combination with a subsequent drying step (most often achieved by supercritical extraction) the result are monolithic, open porous materials with a backbone morphology that can be modeled in terms of three dimensionally interconnected strings of microscopic pearls. Aerosol A colloidal suspension of particles in a gas (the suspension may be called a fog if the particles are liquid and a smoke if the are solid). Aging The term aging is applied to the process of change in structure and properties after gelation. Bond formation does not stop at the gel point. In the first place, the network is initially compliant, so segments of the gel network can still move close enough together to allow further condensation (or other bond-forming processes). Moreover, there is still a sol within the gel network, and then those smaller polymers or particles continue to attach themselves to the network. Alcohol A molecule formed by adding a hydroxyl (OH) group to an alkyl molecule, as in methanol (CH3OH) or ethanol (C2H5OH). Alkane A molecule containing only carbon and hydrogen linked exclusively by single bonds, as in methane (CH4) and ethane (C2H6); the general formula is CnH2n+2.

1

Their literal definitions were taken from http://eande.lbl.gov/ECS/aerogels/satoc.htm, Academic Press Dictionary of Science and Technology and from C.J. Brinker, G.W. Sherer, Sol-Gel Science. Physics and Chemistry of Sol-Gel Processing, Academic Press, New York, 1990.

Glossary of terms

5

Alkoxy A ligand formed by removing a proton from the hydroxyl on an alcohol, as in methoxy ( OCH3) or ethoxy ( OC2H5). Where the dot, , indicates an electron that is available to form a bond. Alkyl A ligand formed by removing one hydrogen (proton) from an alkane molecule producing, for example, methyl ( CH3) or ethyl ( C2H5) Brownian motion In a colloid, the inertia of the dispersed phase is small enough to exhibit Brownian motion (or Brownian Diffusion), a random walk driven by momentum imparted by collisions with molecules of the suspending medium. Ceramic A nonmetallic and inorganic material; included all metal oxides, nitrides, and carbides, both crystalline and noncrystalline. Colloid A mixture in which one substance is divided into minute particles (called colloidal particles) and dispersed throughout a second substance. The dispersed phase is so small ( 1–1000 nm) that gravitational forces are negligible and interactions are dominated by short-range forces, such as van der Waals attraction and surface charges. The mixture is also called a colloidal system, colloidal solution, or colloidal dispersion. Familiar colloids include fog, smoke, and homogenized milk.

Glossary of terms

6

Condensation A condensation reaction occurs when two metal hydroxides (M-OH + HO-M) combine to give a metal oxide species (M-O-M). The reaction forms one water molecule. (OR)3Si-OH + HO-Si(OR)3 or (OR)3Si-OR + HO-Si(OR)3 (OR)3Si-O-Si(OR)3 + ROH. (OR)3Si-O-Si(OR)3 + H2O

By definition, condensation liberates a small molecule, such as water or alcohol. The R represents a proton or other ligand (if R is an alkyl, then OR is an alkoxy group), and ROH is an alcohol; the bar (-) is sometimes used to indicate a chemical bond. Critical point State at which two phases of a substance first become indistinguishable. For example, at pressures higher than 217.6 atm and temperatures above 374°C, the meniscus between steam and liquid water will vanish; the two phases become indistinguishable and called supercritical fluid. Crosslinkage/branching If a polyfunctional unit with 2 is present, the chains can be joined by crosslinks to

form a three-dimensional structure. Polymerization of silicon alkoxide, for instance, can lead to complex branching of the polymer because a fully hydrolyzed monomer Si(OH)4 is tetrafunctional. On the other hand, under certain conditions (e.g., low water concentration) fewer than four ligands will be capable of condensation, so relatively little branching will occur. Emulsion Is a suspension of liquid droplets in another liquid. These types of colloids can be used to generate polymers or particles from which ceramic materials can be made.

Glossary of terms

7

Functionality The number of bonds that a monomer can form is called its functionality, . Typical oxide monomers are bifunctional ( = 2), trifunctional ( = 3), or tetrafunctional ( = 4), any of which may be called polyfunctional ( arbitrary). Gel Point If a monomer can make more than two bonds, then there is no limit on dimensions so that it extends throughout the solution. The point in time at which the network of linked oxide particles spans the container holding the sol. At the gel point, the sol becomes a gel. The gel point corresponds to the percolation threshold, when a single cluster (called the spanning cluster) appears that extends throughout the sol; the spanning cluster coexists with a sol phase containing many smaller clusters, which gradually become attached to the network Gel A gel consists of two parts, a solid part and a liquid part. The solid part is formed by the three-dimensional network of linked oxide particles. The liquid part (the original solvent of the sol) fills the free space surrounding the solid part. The liquid and solid parts of a gel occupy the same apparent volume. Thus, a gel is a substance that contains a continuous solid skeleton enclosing a continuous liquid phase. The gel can be removed from its original container and can stand on its own. The continuity solid structure gives elasticity to the gel (as in the familiar gelatin dessert). Hydrolysis The reaction of a metal alkoxide (M-OR) with water forms a metal hydroxide (MOH). A hydroxyl ion becomes attached to the metal atom, as in the following reaction: Si(OR)4 + H2O HO-Si(OR)3 + ROH

Glossary of terms

8

Depending on the amount of water and catalyst present, hydrolysis may go to completion (so that all of the OR groups are replaced by OH). Si(OR)4 + 4H2O H2 O-Si(OH)4 + 4ROH

or stop while the metal is only partially hydrolyzed, Si(OR)4-n(OH)n. Meniscus A phase boundary that is curved because of the surface tension. Miscible Two liquids are considered miscible or mixable if shaking them together results in a single liquid phase, with no meniscus visible between layers of liquid. Metal alkoxides Are members of the family of metalorganic compounds, which have an organic ligand attached to a metal o metalloid atom. The most thoroughly studied example is silicon tetraethoxide (or tetraethoxy-silane, or tetraethyl orthosilicate, TEOS), Si(OC2H5)4. Organometallic compounds are defined as having direct metal-carbon bonds, not metal-oxygen-carbon linkages as in metal alkoxides; thus, alkoxides are not organometallic compounds. Metal alkoxides are popular precursors because they react readily with water. Monolith Gelation can occur after a sol is cast into a mold, in which case it is possible to make objects of a desired shape. If the smallest dimension of the gel is greater than a few millimeters, the object is generally called a monolith. Polymer A polymer (“many member”) is a huge molecule (also called a macromolecule) formed from hundreds o thousands of units called monomers that are capable of forming at least two bonds.

Glossary of terms

9

Porosity: Microporosity IUPAC definition: pores with mean diameter lower than 2 nm. Mesoporosity Pores with mean diameter between 2 nm and 50 nm. Macroporosity Pores with mean diameter larger than 50 nm. Precursors In the sol-gel process, the precursors (starting compounds) for preparation of a colloid consist of a metal or metalloid element surrounded by various ligands (appendages not including another metal or metalloid atom). The latter is an example of an alkoxide, the class of precursors most widely used in sol-gel research. Shrinkage Shrinkage of a gel, either during syneresis or as liquid evaporates during drying, involves deformation of the network and transport of liquid through the pores. Sol A colloidal suspension of solid particles in a liquid. A solution of various reactants that are undergoing hydrolysis and condensation reactions. The molecular weight of the oxide species produced increases continuously. As these species grow, they may begin to link together in a three-dimensional network. Supercritical fluid A substance that is above its critical pressure and critical temperature. A supercritical fluid possesses some properties in common with liquids (density, thermal

Glossary of terms

10

conductivity) and some in common with gases (fills its container, does not have surface tension). Syneresis Some gels exhibit spontaneous shrinkage; called syneresis, as bond formation or attraction between particles induces contraction of the network and expulsion of liquid from the pores. Xerogel Drying by evaporation under normal conditions by evaporation gives rise to capillary pressure that causes shrinkage of the gel network. The resulting dried gel is named "xerogel", a word issued from the Greek word "xeros" and which means dry. The shrinkage during drying is often extreme (~90%) for xerogels. The no collapse requirement distinguishes aerogels from xerogels.

Ch a pt er I

AEROGELS: AN INTRODUCTION

SECTION OUTLINE
1. GENERAL OVERVIEW ON AEROGELS .....................................................................................12 1.1. 2. COMMERCIAL SILICA AEROGEL...................................................................................... 14

SOL-GEL METHOD.............................................................................................................................15 2.1. 2.2. ANTECEDENTS OF GE L SYNTHESIS .............................................................................. 16 PREPARATION OF SILI CA GE LS ....................................................................................... 16

3. 4.

DRYING PROCEDURE OF GELS .................................................................................................. 20 AEROGEL APPLICATIONS ............................................................................................................. 22 4.1. POROSITY AND SURFACE AREA APPLI CATIONS...................................................... 22 Electrodes in capacitors ................................................................................. 22 Capacitive deionization ................................................................................. 23 Studies of superfluid transitions and phase separation of 3He-4He...................... 23 4.2. 4.3. 4.4. 4.5. 4.6. OPTICAL PROPERTY APPLICATIONS ............................................................................. 23 Çerenkov (particle detection and counters)........................................................ 23 THERMAL INSULATOR APPLICATI ONS........................................................................ .24 ACOUSTICAL AND MECHANICAL APPLICATIONS ................................................... 24 Shock compression experiments ...................................................................... 25 ELECTRICAL AND E LECTRONIC APPLI CATIONS..................................................... 25 SPACE APPLICATIONS .......................................................................................................... 25

5.

REFERENCES....................................................................................................................................... 25

Chapter I. Silica aerogel: An Introduction

12

1.

GENERAL OVERVIEW ON AEROGELS

This section surveys the literature and summarizes the historical background of aerogels development, their production by the sol-gel process, several drying methods, and various structural investigations. Aerogel is defined as a group of extremely light and porous solid materials. Silica-based aerogels are among the lightest ones, can be less than four times as dense as dry air, and some are nearly transparent, its nickname is “solid smoke” or “frozen smoke”. Since this definition is good for most porous materials, the term aerogels became reserved for the porous gels obtained by removing solvent from highly swollen gels at the conditions that no or minimal collapse occurs, which causes the liquid in the gel to become supercritical (in a state between a liquid and a gas) and lose its surface tension. The result is an open porous material with a backbone morphology that can be modeled in terms of three dimensionally interconnected strings of nanoscopic pearls. The length scale of both the “pearls” as well as the interconnected voids can be independently tailored over a wide range, i.e. from a few nanometers to several microns.

Figure I.1 The basic blocks of the structure of silica aerogel are spherical primary particles with five nanometers in diameter and with the same density as bulk silica. These spheres cluster into secondary particles that are linked in chains to create the porous aerogel skeleton (on the range 2050 nm).

One of the striking advantages of aerogels compared to other porous materials is that both porosity and inner surface area can be tuned independently. Porosities of up to 99.9 % are achievable; when microporosity is present, the specific surface area can exceed 1500 m2/g.

Chapter I. Silica aerogel: An Introduction

13

Because of their unique properties, i.e., large surface area, very small pores and very low bulk density, aerogels are potentially important candidates for a wide range of applications. Table I.1 gathers some of the remarkable properties of silica aerogels.
Table I.1 Physical properties of silica aerogels.

Property Apparent density Inner surface area Solid percentage in volume Mean pore diameter Primary particle diameter Index of refraction Thermal tolerance Poisson’s ratio Young’s modulus Tensile strength Fracture toughness Dielectric constant Acoustic impedance Sound velocity through the medium Optical property Thermal conductivity

Value 0.003-0.5 g/cm 3 500-1500 m 2/g 0.13-15 % 20-150 nm 2-5 nm 1.007-1.24 Up to 500 C 0.2 0.1-300 MPa 16 kPa 0.8 kPa.m 1/2 1.1 104 Kg/m 2.s 20-800m/s Transmittance>90%
(630nm)

Comments Most common density is 0.1g/cm 3 ( air = 0.001g/cm 3) As determined by nitrogen adsorption/desorption A cubic centimeter of an aerogel has about the same surface area as one soccer field) Typically 5 % (95 % free space) As determined by nitrogen adsorption/desorption (varies with density) Determined by transmission electron microscopy Very low for solid material (nair= 1.004) Shrinkage begins slowly at 500 C, increases with increasing temperature. Melting point is ~1200ºC Independent of density, similar to dense silica. Determined using ultrasonic methods. Very small (<104) compared to dense silica For density of 0.1 g/cm 3 For density of 0.1 g/cm 3. Determined by 3-point bending For density of 0.1 g/cm 3, very low for a solid material (kair= 1) Determined using ultrasonic methods al KHz frequency. 100 m/s for density of 0.07 g/cm 3, one of the lowest velocities for a solid material Transparent-blue haze

Very low thermal conductivity. 2 cm slab provides 0.02 W/mK (20 C) the same insulation as 30 panes of glass

Aerogel is an extremely adaptable material: aerogels have been prepared from many metal oxides, including tin, tungsten and iron and also, alumina, zirconia, titanic, and magnesia , as well as from organic gels: carbon, gelatin, organic polymers, proteins, and cellulose.

Chapter I. Silica aerogel: An Introduction

14

The laboratory of the Aerogel Research Group at the Material Science Institute of Barcelona (ICMAB) is equipped to produce aerogels in a variety of shapes and configurations (from bulk monoliths to thin films or microspheres), in small to medium-sized batches.
1.1 COMMERCIAL SILICA AEROGEL

A sign of growth of the technology is the increasing number of companies producing aerogels and the increasing number of patents involving aerogels. Some works have been published about aerogel commercialization, technology, markets and costs [29]. In 1930, S.S. Kistler invented the aerogels by supercritically drying of gels, and Montsanto Corp. produced thousands of tons of silica aerogels during 1940s and 1950s, using the substance as an additive in cosmetics and toothpaste. Aerogel research was largely abandoned for the next 50 years. Then, in the 1980s, newer safer production processes to create aerogels were developed under the leadership of A.J. Hunt at the Lawrence Berkeley Laboratory eetd.lbl.goc/ecs/aerogels/kistler/inde.htm, and J. Phalippou at the University of Montpellier, leading to the identification of applications for aerogels as insulators for rocket fuel storage and later as cosmic dust collectors on two shuttle missions. Airglass, in Sweden, (www.airglass.se) is the only current large producer of aerogel for thermal insulation, but Cabot Corp. (www.cabot-corp.com/cabot.nsf) and Aspen Systems Inc. (www.aspensystems.com/aerogel.html) will reach the market in the next months. Nanopore (www.nanopore.com) explores other applications for nanoporous solids. Silica aerogels, attracted international attention early in the 1990s after Livermore Lab. Scientist created a silica aerogel 10 time less dense than the lightest precious version. (http://www.llnl.gov/). Aerogels are also the best thermal insulators ever discovered. NASA used aerogels to insulate the electronics on the intrepid Sojourner from the cold of the Martian night www.science.nasa.gov/aerogel. Aerogels have amazing thermal dissipation properties. Aerogels can also be either electrically conductive (i.e. carbon aerogels) or insulators (silica aerogels). Electrical insulators fabricated with aerogels may double the actual computer speeds. Contemporary circuits boards have dielectric constants, k, between 2.5 and 4 (air has k=1). Decreasing k of the insulating film can increase the speed of the computer by allowing engineers to place components closer together. Researchers have already successfully created aerogel films -made mostly of air- with dielectric values ranging between 2.3 and 2.01. Other aerogels are organic, made of carbon and hydrogen atoms. Organic aerogels are stiffer and stronger than silica aerogels and are measurably better insulators. Organic aerogels have

Chapter I. Silica aerogel: An Introduction

15

extremely high thermal resistance (six times higher than fiberglass) and can be converted to pure carbon aerogels with still retaining many properties of the original aerogel, and at the same time becoming electrically conductive. Carbon aerogels have been used as electrode in energy storage devices known as double-layer capacitors. Such devices are able to deliver power faster than conventional batteries and thus have potential application in electric vehicles, “pure power” stations, telecommunications, and microelectronics. Carbon aerogels capacitors are already in the electronics shops by Cooper Electronics Technologies (www.cooperelectech.com/power/indexIntro.htm). One of the applications uses aerogels as catalysts to reduce nitrous oxide emissions from cars exhaust systems. Some scientists expect aerogels will be used as catalysts within a few years because of their high surface area (a cubic centimeter of an aerogel has about the same surface area as one soccer field). In addition, metallic atoms or metal-oxide particles can be placed in aerogels to cause reactions. Lots of information about aerogels can be obtained from Internet. A good starting point can be the NASA aerogel Web site at the http://www.science.nasa.gov/aerogel. A nice and documented work on the history of aerogels has been prepared by Mike Ayers (LBNL) and can be navigated at eetd.lbl.goc/ecs/aerogels/kistler/index.htm.

2.

SOL-GEL METHOD

The formation of aerogels, in general, involves two major steps, the formation of a wet gel, and the drying of the wet gel, avoiding major shrinkage, to form an aerogel.
2.1 ANTECEDENTS OF GEL SYNTHESIS

Kistler [1, 2] was the first researcher who formulated the idea of replacing the liquid phase by a gas with only a slight shrinkage of the gel back in the 1930s. Eventually, he obtained silica aerogels by a technique known as the „water-glass process‟ outlined below:

Chapter I. Silica aerogel: An Introduction

16

Figure I.2 Left recipient contains a sol /transparent at visible range). Right recipient contains a gel (blue shading).

1. 2. 3. 4.

Preparation of a hydrogel (gels with water as a solvent) in reaction of sodium silicate with hydrochloric acid. Removal of sodium and chlorine ions. This step involves a long and tedious soaking of the gel. Converts the hydrogel into alcogel by replacing water with ethyl alcohol in a lengthy process of solvent replacement. Drying at above critical conditions for ethyl alcohol.

When these steps were followed, an extremely light solid remained; however, the work on solid aerogels was mostly forgotten until 1970s. An improved method of preparing gels took place in the Teichner and Nicholaon group [3] [4] at the Claude Bernard University in Lyon. The procedure was substantially simplified by carrying out the sol¯ gel transition directly in the solvent (that was removed at supercritical conditions) through the use of relatively new class of compounds called metal alkoxides. Alkoxide-based sol-gel chemistry avoids the formation of undesirable salt by-products, and allows a much greater degree of control over the final product.
2.2 PREPARATION OF SILICA GELS

A common way to synthesize gels at room temperature corresponds to a chemical reaction implying metal alkoxides and water in an alcoholic solvent. The majority of silica aerogels prepared utilizes silicon alkoxide precursors. The most common of these are tetramethyl orthosilicate (TMOS or Si(OCH3)4), and tetraethyl orthosilicate (TEOS or Si(OCH2CH3)4). However, many other alkoxides, containing various organic functional groups, can be used to

Chapter I. Silica aerogel: An Introduction

17

impart different properties to the gel [5, 6]. The first reaction is a hydrolysis which induces the substitution of OR groups linked to silicon by silanol Si-OH groups. A condensation reaction occurs when two silanol groups (Si-OH + HO-Si) react together to form Si-O-Si (siloxane) bonds, which lead to the silica network formation. Three reactions are generally used to describe the sol¯ gel process [7]: (Eq. I.1)

(Eq. I.2)

(Eq. I.3)

where R is an alkyl group, Cx H2x+1 The hydrolysis reaction (Eq. I.1) replaces alkoxide groups (OR) with hydroxyl groups (OH). Subsequent condensation reactions (Eq. I.2, Eq. I.3) involving the silanol groups produce siloxane bonds (Si¯ O¯ Si) plus the by-products alcohol (ROH) or water. Because water and alkoxysilanes are immiscible, a mutual solvent such as alcohol is normally used as a homogenizing agent. The final density of the aerogel depends on the concentration of silicon alkoxide monomers in the solution. The balanced chemical equation for the formation of a silica gel is: Si(OR)4 (liq.) + 2H2O (liq.) = SiO 2 (solid)+ 4HOR (liq.) (Eq. I.4) The stoichiometry of the reaction requires two moles of water per mole of alkoxysilane. In practice, this amount of water leads to incomplete reaction, and weak, cloudy aerogels. Therefore, most aerogel recipes use a higher water ratio than is required by the balanced equation (anywhere from 4-30 equivalents). The gel point is the time at which the network of linked oxide particles spans the container holding the sol. At the gel point, the sol becomes a gel. This two-phase material, a solid part and a liquid part, consists of shaped solid exhibiting specific properties. The solid part is formed by the three-dimensional network of linked oxide particles. The liquid part (the original solvent of the sol and a small amount of water) fills the free space

Chapter I. Silica aerogel: An Introduction

18

surrounding the solid part. The liquid and solid parts of a gel occupy the same apparent volume.

Catalyst + Water

Alcohol

TMOS/ TEOS Start of reaction Sol

Skeleton Solvent Gelation

Alcogel
Figure I.3 Scheme of silica aerogel sol-gel synthesis by condensation of silica alkoxide precursor on alcohols.

As condensation reactions progress the gel will gain rigidity. At this point, the gel is usually removed from its mould. However, the gel must be kept covered by alcohol to prevent evaporation of the liquid contained in the pores of the gel. Evaporation causes severe damage to the gel and will lead to poor quality aerogels. Catalysts The kinetics of the above reaction is impractically slow at room temperature, often requiring several days to reach completion. For this reason, acid or base catalysts are added to the formulation. The amount and type of catalyst used play key roles in the microstructural, physical and optical properties of the final aerogel product (sections 3.5, 3.5). Acid catalysts can be any protic acid, such as HCl. Base-catalysis usually uses ammonia, or ammonia buffered with ammonium fluoride. Aerogels prepared with acid catalysts often

Chapter I. Silica aerogel: An Introduction

19

show more shrinkage during supercritical drying and may be less transparent than base catalyzed aerogels. The microstructural effects of various catalysts are harder to describe accurately, as the substructure of the primary particles of aerogels can be difficult to image with electron microscopy (section 3.7). All have small (2-5 nm diameter) particles that are generally spherical or egg-shaped. With acid catalysis, however, these particles may appear less defined than those in base-catalyzed gels. Two-Step Aerogels Typical acid or base catalyzed gels are often classified as "single-step" gels, referring to the "one-pot" nature of this reaction. A more recently developed approach uses pre-polymerized TEOS as the silica source. Pre-polymerized TEOS is prepared by heating an ethanol solution of TEOS with a sub-stoichiometric amount of water and an acid catalyst. The solvent is removed by distillation, leaving a viscous fluid containing higher molecular weight silic on alkoxy-oxides. In a second step, this material is redissolved in ethanol and reacted with additional water under basic conditions until gelation occurs. Gels prepared in this way are known as "two-step" acid-base catalyzed gels. Pre-polymerized TEOS is available commercially from Silbond Corp. (Silbond H-5). These slightly different processing conditions impart important changes to the final aerogel product. Single-step base catalyzed aerogels are typically more brittle than two-step aerogels. Moreover, two-step aerogels have a smaller and narrower pore size distribution and are often optically clearer than single-step aerogels (Chapter II, section 3). Aging and Soaking At the gel point the silica backbone of the gel contains a significant number of unreacted alkoxide groups. Sufficient time must be given for the strengthening of the silica network. This can be enhanced by controlling the pH and water content of the covering solution. Common aging procedures for base catalyzed gels typically involve soaking the gel in an alcohol/water mixture of equal proportions to the original sol. The gels are soaked in this solution for up to 24 hours. This step, and all subsequent processing steps, is diffusion controlled. Diffusion is affected by the thickness of the gel. Then, the time required for each processing step increases dramatically as the thickness of the gel increases.

Chapter I. Silica aerogel: An Introduction

20

After aging the gel, all water still contained within its pores must be removed prior to drying. This is simply accomplished by soaking the gel in pure alcohol several times until all the water is removed. Again, the length of time required for this process is dependent on the thickness of the gel. Any water left in the gel will not be removed by supercritical drying, and will lead to an opaque, white, and dense aerogel. Chapter II shows that variations in synthesis conditions (for example, ratio H 2O/Si, the catalyst type and concentrations, the type of solvent, temperature and pressure of supercritical drying) cause modifications in the structure and properties of the obtained silica aerogels [8]. Thus, porous structure of silica aerogels strongly depends on preparation and drying parameters [9 -18].

3.

DRYING PROCEDURE OF GELS

An aerogel results from a supercritical drying process. This is where the liquid within the gel is removed, leaving only the linked silica network. The difference between classical drying and supercritical drying is shown in Figure I.4. From point 1 to 5, (purple arrow) the liquid is depressurized isothermally (classical drying). Consequently, we can say that xerogels refer to gels dried at temperature close to room temperature and under atmospheric pressure. The supercritical drying is performed inside an autoclave, which allows to overpass the critical point (PC, TC) of the solvent, as shown in Figure I.4 (Path 1-2-3-4-5); or by prior solvent exchange with liquid CO 2 followed by supercritical CO 2 venting (lower temperature drying). The supercritical fluid is a substance that is above its critical pressure and critical temperature; it possesses some properties in common with liquid (density, thermal conductivity) and some in common with gas (fills its container, does not have surface tension). A more detailed description of supercritical fluids can be found in Annex I). Strong inorganic solids are commonly dried using alcohol (or acetone) as solvent or dried using CO 2 as solvent.

Chapter I. Silica aerogel: An Introduction

21

Figure I.4 Scheme of the pressure and temperature variation on the solvent phase diagram during a gel supercritical drying process. The shaded area represents the supercritical region (SCF), where C is the critical point, Tr represents the triple point, and 1 to 5 are random points in the phase diagram.

Under ambient conditions, during the evaporation of the solvent, a liquid-vapor interface is formed within the pores of the gel. The surface tension of the liquid creates a concave meniscus in each capillary. By evaporation, the meniscus recedes and the compressive force on the wall of the pores produces the collapse of the initial gel framework, or shrinkage (Figure I.5). A liquid-vapor interface or the presence of a liquid in equilibrium with the vapor is only observed below the critical temperature and pressure of the solvent. Above the critical point (Figure I.4) the liquid no longer existed. Supercritical fluid is a gaseous like-phase, so the liquid meniscus and its interfacial tension would not form in these conditions.
Vapor
p
Meniscus

2

cos r

, capillary pressure

is the surface tension of the liquid r is the pore radius

Liquid

r, pore radius
Figure I.5 The liquid-vapor interface formed in the gel capillary during drying.

Using the high temperature drying procedure some problems may arise from the combination of high pressures and high temperatures (methanol critical parameters: Pc=81 bar, Tc=240 C) , i.e. flammability of the solvents. Alternatively, supercritical drying with CO 2 has been developed by substituting, under pressure, alcohol in the gel by liquid carbon

Chapter I. Silica aerogel: An Introduction

22

dioxide and then drying the aerogel with carbon dioxide at supercritical conditions. CO 2 is of particular interest due to its low critical temperature (31 C), non-flammability, and nontoxicity. The process results in a reduction of the temperature and pressure required for drying aerogels.

4.

AEROGEL APPLICATIONS*

Aerogels were discovered more than 70 years ago. During these years, many potential applications were described [19-22] and more new applications are mentioned in recent reviews [23-28]. This section reviews some of the aerogels applications. In addition to being the best thermal insulators ever discovered, aerogels have the lowest dielectric constant, and the lowest sound velocity of any known solid material, sound propagates more slowly through aerogels than through air. Other possible applications include, substrates for chemical catalysis, ultrafilters, seawater desalinization, battery electrodes, solar collector covers, acoustic delay lines, refrigerator insulation, replacements for the air between the panes of double-glazed windows, to detect high-energy subatomic particles emitted by particle accelerators, micrometeoroid collectors, and supercapacitors, adsorbents, sensors and fuel cells, and even safe insecticides. The following applications for aerogels are associated with certain properties of aerogel materials. In many cases, the application is associated with a single property even if the aerogels have a combination of properties appropriate to the given application.
4.1 POROSITY AND SURFACE AREA APPLICATIONS

Due to their high porosity, their very large inner surface area (easily accessible because of the open porosity), and the controllable dispersion of the active component, they are especially active catalysts or catalytic substrates [30-36]. There are numerous references of this application for various aerogels and doped aerogels [37-43]. Moreover, the high porosity and large surface areas lead to applications as filters [44], absorbing media for desiccation [45,46,47], filters, reinforcement agents, pigments, gellifying agents [48], waste containment [49], encapsulation media [50], and pesticides [23].

*

Lawrence W. Hrubesh April 1998 Journal of Non-Crystalline Solids Volume 225, Issue 1 Pages 335-342 and from C.J. Brinker, G.W. Sherer, Sol-Gel Science. Physics and Chemistry of Sol-Gel Processing, Academic Press, New York, 1990.

Chapter I. Silica aerogel: An Introduction

23

Electrodes in capacitors The carbon aerogels have been used as electrodes capacitors in energy storage devices known as double layer capacitor because they are electrically conductive with a very large surface area [51-53]. The stored energy in these devices can be released faster than conventional batteries with high power densities. Thus, have potential application in electric vehicles, microelectronics, and hydrogen fuel storage [54]. Capacitive deionization One of the promising new applications for aerogels is in a cost-effective purification process [55]. The carbon aerogel capacitive deionization process works by sending solutions with various positively and negatively charged ions through an electrochemical cell consisting of numerous electrodes containing carbon aerogels in the form of sheets. The aerogel process can have a variety of uses ranging from extracting harmful contaminants from industrial waste water [56] to desalinizing seawater. Studies of superfluid transitions and phase separation of 3He¯ 4He Low-density silica aerogels are used to study the superfluid transition of 4He and phase separation of the 3He¯ 4He mixture. The aerogels provide a random disordered structure that modifies the normal superfluid and phase separation behavior with helium. [57- 62].
4.2 OPTICAL PROPERTY APPLICATIONS

Aerogel is transparent when its microstructural components are very small compared with the wavelength of light. Transparent aerogels, together with their exceptional thermal insulation ability, have been considered for use as super-insulating sheets in double walled window systems because help considerably to reduce thermal losses in windows [63- 69]. Translucent aerogels have been proposed to improve the efficiency of solar thermal energy storage devices [69-75]. Moreover, the ultra-low density aerogels can be used as lightweight mirror backings [76]. Aerogels have been used to prepare ultra-pure, full-density silica glass by sintering at temperatures below the melting temperature of silica [77- 80]. Silica aerogels with silicon exhibits strong photo-luminescence (luminescence stimulated by visible or ultraviolet radiation). Silica aerogel, doped with radioactive tritium and phosphor, makes an efficient radio-luminescent light source [81]. There is also evidence for quantum confinement in nanoparticle-loaded silica aerogels [82] for producing blue light emission.

Chapter I. Silica aerogel: An Introduction

24

Çerenkov (particle detection and counters) The first modern application, in the early 1980s, involved the use the silica aerogels in detectors called Çerenkov counters. The Çerenkov detector measures the velocity of elementary particles and cosmic rays [83-84]. Since the speed of light depends on the refraction index of the medium, media with different refraction indices were searched. Silica aerogels with refraction indices between 1.007 and 1.024 offer specific refractive indexes for range threshold detectors. [86-92]. Aerogel are used for particle detectors and counters continue in space, at accelerators around the world [93]. A low-density silica aerogel was used in radiation detection vacuum tubes to support the high voltage wire [94].
4.3 THERMAL INSULATOR APPLICATIONS

Aerogel materials, known for exhibit the lowest thermal conductivity of any of the solid or porous materials, are excellent for applications requiring thermal insulation [95]. These include development of electric automobiles equipped with batteries that operate at high temperatures and that need heat storage [95- 97], and insulation for architectural purposes [98]. A layer of transparent aerogel allows the penetration of the sun radiation to the wall, but not the escape of the heat generated [99]. Then, aerogels can be used in heat and cold storage devices [100], automotive exhaust pipes, transport vehicles, and vessels.
4.4 ACOUSTICAL AND MECHANICAL APPLICATIONS

Aerogels may also have acoustic and mechanical applications. Because of their unusual structure, aerogels have low sound velocities, as low as 30 meters per second. Another important acoustic property of aerogel is its mechanical impedance. The impedance is the product of density and the sound velocity of the material. Since both are low, silica aerogel has the lowest impedance of all solid material. This allows the aerogels to be used for coupling sound waves in air to a transducer (device that converts energy from one form to another), this may be useful either to generating or detecting sound. Therefore, they should be efficient ultrasonic devices as acoustic impedance matching [101-103], and sound absorption (anechoic chambers) [104, 105].

in Ardon (Switzerland) a house was built using aerogel granulate as a translucent insulating material

Chapter I. Silica aerogel: An Introduction

25

Shock compression experiments Aerogels have also been proposed as a shock absorbing material. One of the earliest experiments was to measure shock compression in silica aerogels [106]. The low density of the silica aerogel allowed more internal energy could be deposited in it.
4.5 ELECTRICAL AND ELECTRONIC APPLICATIONS

Silica aerogel is an electrical insulator with a low dielectric constant, k (k is the measure of the ability of a material to store electrical potential energy under the influence of an electric field). The velocity of signal propagation in a chip is dependent on the dielectric constant of the surrounding electrical insulation. The lower the dielectric constant, the higher the velocity. Therefore, thin aerogel films are almost ideal dielectrics for ultra-fast integrated circuits [107109]. The bulk aerogels can be used for microwave electronics and high voltage insulators [110]. The pure carbon aerogels are quite electrically conductive, so they have applications as electrodes for batteries, fuel cells, and capacitors [111]. Other metal oxide aerogels have been made, which exhibit super-conducting behavior [112], thermoelectric behavior [113], and piezoelectric properties [114].
4.6 SPACE APPLICATIONS

Aerogels have already captured cosmic dust while on the European Retrieval Carrier (EURECA) satellite and in Space Shuttle experiments [115], and will capture cometary‟s dust in NASA's STARDUST project. Lightweight silica aerogels have also been proposed as a contaminant collector, to protect space mirrors from volatile organics [116]. Aerogels were used to insulate the Mars Rover, where its lightness and strength were established as ideal.

5.
1. 2. 3. 4.

REFERENCES
S.S. Kistler. Nature 127 (1931), p. 741. S.S. Kistler. J. Phys. Chem. 36 (1932), p. 52. G.A. Nicholaon and S.J. Teichner. Bull. Soc. Chim. Fr. 5 (1968), p. 1906. J. Fricke, R. Caps, D. Buttner, V. Heinemann, E. Himmer, G. Reichenamer, Structural, elasto-mechanical and thermal properties of silica aerogels, in: K.K. 6. 5. Kruger et al. (Eds.), Characterization of Porous Structure, vol. 629, Elsevier, Amsterdam, 1988 J. Fricke, in: J. Fricke (Ed.), Aerogels, vol. 2, Springer, Berlin, 1986 M. Gronauer, A. Kadur, J. Fricke, in: J. Fricke (Ed.), Aerogels, vol. 167, Springer, Berlin, 1986

Chapter I. Silica aerogel: An Introduction
7. C.J. Brinker, G.W. Sherer, Sol¯Gel Science. Physics and Chemistry of Sol¯Gel Processing, Academic Press, New York, 1990 8. 9. J. Livage and C. Sanchez. J. Non-Cryst. Solids 11 (1992), p. 145. D.R. Uhlmann, B.J. Zeliñski, L. Silverman, S.B. Warner, B.D. Fabes, W.F. Doyle, Kinetic processes in sol-gel processing, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Processing, vol. 173, Wiley, New York, 1986 10. J.D. Mackenzie, Applications of the sol¯ gel method: some aspects of initial processing, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Processing, vol. 113, Wiley, New York, 1986 11. M. Prassar, J. Phalippou, J. Zarzycki, Sintering of monolithic silica aerogel, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Processing, vol. 156, Wiley, New York, 1986 12. S.J. Teichner, in: J. Fricke (Ed.), Aerogels, vol. 22, Springer, Berlin, 1986 13. J. Zarzycki, T. Wognier, in: J. Fricke (Ed.), Aerogels, vol. 42, Springer, Berlin, 1986 14. G.M. Pajonk. Rev. Phys. Appl. 24 (1989), pp. C4¯ 13. 15. S.Y. Chang, T.A. Ring, J. Non-Cryst. Solids 147¯ 148, 56 (1992) 16. G.M. Pajonk, M. Repelin-Lacroix, S. Abouarnadasse, J. Chaouki and D. Klvana. J. Non-Cryst. Solids 121 (1990), p. 66. 17. J. Walendziewski, M. Stolarski, M. Steininger and B. Pniak. React. Kinet. Catal. Lett. 58 1 (1996), p. 85. 19.

26
18. C.W. Turner, K.J. Franklin, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Chemical Processing, New York, 1986, p. 81 J. Fricke, Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986. 20. R. Vacher, J. Phalippou, J. Pelous, T. Woignier, Proc. 2nd Int. Symp. on Aerogels, J. Phys. C 4 (1989). 21. J. Fricke, Proc. 3rd Int. Symp. on Aerogels, J. Non-Cryst. Solids 145 (1992). 22. R.W. Pekala, L.W. Hrubesh, Proc. 4th Int. Symp. on Aerogels, J. Non-Cryst. Solids 186 (1995). 23. J. Fricke and T. Tillotson, Aerogels: production, characterization, and applications Thin Solid Films Volume 297, Issues 1-2 1997 Pages 212-223 24. J. Fricke, and; Emmerling, Journal of the American Ceramic Society Volume 75, Issue 8 1992 Pages 2027-2036 25. Gesser, Hyman D.; Goswami, Prabhat C. Chemical Reviews Volume 89, Issue 4 June 1989 Pages 765-788 26. J. Fricke, A. Emmerling, in: R. Reisfeld, C.K. Jorgensen (Eds.), Chemistry, Spectroscopy and Applications of Sol-Gel Glasses, Springer Series in Structure and Bonding, Vol. 77, Springer, Heidelberg, 1991, p. 37. 27. J. Fricke and A. Emmerling. J. Am. Ceram. Soc. 75 (1992), p. 2027. 28. J. Fricke and T. Tillotson. Thin Solid Films 297 (1997), p. 212. 29. J. Richardson, G. Carlson, K. McKinley, D. Lewis and T. Tillotson Journal of Non-

Chapter I. Silica aerogel: An Introduction
Crystalline Solids Volume 186 June 1995 Pages 372-387 30. S.J. Teichner, in: J. Fricke (Ed.), Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 22. 31. F. Blanchard, J.P. Reymond, B. Pommier and S.J. Teichner. J. Mul. Catal. 17 (1982), p. 171. 32. J.N. Armor and E. Carlson. Appl. Catal. 19 (1985), p. 32. 33. L. Wang, K. Eguchi and H. Arai. Appl. Catal. 33 (1987), p. 107 34. G.C. Bond and S. Flamerz. Appl. Catal. 33 (1987), p. 219 35. D. Kalvana, J. Chaouki, D. Kusohorsky, C. Chavarje and G.M. Pajonk. Appl. Catal. 42 (1988), p. 121. 36. G.M. Pajonk. Appl. Catal. 72 (1991), p. 217 37. G.M. Pajonk, S.J. Teichner, in: J. Fricke (Ed.), Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 193. 38. S.J. Teichner, in: R. Vacher, J. Phalippou, J. Pelous, T. Woignier (Eds.), Proc. 2nd Int. Symp. on Aerogels, J. Phys. C 4 (1989) 1. 39. G.M. Pajonk. Appl. Catal. 72 (1991), p. 217. 40. Y. Mizushima and M. Hori. Appl. Catal. A: General 88 (1992), p. 137. 41. E.I. Ko, Chemtech (1993) 31. 42. R.J. Willey, C.-T. Wang, J.B. Peri, in: R.W. Pekala, L.W. Hrubesh (Eds.), Proc. 4th Int. Symp. on Aerogels, J. Non-Cryst. Solids 186 (1995) 408.

27
43. M. Moner Girona, E. Martínez, J. Esteve, A. Roig, R. Solanas, and E. Molins Applied Physics A 74 1 (2002) 119-122 (rapid communication). 44. D.W. Cooper. Part. Sci. Technol. 7 (1989), p. 371. 45. H.D. Gesser and P.C. Goswami. Chem. Rev. 89 (1989), pp. 765¯788. 46. C. Liu, S. Komarneni, in: S. Komarneni, D.M. Smith, J.S. Beck (Eds.), Advances in Porous Materials, Mater. Res. Soc. Symp. Proc. 371, Materials Research Society, Pittsburgh, 1995, p. 217. 47. S. Komarneni, R. Roy, U. Selvaraj, P.B. Malla and E. Breval. J. Mater. Res. 8 (1993), p. 3163. 48. H.D. Gesser and P.C. Goswami. Chem. Rev. 89 (1989), p. 765. 49. Y.A. Attia, M.S. Ahmed, M. Zhu, in: Y.A. Attia (Ed.), Sol¯Gel Processing and Applications, Plenum, New York, 1994, p. 311. 50. B.C. Dave, B. Dunn, J.S. Valentine, J.I. Zink, in: R.F. Lobo, J.S. Beck, S.L. Suib, D.R. Corbin, M.E. Davis, L.E. Iton, S.I. Zones (Eds.), Microporous and Macroporous Materials, Mater. Res. Soc. Symp. Proc. 431, Materials Research Society, Pittsburgh, 1996, p. 285. 51. R.W. Pekala, S.T. Mayer, J.L. Kaschmitter, F.M. Kong, in: Y.A. Attia (Ed.), Sol¯Gel Processing and Applications, Plenum, New York, 1994, p. 369. 52. R.W. Pekala. J. Mater. Sci. 24 (1989), p. 3221.

Chapter I. Silica aerogel: An Introduction
53. S.T. Mayer, R.W. Pekala and p. 446. 54. S.T. Teichner, M. Khalfallah, D. Bianchi, J.-L. Gass, in: Y.A. Attia (Ed.), Sol¯Gel Processing and Applications, Plenum, New York, 1994, p. 323. 55. J.C. Farmer, D.V. Fix, G.V. Mack, R.W. Pekala and J.F. Poco. J. Electrochem. Soc. 143 (1996), p. 159. 56. M.S. Ahmed and Y.A. Attia. J. Non-Cryst. Solids 186 (1995), p. 402 57. J. Ma, S.B. Kim, L.W. Hrubesh and M.H.W. Chan. J. Low-Temp. Phys. 93 (1993), p. 945. 58. M.H.W. Chan, K.J. Blum, S.Q. Murphy, G.K.S. Wong and J.D. Reppy. Phys. Rev. Lett. 61 (1988), p. 1950. 59. R. Maynard and G. Deutscher. Europhys. Lett. 10 (1989), p. 257 60. W.M. Snow and P.E. Sokol. J. Low-Temp. Phys. 80 (1990), p. 197. 61. J. Ma, S.B. Kim, L.W. Hrubesh and M.H.W. Chan. J. Low-Temp. Phys. 93 (1993), p. 945. 62. J. Yoon, N. Mulders, L.W. Hrubesh and M.H.W. Chan. Czech. J. Phys. 46 (1996), p. 157. 63. P.H. Tewari, A.J. Hunt, K.D. Lofftus, in: J. Fricke (Ed.), Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 31. 64. J. Fricke, in: J. Fricke (Ed.), Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 94. 65. E. Schreiber, E. Boy, K. Bertsch, in: J. Fricke (Ed.), Aerogels, Springer J.L.

28
Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 133. 66. E. Boy, M. Munding, V. Wittwer, in: R. Vacher, J. Phalippou, J. Pelous, T. Woignier (Eds.), Proc. 2nd Int. Symp. on Aerogels, J. Phys. C 4 (1989) 99. 67. V. Wittwer. J. Non-Cryst. Solids 145 (1992), p. 240. 68. P.H. Tewari, A.J. Hunt, K.D. Lofftus, in: J. Fricke (Ed.), Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 31. 69. M. Rubin and C.M. Lampert. Solar Energy Mater. 7,1 (1983), p. 393. 70. D. Buttner and J. Fricke. Int. J. Sol. Energy 3 (1985), p. 89. 71. P.H. Tewari and A.J. Hunt, 1986 US Pat 4610863. Chem. Abstr. 105 (1986), p. 214727C. 72. R. Caps and J. Fricke. J. Sol. Energy 36 (1986), p. 316. 73. J. Fricke, R. Caps, D. Buttner, U. Heinemann and E. Hummer. Sol. Energy Mater. 16 (1987), p. 267 74. K.I. Jensen. J. Non-Cryst. Solids 145 (1992), p. 237. 75. S. Svendson. J. Non-Cryst. Solids 145 (1992), pp. 240¯ 243. 76. S.P. Hotaling. J. Mater. Res. 8 (1993), p. 352. 77. C. Mulder, J.G. van Lierop Aerogels, in: J. Fricke (Ed.), Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 68. 78. R. Sempere, D. Bourret, J. Bouaziz, A. Sivade, in: R. Vacher, J. Phalippou, J. Pelous, T. Woignier (Eds.), Proc. 2nd Int.

Kaschmitter. J. Electrochem. Soc. 140 (1993),

Chapter I. Silica aerogel: An Introduction
Symp. on Aerogels, J. Phys. C 4 (1989) 227. 79. B. Dunn and J.I. Zink. J. Mater. Chem. 1 (1991), p. 903. 80. T.M. Tillotson, W.E. Sunderland, I.M. Thomas and L.W. Hrubesh. J. Sol¯Gel Sci. Technol. 1 (1994), p. 241. 81. C.S. Ashley, S.T. Reed, C.J. Brinker, R.J. Walko, R.E. Ellefson, J.T. Gill, in: L.L. Hench, J.K. West (Eds.), Chemical Processing of Advanced Materials, Wiley, New York, 1992 p. 989. 82. T.J. Goodwin, V.J. Leppert, C.A. Smith, S.H. Risbud, M. Niemeyer, P.P. Power, H.W.H. Lee, L.W. Hrubesh, in: J.S. Beck (Ed.), Microporous and Mesoporous Materials, Materials Research Society Symposium 1996. 83. D.E. Fields, H. van Hecke, J. Boissevain, B.V. Jacak, W.E. Sondheim, J.P. Sullivan, W.J. Willis, K. Wolf and E. Noteboom. Nucl. Instrum. Methods A 349 (1994), p. 431. 84. R.M. Bionta, H.S. Park, E. Abels, T.E. Cowan, F.S. Dietrich, E.P. Hartouni, K.A. Van Bibber, Am. Nucl. Soc. Proc., Accelerat. Appl., Nov 1997. 85. M. Cantin, M. Casse, L. Koch, R. Jouan, P. Mestran, D. Roussel, F. Bonnin, J. Moutel and S.J. Teichner. Nucl. Instrum. Methods 118 (1974), p. 177. 86. S. Henning and L. Svensson. Phys. Scr. 23 (1981), p. 697. 87. G. Poelz and R. Riethmuller. Nucl. Instrum. Methods 195 (1981), p. 491. Proceedings, Pittsburgh,

29
88. G. Poelz, in: J. Fricke (Ed.), Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 176. 89. P. Carlson. Nucl. Instrum. Methods A 248 (1986), p. 110. 90. G. Poelz. Nucl. Instrum. Methods A 248 (1986), p. 118. 91. I.L. Rasmussen, in: R. Vacher, J. Phalippou, J. Pelous, T. Woignier (Eds.), Proc. 2nd Int. Symp. on Aerogels, J. Phys. C 4 (1989) 221. 92. S. Henning, in: J. Fricke (Ed.), Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 38. 93. L. Koch-Miramond, in: J. Fricke (Ed.), Aerogels, Springer Proceedings in Physics, Vol. 6, Springer, Heidelberg, 1986, p. 188. 94. C. Weust, T. Tillotson, US patent 5,416,376 (1992). 95. G. Herrmann, R. Iden, M. Mielke, F. Teich, B. Ziegler, in: R.W Pekala, L.W. Hrubesh (Eds.), Proc. 4th Int. Symp. on Aerogels, J. Non-Cryst. Solids 186 (1995) 380. 96. J. Fricke. Phys. Unserer Zeit. 20 (1989), p. 189 97. J. Fricke, M. Arduini, D. Buttner, U. Heinemann and E. Hummer. Thermal Cond.. 21 (1990), p. 235 98. G.M. Pajonk, E. Elaloui, M. Durant, J.L. Chevalier, B. Chevalier, P. Achard, in: Y.A. Attia (Ed.), Sol¯Gel Processing and Applications, Plenum, New York, 1994, p. 267. 99. B. Wolff and G. Seybold. Chem. Abstr. 112 (1990), p. 828294

Chapter I. Silica aerogel: An Introduction
100. J. Fricke, X. Lu, P. Wang, D. Buttner and U. Heineman. Int. J. Heat Mass Transfer 35 (1992), pp. 2305¯2309. 101. M. Gronauer and J. Fricke. Acoustica 59 (1986), p. 177. 102. (T. E. Gómez Álvarez, F. R. Montero, M. Moner-Girona, E. Rodríguez, A. Roig and E. Molins. Viscoelasticity of silica aerogels at ultrasonic frequencies, Applied Physics Letters (accepted) 103. R. Gerlach, O. Kraus, J. Fricke, P.-Ch. Eccardt, N. Kroemer and V. Magori. J. Non-Cryst. Solids 145 (1992), p. 227. 104. A. Zimmermann, J. Gross, J. Fricke, in: R.W. Pekala, L.W. Hrubesh (Eds.), Proc. 4th Int. Symp. on Aerogels, J. Non-Cryst. Solids 186 (1995) 238. 105. V. Gibiat, O. Lefeuvre, T. Woignier, J. Pelous, J. Phalippou, in: R.W Pekala, L.W. Hrubesh (Eds.), Proc. 4th Int. Symp. on Aerogels, J. Non-Cryst. Solids 186 (1995) 244. 106. N.C. Holmes, H.B. Radousky, M.J. Moss, W.J. Nellis and S. Henning. Appl. Phys. Lett. 45 (1984), p. 626. 107. L.W. Hrubesh, in: T.M. Lu, S.P. Murarka, T.-S. Kuan, C.H. Ting (Eds.), LowDielectric Constant Materials¯¯ Synthesis and Applications in Microelectronics, Mater. Res. Soc. Symp. Proc. 381 (1995) 267¯ 272. 108. D.M. Smith, J. Anderson, C.C. Cho, B.E. Gnade, in: S. Komarneni, D.M. Smith, J.S. Beck (Eds.), Advances in Porous Materials, Mater. Res. Soc. Symp. Proc. 371, Materials Research

30
Society,

Pittsburgh, 1995, p. 261. 109. D.M. Smith, J. Anderson, C.C. Cho, G.P. Johnston, S.P. Jeng, in: T.M. Lu, S.P. Murarka, T.-S. Kuan, C.H. Ting (Eds.), Low-Dielectric Constant Materials¯¯ Synthesis and Applications in Microelectronics, Mater. Res. Soc. Symp. Proc. 381, Materials Research Society, Pittsburgh, 1995, p. 261. 110. L.W. Hrubesh, R.W. Pekala, in: Y.A. Attia (Ed.), 363. 111. R.W. Pekala, S.T. Mayer, J.L. Kaschmitter, F.M. Kong, in: Y.A. Attia (Ed.), Sol¯Gel Processing and Applications, Plenum, New York, 1994, p. 369. 112. B. Pommier, S.J. Teichner, P. Lejay, A. Sulpice, R. Tournier, in: R. Vacher, J. Phalippou, J. Pelous, T. Woignier (Eds.), Proc. 2nd Int. Symp. on Aerogels, J. Phys. C 4 (1989) 41. 113. K.E. Swider, C.I. Merzbacher, P.L. Hagans and D.R. Rolison. Chem. Mater. 9 (1997), p. 1248. 114. P. Lobmann, W. Glaubitt, J. Gross, J. Fricke, in: R.W Pekala, L.W. Hrubesh (Eds.), Proc. 4th Int. Symp. on Aerogels, J. Non-Cryst. Solids 186 (1995) 59. 115. P. Tsou. J. Non-Cryst. Solids 186 (1995), p. 415. 116. S.P. Hotaling, Rome Laboratory Report RL-TR-93-148, July 1993. Sol¯Gel Processing and Applications, Plenum, New York, 1994, p.

Ch a pt er II

SYNTHESIS OF SILICA AEROGELS

SECTION OUTLINE
1. 2. INTRODUCTION ................................................................................................................................ 32 PREPARATION OF AEROGELS .................................................................................................... 33 2.1. 2.2. 2.3. USED REACTIV ES ................................................................................................................. 33 SYNTHESIS PROCEDURE ................................................................................................. 34 DRYING PROCEDURE ........................................................................................................ 36 2.3.1 Supercritical drying at high temperature................................................................... 36 2.3.2 CO2 supercritical drying................................................................................................ 38 3. 3.1. SYNTHESIS ROUTES: EFFECT OF DIFFERENT ALKOXIDE PRECURSORS ..... 39 TETRAMETHOXYSILANE: TMOS AEROGELS ........................................................ 40 3.1.1 3.1.2 3.1.3 3.2. The effect of the TMOS concentration...................................................................... 45 The effect of the nature of the solvent ...................................................................... 46 The effect of the hydrolysis solution .......................................................................... 47 Water amount.............................................................................................. 47 TETRAETHOXYSILANE: T EOS AEROGELS ............................................................. 49 3.2.1 The effect of the TEOS concentration ...................................................................... 53 Neutral....................................................................................................... 53 Acid catalyst ................................................................................................ 54 Base-catalyst ................................................................................................ 56 3.2.2 The effect of hydrolysis solution ................................................................................. 58 Water amount.............................................................................................. 58 Influence of the amount of the catalyst ............................................................. 61 Influence of the nature of the catalyst .............................................................. 64 3.3. ‘TWO-STEP’ SYNTHESIS .................................................................................................... 66 Effect of precursor concentration...................................................................... 67 Effect of water amount .................................................................................. 69 Influence of the amount of the catalyst ............................................................. 70 4. 5. SUMMARY AND CONCLUSIONS.............................................................................................71 REFERENCES................................................................................................................................. 72

Chapter II. Synthesis of silica aerogels

32

1.

INTRODUCTION

The aim of this section is to present detailed description of the conditions at which silica aerogels were prepared through out the thesis and the influence of the synthesis routes on some of the silica aerogel final properties. Hydrolysis and polycondensation of a silicon alkoxide is a well-known route to prepare silica gels [1]. Hydrolysis and condensation reactions compete with each other during all the stages of the sol-gel process, and are additionally influenced to a different degree by many parameters. The influence of the different parameters on the network formation is very complex, since m any parameters change progressively as polycondensation proceeds. Synthesis of silica gels has been carried out by hydrolysis of several silicon alkoxide precursors in different solvent solutions. To tailor the structure and properties of the final material the influence of different parameters have been studied. The varied parameters were: 1. The type of metal alkoxide(s) 2. The type of solvent 3. The relative and absolute concentration of the metal alkoxide and the solvent 4. The concentration of alkoxy group to water ratio 5. The type of catalyst 6. The pH of hydrolysis A data–base computer file containing all the information since 1995 to these days was used with the aim to classify synthesis and sample information of all products prepared in our laboratory. Twenty characterization parameters were used together with a code name to identify each sample. The Database allowed us to develop a statistical study of different parameters of all the synthesis prepared until now. A simple code name was used in order to name the samples from different experimental conditions. As an example TE01AA00 means: TE TEOS precursor, (TM when TMOS was used, H5 when Prepolymerized TEOS) 01 2001 year, AA name of the synthesis process, in a chronological order

01 number of the sample with AA synthesis. Another example: H501AB97 meaning H5 year, AB Prepolymerized TEOS precursor, 97 1997

name of the synthesis process, 02 number 02 of the sample with AB synthesis.

Chapter II. Synthesis of silica aerogels

33

Few aerogels that have been thoroughly characterized and that will appear ‘recurrently’ on the thesis are labeled in a short form as acetone series A1, A2, A3, and A4 and methanol as M. These syntheses are described in section 4.

2.

PREPARATION OF AEROGELS
2.1 USED REACTIVES

Sols were prepared by using three different silicon alkoxide precursors: (a) tetraethoxysilane (TEOS) (b) tetramethoxysilane (TMOS), and (c) prepolymerized tetraethoxysilane (H5). Their purity was above 98% (GC) and they were used as supplied. The solvents used were ethanol, methanol, and acetone. The hydrolysis and catalyst solutions were done using one of the following catalysts: HCl, C6H8 O7, HNO3, NH3, CH3COOH, KOH, C2H2 O4 + NH 4OH, NH4 F+NH3 , NH4 OH+CH3 COOH in the form of solutions in demineralized H 2O. Table II.1 summarizes the properties of the reactives used in the sol-gel synthesis, molar density, M, density , purity, melting and boiling points (mp and bp) and commercial trade.

Table II.1

Properties of the synthesis reactive: molar density, M, density , purity, melting and boiling points (mp and bp) and commercial trade. M (g/mol)
208.33

Reactive
Tetraethoxysilane, TEOS Si(OCH2CH3)4 Prepolymerized Tetraethoxysilane, H5 Tetramethoxysilane, TMOS Si(OCH3)4 Acetone (CH3)2CO Citric Acid C6H8O7 Clorhidric Acid HCl Formic Acid HCOOH Phosphoric Acid H3PO4 Nitric Acid HNO3 Ammonia NH3 Ethanol CH3CH2OH Hydroxide sodic NaOH

(g/cm )
3

Purity (%)
98+ 98+

mp-bp ( C)
163-167

Trade
Fluka Silbond

0.933

152.22 58.08 192.12 36.46 46.03 98.00 63.01 17.03 46.070 39.996

1.027 0.789 1.18 1.017 1.220 1.685 1.38 0.88 0.789 -

98+ 99.5 99.5 35 0.9834N 95-97 85 60 32 99.8 v/v 97+

118-122 100-101 78.5 -

Fluka Panreac Fluka Panreac Aldrich Aldrich Aldrich Panreac Merck Carlo Erba Carlo Erba

Chapter II. Synthesis of silica aerogels

34

CH3COOH Acetic acid Methanol CH3OH

60.05 32.04

1.05 0.790

99 99+ -

Panreac Aldrich

2.2

SYNTHESIS PROCEDURE

The sol-gel syntheses of the silica aerogels comprises three steps: (i) hydrolysis and condensation of alkoxide precursor, (ii) gelation and aging, and (iii) drying. The gels were cast into several sized and shaped recipients (summarized in Table II.2): Pyrex® test tubes with a different inner diameter and height, and disks with different inner diameter and height were used in order to obtain aerogels with several size and shape. The specific shape (rod, plate or square) of the gels was needed for some of the measurements of the aerogel properties [2, 3] (Chapter III. Bulk characterization). Table II.2
Recipient Glass tube Glass tube, g Glass tube, p Quimiboro tube Culture tube Petri Dish Material Pyrex® Pyrex® Pyrex® Pyrex® Polystyrene Polystyrene Characteristics of the recipients Volume (cm3) 50 25 15 750 5 38.5 60 75 10 High (mm) 10 140 Diameter (mm) 30 15 12 32 12 35

The following steps were common to all routes. A solution was firstly prepared by adding the solvent to metal precursor drop-wise while stirring. After five minutes, the water was added, eventually containing the catalyst. The solutions of precursors in alcohol were brought to desired pH by introducing the catalyst with a precision micropipette (Gilson P1000). pH of reaction mixture during hydrolysis was monitored in some of the cases and values ranged from 2.3 to 7.8. After stirring for fifteen additional minutes, the solution was distributed in recipients. The recipients were tightly closed and kept either at room temper ature or in a constant temperature chamber (40°C) until gelification took place, then the gels were covered with their respective solvents and left to age until supercritical drying. Gelation time depends strongly on the initial conditions, it ranges from a few minutes to months. Some of the obtained alcogels were aged at 40°C to accelerate the aging rate. In some synthesis, before the supercritical drying, the alcogel was washed 3 times for 24 h, at room temperature, in a fresh pure alcohol bath to remove water and oligomers that were still present in the liquid phase

Chapter II. Synthesis of silica aerogels

35

[4]. In order to control the reproducibility, at least two samples were prepared at identical conditions. Next figure shows a photo of the sample holder for those samples that were soaked in the washing solution. This holder configuration allowed to facilitate the washing process. Sample-holder

Etanol bath

Gel samples

Figure II.1 Sample holder formed by six independent shelves. The net will allow that the gels follow a washing process.

Table II.3 gathers the experimental runs for gel synthesis with TMOS as alkoxide precursor and Table II.4 with TEOS:

Table II.3

Synthesis experimental conditions: TMOS as alkoxide precursor, two different kind of solvent (methanol and acetone), with several acid and base catalysts

Solvent Methanol Methanol Methanol Methanol Acetone Acetone Acetone -

Catalyst HCl KOH NH4 OH+CH3COOH NH4 OH NH4 OH KOH HCOOH

Chapter II. Synthesis of silica aerogels

36

Table II.4

Synthesis experimental conditions: TEOS and H5 as precursor, three different kind of solvent, with several acid and base catalysts

Precursor TEOS TEOS TEOS TEOS TEOS TEOS TEOS TEOS TEOS H5 2.3

Solvent Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Ethanol Acetone Methanol Ethanol

Catalyst C6 H8O7 HCl HNO3 NH4 OH C2 H2O4 +NH4 OH CH3 COOH HNO3 NH3

DRYING PROCEDURE

2.3.1

Supercritical drying at high temperature

Supercritical extraction took place in a high-temperature and high-pressure plant [5,6]. See Annex II for the technical details of the equipment. Silica gels were placed inside the vessel filled with the corresponding solvent. It allowed to maintain the solid part of the gel covered with solvent until the two phases (gas and liquid) were no longer distinguishable. Supercritical drying with alcohol requires a cautious manipulation of the autoclave because the alcohol is flammable and has a high critical temperature. Alcohol supercritical drying has some advantages in producing silica aerogels such as, good transparency and hydrophobicity (characterization, Chapter II). As an example, Figure II.2 shows a process of a supercritical drying cycle for a real experiment of the methanol aerogels. Each step of the process is labeled. The methanol liquid-gas interface has been depicted (Pc=77bar, T c=240°C). Every point of the graph corresponds to an elapsed time of five minutes.

Chapter II. Synthesis of silica aerogels

37

Supercritical Cycle
200

(ii)
150

(iii)

Pressure (atm)

(i)
100
Methanol Supercritical Region

50

Liquid

(v)
0 0 50 100 150

(iv)
Gas

200

250

300

350

400

Temperature

(oC)

Figure II.2 Supercritical drying cycle used for a set of alcogels with methanol as a solvent.

Before starting the drying sequence, the reactor was sealed and flushed for a few minutes with CO2 gas at 20 ¯25°C. Then, the pressure was raised up until the pressure reached 150 bars (100 bar for the acetone series) (step i). The pressurization was accomplished with compressed CO2 and the pressure was monitored and kept stable with great accuracy. Once the final pressure was reached, the chamber was slowly heated from room temperature to a final temperature to avoid thermal shock, varying between 230°C and 280°C (which is above the critical temperature of alcohol) (step ii). Care must be taken not to reach too high temperatures to avoid solvent decomposition or even its autoignition. The rate of heating was about 100°C/h. The autoclave was flushed with CO 2 for 2 hours after reaching the predetermined conditions (step iii) keeping the high temperature and high pressure. The samples were kept in the reactor for one more hour. Then, the solvent was removed by slow depressurization over a period of 2h at a constant rate of 10bar/h (flow about 6ml/min) while the temperature was maintained (step iv). After the pressure inside the autoclave reached atmospheric pressure, autoclave was cooled down to room temperature at 40 °C /h (step v), before that, the reactor was again flushed with CO2 for a few minutes. Finally, the vessel was opened and the aerogels were removed [8- 10]. Figure II.3 shows a photograph of the sample holder for those samples that were dried at high temperature without solvent washing. In that case, the gels were not subtracted from its respective recipients.

Chapter II. Synthesis of silica aerogels

38

Sample-holder

Pyrex tubes Gel

Figure II.3 Sample holder for the gels dried under, ethanol, methanol or acetone supercritical conditions without washing process.

Table II.5 shows the critical temperature and critical pressure of the used solvents, ethanol, methanol, acetone, CO2, and other supercritical fluids frequently used. Table II.5
Critical pressure, Pc, and critical temperature, Tc, of various solvents used as pore liquid Solvent H2 0 NH3 CO2 CH3 CH2OH CH3 OH CH3 CN Pc (atm) 216 110 70 62 77 47 Tc (°C) 374 132 31 243 240 275

Few experiments were not successful due to that the drying pressure was below the threshold pressure (below which the gel network begins to shrink) [14] and consequently the dried gels showed a significant shrinkage, even up to 70%. 2.3.2 CO2 supercritical drying

Supercritical drying with CO 2 is widely used because it is a safer and cheaper method than alcohol supercritical drying: CO2 is non-flammable and has a low critical temperature [15, 16, 17]. The gels were placed in a 2000 ml vessel and covered with the corresponding solvent.

Chapter II. Synthesis of silica aerogels

39

The vessel was sealed and liquid CO 2 was pumped inside at room temperature until the pressure reached about 100 bars. Then the micrometer valve at the autoclave bottom outlet was opened to allow the ethanol to flow out. The flow was about 6ml/min. The displacement of ethanol, methanol or acetone by liquid CO2 took from about 4h to 12h, which allowed the liquid CO2 to diffuse into the gel pores displacing the solvent. The solvent was collected in another reactor for evaluation. After a complete substitution of the solvent for liquid CO2, the outlet valve was closed, the pump was turned off, and the temperature was raised up to 45°C (above the critical temperature of CO2). The ramping took about 30min, after which the vessel remained closed for another hour. Then the micrometer valve was opened, the pump was turned on, and the system was flushed for 30min. The CO 2 flow was stopped and the system was slowly depressurized, over a period of 1 hour at a constant rate of 10bar/h while the temperature was maintained at 45°C. After the autoclave reached atmospheric pressure, the vessel was opened and the aerogels were removed [18]. The characterization of the aerogels is shown in Chapter III (Bulk characterization).

3.

SYNTHESIS PRECURSORS

ROUTES:

EFFECT

OF

DIFFERENT

ALKOXIDE

The effect of various precursors such as (a) tetraethoxysilane (TEOS) [19- 23], (b) tetramethoxysilane (TMOS) [24- 32], and (c) prepolymerized tetraethoxysilane (H5) [33- 35] will be presented and discussed in this section. For each type of alkoxide precursor, sol -gel reactions were performed under acidic, neutral or basic conditions, in alcohols (methanol or ethanol) or acetone. The use of these precursors allowed synthesis of a very large variety of monolithic transparent, translucent, and opaque silica aerogels. A systematic and detailed study was undertaken regarding the comparison of physical properties such as monolithicity, bulk density, optical transmission, total surface area, porosity, pore size distribution, and total pore volume (see chapter III: Bulk characterization). It was shown that these values are strongly correlated. The wet gels were also characterized by means of the gelification time, t g. The gelification time is a parameter that characterizes the sol gelification velocity, and at the same time determines the aerogel microstructure, resulting in a more polymeric aerogel for longer gelification times.

Chapter II. Synthesis of silica aerogels

40

3.1

TETRAMETHOXYSILANE: TMOS AEROGELS

The first series of silica gels were prepared from TMOS (tetramethoxysilane) in different concentrations, different combinations of solvent (methanol and acetone) and catalyst (none, HCl, potassium hydroxide, ammonium hydroxide, and NH 4OH+CH3COOH). Tables II.6, and II.8 gather the synthesis experimental conditions for the TMOS aerogels, when the used solvent were methanol and acetone, respectively.

Table II.6

Synthesis experimental conditions, TMOS as precursor, methanol as solvent and different type of catalyst, several TMOS molar concentration (m=solvent/TMOS) versus water concentration (h=H2 O/TMOS), and several catalyst concentrations (c).

Catalyst HCl KOH NH4 OH+CH3COOH NH4 OH NH4 OH NH4 OH NH4 OH

Label
TM99AQ TM99AR TM96C-D

m 8 8 12.25 12.25 3 4 4

h 4 4 4 4 2 2 4

c 0.05 0.05 0.065 0.065

M TM96B-E-F-H-97F-O98A-H-I-99AU TM00AR TM00AS TM00AU

The gels synthesized with TMOS and methanol as solvent under NH4OH catalyst
TMOS/EtOH/H2O= 1/12.25/4 were labeled as M gels. Those samples offered a good

reproducibility and very good quality.

Chapter II. Synthesis of silica aerogels

41

Moreover, the gels series synthesized with TMOS with H2 O/TMOS fixed at 4 and a variable concentration of acetone as solvent was labeled as A-series gel. The gels were labeled as A1, A2, A3, A4, when m= EtOH/TMOS= 1.22, 0.54, 0.32, 0.20. Those samples offered a good reproducibility and good quality. Next Table II.7 lists these experiments.

Table II.7

Synthesis experimental conditions, TMOS as precursor, acetone as solvent and different type of catalyst, several precursors (m) versus water concentration (h), and several catalyst concentrations (c).

Catalyst NH4 OH KOH -

Label
TM97E TM96A-I-J TM00AB-AW A05 TM98F-G TM98O A1TM96N-97A-N-98E-99AO A2 TM96K-R-97B-G-H-I-J-KM-P-Q-98A-B-99AJ-AN-AP-D00AC-AE A3 TM96M-Q-97C-99AL-AQ A4 TM96L-97D-L-P-98C-N-SAC-99Q-AM-AR-AS-00AD TM99O TM98J-Q TM98L-T TM98M-U TM98V TM98K-R

m 12.25 12.25 0.1 3.87 3.87 1.22 0.54 0.32 0.20 0.54 0.20 0.20 0.20 0.20 0.20

h 4 4 4 4 2 4 4 4 4 2 2 6 8 16 3

c 0.065 0.065 -

Another type of sol-gel syntheses route was performed at low temperature without needing to use water. In these syntheses, supercritical CO 2 was used as solvent, and HCOOH as the condensation agent. Because the use of supercritical CO2 as solvent, it was necessary to synthesize the gels directly inside the reactor. Next Figure II.4 shows a scheme of this process.

Chapter II. Synthesis of silica aerogels

42

Si (OR)4 + HCOOH

4SiO 2 + 4HCOOR

Figure II.4 Aerogels produced with TMOS as alkoxide precursor, supercritical CO 2 as solvent, and HCOOH as the condensation agent.

In parallel to this synthesis, some experiments were performed out of the reactor in order to have an estimation of the gelification rate inside the reactor. Table II.8 lists several
HCOOH/TMOS molar ratios used.

Table II.8

Synthesis experimental conditions, TMOS as precursor and with HCOOH as condensation agent

Gel label TM99F TM99G TM99H TM99I

HCOOH/TMOS 6.67 6 4 3

Two TMOS one-step routes were selected because of the quality and reproducibility of the resulting products. The first set consisted of methanol as solvent and ammonium hydroxide (NH4OH at 32%) as catalyst, M labeled samples. The total molar ratio of the reagents was kept constant precursor/solvent/water/catalyst = 1/12.25/4/6.5·10 -2 [36]. In the second set, no catalyst was added, being acetone the solvent [37]. In this case, different concentrations of solvent were used. The water molar ratio, TMOS/water, was kept at four: A-series. The scheme below shows these two synthesis routes:

Chapter II. Synthesis of silica aerogels
M
TMOS + MetOH NH 4OH + H 2O

43
A-series
TMOS + Acetone H 2O

Polymerization

Hydrolisis

Polymerization

Hydrolisis

Gelling

Gelling

Evaporation

Evaporation
Supercritical drying

Supercritical drying

Figure II.5 The two selected synthesis routes for the TMOS aerogels, M-series and A-series.

Moreover, a second route was prepared to compare two different drying cycles: some of the gel samples were submitted to supercritical drying in acetone while the others were dried by CO 2 exchange (see supercritical drying section). The two selected synthesis routes and a list of the gelation times is collected in Table II.9, the given values were averaged for a number of synthesis processes.

Table II.9

Effect of synthesis conditions on gelation time for M and A-series: type of solvent, molar ratio, volume ratio and gelation time.

Label M A05 A1 A2 A3 A4

Solvent Methanol Acetone Acetone Acetone Acetone Acetone

Solvent Precursor
12.25 3.874 1.224 0.544 0.317 0.204

V

TMOS

V( TMOS+solvent)
0.08 0.05 0.10 0.20 0.30 0.40

Gelation time (Mean value) 5 minutes 180 days 90 days 16 days 7 days 2 days

Chapter II. Synthesis of silica aerogels

44

Figure II.6 shows gelification times for all the gels synthesized following the same A2 route. Two groups can be differentiated. The first one shows a longer gelification time corresponding to the gels with larger volume, 750 ml. Its mean gelification time was 30 days and the standard deviation was of 4 days. The other group corresponding to 50 and 25 ml presented a mean gelification time of 16 days and its standard deviation was of 4 days.

50 45 40 35
4 days 30 days

t gelification (days)

30 25 20 15 10 5 0 0
16 days

Large tubes

4 days

Small tubes

10

20

30

A2 samples

Figure II.6 Gelification time for the samples with 0.2 and h=4. The mean value for the gelification time was of 20 days for large tubes and 18 days for small tubes.

These results show that the size of the recipient it is an important factor influencing the gelification time. The gel point was defined as the point in time at which the network of linked silica oxide particles spans the container holding the sol. Then, it can be observed that, larger recipient implied longer gelification time. A similar study was done comparing samples that remained either at 40 C or at room temperature. At 40 C, the mean gelification time was reduced for the 50 ml gels from 18 to 7 days (with a standard deviation of 30 hours) verifying that increasing temperature accelerates the gelification rate. The sol-gel reactions lead to a progressive decrease of the solution pH with time because the hydrolysis reaction is generally more rapid and complete under acidic conditions, [ 38] whereas the average condensation rate is generally maximized near pH=4. Figure II.7 shows a decrease of pH during the gelation process in A1 gels.

Chapter II. Synthesis of silica aerogels

45

7,4 7,2 7,0 6,8 6,6 6,4

A1 gel

pH

6,2 6,0 5,8 5,6 5,4 0 20 40 60 80 100

time (hours)

Figure II.7 pH versus time during gelation process of TMOS at room temperature in acetone solution (A1 type gel).

3.1.1

The effect of the TMOS concentration

In the TMOS set, when acetone was used as solvent, different concentrations of acetone were used. The water molar ratio, TMOS/water, was kept at value 4. The concentration of the alkoxide was given by ,
v VTMOS VTMOS Vacetone

(Eq. II.1)

The

value was varied from 0.05 to 0.4. The samples were labeled as A05, A1, A2, A3 and = 0.05, 0.1, 0.2, 0.3 and 0.4, respectively. In turn, these values

A4 corresponding to

correspond to molar ratios of Acetone/TMOS of 3.874, 1.224, 0.5434, 0.317 and 0.204. The dependency of the gelification time with the volume concentration, , was studied. Figure II.8 shows the gelification time versus the concentration of TMOS in acetone. The gelification times ranged from an average of three months for A1 to three days for A4, longer times as expected, for more diluted sols [39]. The gelification time decreases exponentially as a function of the TMOS/Acetone volume concentration. Table II.10 gathered several characteristics of the different samples. The obtained values were averaged for a number of synthesis processes.

Chapter II. Synthesis of silica aerogels

46

180 150 Fit y0+Ae y0=0, A=180, t=0.06
(-x/t)

t gelification (days)

120 90 60 30 0 0,0 0,1 0,2 0,3 0,4 0,5

v

Figure II.8 Gelification time versus concentration, v for TMOS/acetone gels. The exponential fitting results in tgeli fication =180.e(-v/0.06).

The influence of the TMOS/acetone concentration of the sol on the aerogels can be assume that when value decreases, i.e. decreasing the concentration of the precursor, the excess of acetone increases the distance between the reacting species and hinder the progress of crosslinkage of the siloxane chains (Si-O-Si) leading to the separation of SiO2 clusters in the sol. This process leads to a decrease in the reaction rate and hinders the formation and growth of the gel network particles, resulting in smaller particles and larger pore sizes [40] (see chapter III: Silica aerogel characterization). 3.1.2 The effect of the nature of the solvent

The TMOS series of silica gels were prepared under different conditions by using various solvents as pore liquids: methanol, ethanol, acetone, and CO2 . Table II.5 showed their critical pressure and temperature: Pc, and T c [41- 44]. Because water and alkoxysilanes are immiscible, a mutual solvent is normally used as a homogenizing agent. The alcohol is not simply a solvent since, as indicated in equations I.2 and I.3, it can participates in esterification or alcholysis reactions. The gelification times for methanol were of few minutes, for the acetone series they ranged from an average of three months for A1 to three days for A4, longer times as expected for longer solvent chains. The effects of the solvent, methanol or acetone, on the differences in gelation time of the two solvents can be explained by considering two retarding factors: i) the

Chapter II. Synthesis of silica aerogels

47

hydrogen bonding and ii) the steric hindrence [36]. Steric (spatial) factors exert a great effect on the hydrolytic stability of organoxylanes [45]. Any obstacle of the alkoxy group retards the hydrolysis of alkoxysilanes, but the hydrolysis rate is mainly lowered by branched alkoxy groups. If one compares the gel time under the same conditions, the retarding effect of the ethoxide group in TEOS is evident. In the case of methanol, these two factors have very little effect and hence the shortest gelation time was observed. Complexes are formed between silicic acid and esters through hydrogen bonding [46] which retard the polymerization process. The relative effectiveness of hydrogen bonding activity is the shortest for methanol, and the highest for acetone, therefore the gelation time using methanol is shorter than for acetone. Steric hindrence increases when acetone is used as solvent which will lead to larger pores and hence a decrease in transparency of the aerogels (see chapter III: characterization). With respect to supercritical drying, an amount of solvent was added into the autoclave. This additional solvent can take part in the further dissolution of the silica gel [47]. Summarizing the effect of the solvent in TMOS gels: i) Gelification time for methanol samples is shorter than for acetone samples due to the effect of the hydrogen bonding and the steric hindrence of the solvents. iii) Methanol gels are very transparent while acetone aerogels had white shading; their opacity decreases with increasing TMOS content. iv) When ethanol was used as a solvent (using TMOS as a precursor) cracked gels were obtained. v) Two good quality routes were selected for obtaining acetone monolithic structures without cracks. The M gels were very transparent and strong. The A1 gels were especially fragile. Further study on the effects of the supercritical drying media on aerogel properties and microstructures is essential for developing means of quality control in creating aerogels. 3.1.3 Water amount The amount of water used at the hydrolysis step was found to have a significant effect on the texture of aerogels. The effect of water concentrations was examined for the samples prepared at acetone/TMOS molar concentrations of 0.204 (v=0.4). The effect of hydrolysis solution

Chapter II. Synthesis of silica aerogels

48

The dependency of the gelification time with the molar ratio h, h

H 2O , was studied. TMOS

The reaction time increases very quickly with the water molar ratio, h. With an increase from h=2 to a water excess over the stoichiometric amount (h=16), the time of gelation was reduced from 3 days to 56 min. This effect is reflected in the exponential decreases of the gelification time as a function of the water molar ratio (Figure II.9).

1,6x104 1,4x104 1,2x104

t gelificación (min)

tgelification =400+16.103.e-h/3.1.
Chi2 = 248014 y = 398.1±309.0
0

1,0x104 8,0x103 6,0x103 4,0x103 2,0x103 0,0 0 2 4 6 2 8 10 12 14 16 18

A= 15770±1493 t = 3.1±0.38

[H O]/[TMOS]

Figure II.9 Gelification time as a function of the hydrolysis constant, h, for gels with acetone/TMOS molar ratio of 0.204. tgel decreases exponentially as a function of water molar ratio.

Figure II.10 shows the variation of pH in a gel with acetone/TMOS molar ratio of 0.204 when water molar ratio, h, was increased from 2 to 16. The pH variation will be controlled by the variation in hydrolysis and condensation rates.

Chapter II. Synthesis of silica aerogels

49

7,2 7,0 6,8 6,6 6,4

Acetone/TMOS 0.204/1

pH

6,2 6,0 5,8 5,6 5,4 0 2 4 6 8 10 12 14 16 18

h (H2O/TMOS)

Figure II.10 pH versus water amount for gels with acetone/TMOS molar ratio fixed at 0.204

3.2

TETRAETHOXYSILANE: TEOS AEROGELS

As the fumes from TMOS are toxic and may cause blindness, other esters of orthosilicic acid like TEOS were used to obtain silica aerogels. TEOS is not only less toxic when compared to TMOS but it is cheaper too. Hence, TEOS is a suitable precursor for the commercial production of silica aerogels. The experimental results on the influence of molar ratios of precursor, solvent and water of TEOS silica aerogels are reported in this section. Alcogels were prepared by hydrolysis and polycondensation of tetraethoxysilane (TEOS) in ethanol using either C 6H8O 7, HCl, NH4 OH, or NH 4F+ NH4OH as a variable catalyst solution [48 - 50]. In order to identify the optimal condition for producing the best quality TEOS silica aerogels in terms of monolithicity, density and transparency, the molar ratios of EtOH/TEOS (0.15 m 9) and H2 O/TEOS (0.23 h 10) were systematically varied. The synthesis conditions are summarized in Table II.10, 11, 12, and 13.

Chapter II. Synthesis of silica aerogels

50

Table II.10

Synthesis experimental conditions, type of precursor TEOS, as solvent EtOH, without presence of catalyst, precursor (m) and water concentration (h)

Label
TE99M07-N17 TE00AA-AF-AK-N5 TE99BS TE99BG-M05-N13 TE99BU-M-N TE99BW TE99BV TE00AA-W-CD-BZ-99M03-N7 TE00AM5b TE99BI TE00AMa TE99C1 TE99C2 TE99C3 TE98W TE99B TE99C6 TE99C7 TE99C8 TE99C8

m 7 5 9 7 5 4 3 7 6.9 7.6 3.8 4 3.45 2.87 2.9 2.8 2.3 0.15 0.57 0.29

h 8 7 6 6 6 6 6 5 5 5.4 3.3 3.17 2.72 2.26 2.2 2.2 1.81 0.91 0.45 0.23

Table II.10 shows m and h values of TEOS gels produced without catalyst. m (EtOH/TEOS molar ratio) has been changed from 0.3 to 7.6 and h (H 2 O/TEOS molar ratio) from 0.23 to 8. The most reproducible samples were TEOS/EtOH/ H 2 O molar ratio equal to 1/7/5 and 1/5/7.

Chapter II. Synthesis of silica aerogels

51

Table II.11

Synthesis experimental conditions when using TEOS as alkoxide precursor, EtOH as solvent, several type of acid-catalyst, with a variable precursor and water concentration (m/h), and catalyst concentration (c).

Catalyst C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 C6 H8O7 HCl HCl HCl HCl HCl HCl HCl HCl HCl HCl HCl HCl HCl HNO3 HNO3 HNO3 HNO3 HNO3 HNO3 HNO3 HNO3 HNO3

Label
TE98X07bb TE98X07 TE98X07bc TE98X07bd TE98X09-12 TE98X13-18 TE98X19-20 TE00AT TE00AV-99AM TE98X01-99S1 TE98X01-99S2 TE99AO TE99AR TE00AA-99AN-AQ TE99AP TE98X03 TE98X03bb TE98X05 TE99AS TE99AT TE99AU TE99AB TE99AF TE99BE TE99BF TE99AI00-02 TE99AI03-04 TE99AI05-06 TE99BK TE99AI07-08 TE99AI09-10 TE99AI11-12 TE99BK TE99BH TE99AG TE99AH01-02 TE99AH03-04 TE99AH05-06 TE99AH07-08 TE99AH09-10 TE99AH11-12 TE99AJ TE99AK

m/h 3/5 5/5 6/5 9/5 5/6 5/7 5/8 7/5 7/5 7/5 7/5 7/5 7/6 7/6 7/6 7/6 7/7 7/8 7/8 7/8 7/8 6.4/7.5 6.8/4.6 6.9/4 6.9/4 6.9/5.2 6.9/5.7 6.9/6.2 6.9/6.2 6.9/6.7 6.9/7.23 6.9/7.75 2.3/6.5 7/4.8 6.8/5.5 2.7/0.4 2.7/0.5 2.7/0.6 2.7/0.7 2.7/0.9 2.7/1 3/10 3/9.6

c 0.0001 0.0009 0.0001 0.0001 0.0001 0.0001 0.0001 0.003 0.0005 0.0009 0.0004 0.01 0.01 0.003 0.0005 0.0001 0.0001 0.0001 0.0005 0.003 0.01 0.51 0.058 0.13 0.2 0.21 0.23 0.25 0.51 0.27 0.3 0.32 0.53 0.1 0.03 0.23 0.23 0.23 0.23 0.23 0.23 0.3 0.5

Chapter II. Synthesis of silica aerogels

52

Table II.12 shows TEOS gels synthesized with ethanol as solvent and three types of acidcatalysts: C6 H8O7 , HCl, and HNO3. When C6H8 O7 was used, m (EtOH/TEOS) was ranged from 3 to 9 and h (H2O/TEOS) from 5 to 8, the concentration of C6 H8O7 was ranged from 1.10 -3 to 1.10 -2..

Table II.12

Synthesis experimental conditions when using TEOS as alkoxide precursor, EtOH as solvent, several base-catalyst, and a variable precursor and water concentration (m, h), and catalyst concentration (c).

Catalyst NH4 OH C2 H2O4 +NH4 OH C2 H2O4 +NH4 OH C2 H2O4 +NH4 OH C2 H2O4 +NH4 OH CH3 COOH

Label
TE99AV TE99AW TE99BA TE99AY TE99AZ-BB TE99AX

m/h 5/4 5/4 5/5 5/5 5/5 5/4

c 0.01 0.01 0.05 0.01 0.005 0.01

Table II.13

Synthesis experimental conditions when using TEOS as alkoxide precursor, acetone or methanol as solvent, several catalyst, precursor and water concentration (m, h), and catalyst concentration (c).

Solvent Acetone Acetone Methanol

Catalyst HNO3

Label
TE97A0 TE97B0 TE00AM'-AN-AÑ-AP

m/h 0.317/4 0.204/4 4.3/ 5

c 0.05

The solutions were kept either at room temperature, 25°C or at 40°C for gelation. In some cases, to accelerate the aging time in base-catalyzed gels, the gels were first soaked in an aging solution, that is produced by water and catalyst diluted in ethanol (of equal proportions to the original sol), for 24 hours at room temperature. In addition, in a second step were soaked in a washing bath of ethanol for 3 times from 6 to 72 hours at room temperature. This step is diffusion controlled, then the time required for washing increases strongly whit the gel thickness. Generally, the volume of the washing and aging solution was approximately three times the volume of the gels. It is observed that during aging, the wet gels gain weight. A statistical study was performed on the variation of the gelation time on the aerogels obtained using the same synthesizing route, TEOS/EtOH/H2O=1/7/5, to ensure reproducibility of the series.

Chapter II. Synthesis of silica aerogels

53

3.2.1 Neutral

The effect of the TEOS concentration

A study was done using the EtOH/TEOS series without presence of catalyst. The molar ratio water/TEOS, h, was fixed at 6 and the EtOH/TEOS molar ratio was varied from 3 to 9. Monolicithy and homogeneity of the gels obtained were good except for samples with too high TEOS concentration, which had cloudy parts in the aerogel center as reported in chapter III. Next Figure studies the dependency of gelation time with the molar ratio EtOH/TEOS when h was fixed at 6. The gelation time was large compare to those gels synthesized when using catalyst.

336 288 240 192 144 96 48 0 3 4 5 6 7 8 9
y0 A t0 0 0.37 1.33 0 0.03 0.02

Water/TEOS= 6 no catalyst y = y0 + Ae
x/t0

Gelation time (hours)

molar ratio EtOH/TEOS

Figure II.11 Gelation time versus EtOH/TEOS molar ratio for water/TEOS=6 and without using catalyst.

The gelation time showed an exponential dependency versus EtOH/TEOS molar ratio. Summarizing the effect of ethanol content on the TEOS gels, it can be concluded, that an increase in solvent content reduces the probability of mutual collisions of hydrolyzed alkoxides molecules (Si-OH), resulting in a decrease in the rate of polymerization reaction. Moreover, although ethanol acts as homogenizing agent to promote hydrolysis of TEOS, an increase of the ethanol content reversed the hydrolysis and polymerization processes and promoted esterification (Eq. II.2 and Eq. II.3): Si-(OH) + C 2H5OH Si-O-Si + C2H5 OH Si-(OC2H5 ) + H2 O Si-(OC 2H5) + (HO)-Si Esterification ( Eq. II.2) Alcholysis (Eq. II.3)

Chapter II. Synthesis of silica aerogels

54

Acid catalyst To establish the effect of precursor concentration in alcohol the gels were prepared by fixing the molar ratio of H 2O/TEOS ,h, constant at h=5 (excess over the stoichiometric amount) and the catalyst (citric acid) concentration at 0.0001M. The molar ratio of EtOH/TEOS (m) was changed from 3 to 9. All samples were treated in the same way. As the ethanol content increased, the gelling process was significantly retarded, as shown in Figure II.12. This was due to the fact that excess of ethanol separates the molecular species formed and hinders the progress of cross-linkage of the siloxane bond chains (Si-O-Si), leading to the separation of sol clusters.
60

55

Water/TEOS= 5 0.0001M
y0 A1 t1 36.02 ±0.16 0.44 ±0.03 1.88 ±0.03

Gelation time (hours)

y = y 0 + A 1e

x/t1

50

45

40

35 3 4 5 6 7

molar ratio EtOH/TEOS

Figure II.12 Gelation time versus EtOH/TEOS molar ratio at h=5 and 0.0001M of citric acid. The gelation time increased exponentially with the EtOH/TEOS molar ratio.

The time of gelation increased from 30 to 60 hours when increasing the EtOH/TEOS molar ratio from 3 to 9. The same study was repeated adding water concentration at 6, 7, 8, and 10 or at lower values from 3 to 4. Figure II.13 shows the t g dependency on EtOH/TEOS molar ratio when h (water/TEOS molar ratio) was fixed at 8.

Chapter II. Synthesis of silica aerogels

55

28

Water/TEOS= 8 0.0001M
24

Gelation time (hours)

y0 A1 t1 20

13.25 0.23 1.83

±0.41 ±0.08 ±0.16

y = y0 + Ae

x/t

16

12 3 4 5 6 7

molar ratio EtOH/TEOS

Figure II.13 Gelation time versus EtOH/TEOS molar ratio for samples with water/TEOS ratio of 8 and acid citric 0.0001M as catalyst

When h was fixed at 8 the rate of gelation when increasing TEOS concentration increased faster than for h=5, so increasing the water concentration the gel rate of reactions are more sensitive to the rise of ethanol concentration. The acid-catalyst used in the following series was 52%HF. The acid TEOS series was obtained by first synthesizing the more concentrated solution, A HF1, and then diluting it in different volumes of ethanol, AHF2, to AHF5. Next table shows the acid-catalyzed gels (HF) with water/TEOS fixed at 25. Table II.14
Experimental parameters of TEOS gels with acidcatalyst (HF), with water/TEOS molar ratio fixed at 25.
Optical transparen cy Transparent Transparent Transparent Transparent Transparent EtOH 80ml 52% HF 0.4ml

Label AHF1 AHF2 AHF3 AHF AHF5 Label A1

EtOH/TEOS 12.23 18.85 26.25 33.65 41.05 H2O 50 ml

TEOS 25ml

Chapter II. Synthesis of silica aerogels

56

All the series of acid aerogels obtained with TEOS, acid-catalyst (HF), and with water/TEOS molar ratio fixed at 25 were monoliths very transparent and without cracks.

EtOH + H2O +52% HF

TEOS + EtOH

SOL
Gelification time

GEL

Figure II.14 Synthesis scheme for the TEOS gels with acidcatalyst (HF). In this case, the alkoxide solution was dissolved in ethanol and then mixed with the hydrolysis solution dissolved in ethanol.

Base-catalyst The base-catalyzed gels were obtained using a base-catalyst of 30%NH3 +NH4 F 0.5M. The series was obtained by first synthesizing the more concentrated solution, B1, and then diluting it in different concentrations.

EtOH + H2O + 30%NH3+ 0.5M NH4F

TEOS + EtOH

SOL
Gelification time

GEL

Figure II.15 Synthesis scheme for the TEOS gels with basecatalyst (NH3 +NH4 F)

Chapter II. Synthesis of silica aerogels

57

Table II.15 summarizes the basic TEOS gels produced at several dilutions with a fixed water ratio (h= 10) and with h=25. Table II.15
Experimental parameters of TEOS gels with water/TEOS molar ratio fixed at 10 and 25 and base-catalyst (30%NH3 +0.5MNH4 F) concentration of 3.3.10-3 .
Optical transparen cy Transparent Transparent Translucent Translucent Opaque Transparent Transparent Transparent Transparent Transparent 30%NH3 0.055ml 0.055ml 0.5MNH4F 0.055ml 0.055ml

Label B1 B2 B3 B4 B5 B1’ B2’ B3’ B4’ B5’ Label B1’ B1 TEOS 25ml 25ml

EtOH/TEOS 17 25 66 91 116 12.23 18.85 26.25 33.65 41.05 H2O 50 ml 20 ml EtOH 80ml 110ml

The obtained samples presented different shrinkage and transparency. Some of the aerogels with highest density were cracked (B1 and B2). In order to obtain more transparent aerogels the water/TEOS molar ratio was increased up to 25. When h=25, the gels were slightly more transparent than when water amount was 10. All gels were monolithic. In some samples, acetone was used as a solvent and non-monolithic gels were obtained. The acetone amount was fixed at two and the water amount was varied from 0.017 to 0.2 (TE97A). The initial solution appeared translucent and, in the cases with lowest h, divided in two phases. Upper phase was more opaque and lower phase was transparent. For the largest h, appeared as translucent solution including a white precipitated (indicating that the amount of water was too large). Therefore, no monolithic gels were produced when synthesizing TEOS gels with acetone as solvent. In conclusion, the aerogels had better quality when TEOS was diluted with its respective parent alcohol (EtOH) because it avoided trans-esterification.

Chapter II. Synthesis of silica aerogels

58

3.2.2 Water amount

The effect of hydrolysis solution

The amount of water used at hydrolysis step was found to have a significant effect on the texture of aerogels. Water directly participates in the hydrolysis reaction, and can be described by three successive steps: (OH)nSi(C2H5 O)4-n+4H2O where n=0, 1, 2, 3, and 4. From Equation II.4, an increased value for h is expected to promote hydrolysis reaction. Depending on the water/TEOS molar ratio, the following two condensation reactions occurred after the initial hydrolysis: (Eq. II.5) (Eq. II.6) (OH)n+1Si(C 2H5O)3-n +C2H 5OH (Eq. II.4)

Then, the initial relative amount of water determined the distribution and number of the hydrolyzed monomers formed. The amount of water formed during the condensation reactions (Eq. II.6) is half to the water amount used for the formation of silanols (Si-OH) (Eq. II.5). The effect of water concentrations was examined by keeping the EtOH/TEOS molar concentration constant at 7. At the same time, the catalyst concentration was kept constant at 0.001M. The dependency of the gelification time with the molar ratio h, H 2O/TEOS, was studied (Figure II.16).

Chapter II. Synthesis of silica aerogels

59

84 78 72

EtOH/TEOS = 7 acid citric 0.0001M
y=y0+Ae y0 22.77 0.66 A 5623.9 1661.0 t0 0.97 0.05
-x/t0

Gelation time (hours)

66 60 54 48 42 36 30 24 4 5 6 7 8 9

molar ratio water/TEOS

Figure II.16 Gelation time versus water/TEOS molar ratio for gels with EtOH/TEOS molar ratio fixed at 7 and acid catalyst 0.0001M.

The same dependency was observed for gels with acid citric as a catalyst but with smaller gelation time. The most obvious effect of increasing h value is the acceleration of hydrolysis reactions (Eq. II. 4), the reaction time increased very quickly with the water molar ratio, h. The same study was performed in EtOH/TEOS fixed at 7 without the presence of catalyst. The tg dependency is more pronounced than with acid catalyst but the gelation time was much slower.

Chapter II. Synthesis of silica aerogels

60

192 168 144 120 96 72 48 24 4 5 6

EtOH/TEOS= 7 no catalyst y = y0 + Ae
y0 A t0 46.67 157478.31 0.64
-x/t0

Gelation time (hours)

7

8

9

molar ratio water/TEOS

Figure II.17 Gelation time versus water/TEOS molar ratio for gels with EtOH/TEOS molar ratio fixed at 7 and no use of catalyst

In Figures II.16 and 17, gelation time, tg, was shown as a function of water/TEOS molar ratio, h. As the h value increase, gelation time first decreased sharply, then for h values greater than 6 there was a gradual decrease in gelation. This means that for a complete hydrolysis, h should be at least 6. This higher value over the theoretic stoichiometric value is because of the steric hindrance of Si-OC2H5 groups. Then, adding water for ratios h=6, the corresponding value for the complete consumption of the initial water, will not decreases very strongly the gelification time. It was found that at low h values (h 4) the tg was very large. For h values 4, the hydrolysis reaction proceeded rapidly to the complete consumption of the initial water. This observation indicates that the rate of hydrolysis reaction (Eq. II.1) was much faster than the sum of the rates of the water and ethanol producing condensation reactions (Eq. II.2)+ ( Eq. II.3). Then, the t g was very large because the low number of condensation reactions. Also, in this h range, was observed that gelation time decreased when h increased. With h 4 an increase of t g is more pronounced because the hydrolysis and the resulting condensation reactions were not completed, leading to a very limited cross-linking of the silanols. For larger h values (4<h<6) it was observed a general decreased in t g. This indicated that when adequate amount of water is present, t g was probably governed primarily by condensation. For 4 h 6, the ethanol producing reaction (Eq. II.2) dominated, while waterproducing condensation (Eq.II.3) dominated for h 6 [51]. The consequence of these

Chapter II. Synthesis of silica aerogels

61

reactions was a decrease in the concentration of monomeric molecules and an increase in the concentration of oligomers. On the contrary, at h 6, the rate of hydrolysis increased, enhancing the gelation process that increased the cross-linkage of siloxane bonds chains (Si-O-Si) leading to a three-dimensional gel network. This explains the general decrease in t g at larger h values. Influence of the amount of the catalyst The influence of the amount and the type of the catalyst on the properties of aerogels was studied. Tetraethoxysilane easily hydrolyzes in the presence of water, the rate of hydrolysis and condensation reactions depends on pH of the solution [52, 53]. The conditions that were considered the optimal concentrations of reagents were for 7 initial molar concentration of TEOS in ethanol, and with excess of stoichiometric amount of water 5, 6, and 8. Therefore, the influence of catalyst on these three ratios was studied. The following range of acid citric ratio was tested: 0.0005 < Ccitr ic acid < 0.1 TEOS/EtOH/H2 O 1 / 7 / 5, 6, 8

The variation of citric acid concentration leaded to change in pH as shown in Figure II.18 and then, induced changes in the rate of reaction (Figure II.19).

Chapter II. Synthesis of silica aerogels

62

5,0 4,8 4,6 4,4 4,2

pH 1/7/8

pH

4,0 3,8 3,6 3,4 1E-3 0,01 0,1

log10(catalyst concentration)

Figure II.18 pH of the sol versus the citric acid concentration in TEOS/EtOH/H2 O gels 1/7/8.

Increasing the citric acid concentration from 0.0005 to 0.1, the pH was changed from 5 to 3.5.

Table II.16

Synthesis experimental conditions for TEOS as precursor, ethanol as solvent, citric acid as catalyst, and several precursor and water concentration (EtOH/H2 O), and catalyst concentration (C citr ic acid ). Gelation time (tg) and transparency of the resulting gels.

EtOH/H2O 7/5 7/6 7/8

Ccitric acid 0.0005 0.003 0.01 0.0005 0.003 0.01 0.0005 0.003 0.01

tg (h) 44-141 47 138 44 41 69 23 23 46

transparency translucent transparent very transparent translucent transparent transparent opaque opaque very transparent

Chapter II. Synthesis of silica aerogels

63

Gelification was quite rapid for all the set samples mostly for 7/8. Between 0.01 and 0.0005 M, gels were monolithic. The gels obtained at EtOH/H 2 O = 7/5, 7/6, 7/8 have no cracks and give a good quality aerogels.

80

70

Gelation time (hours)

60

50

40

30

10

-4

10

-3

10

-2

log10(concentration of the catalyst (citric acid))

Figure II.19 Gelation time as a function of the citric acid concentration for 1/7/6 TEOS/EtOH/water molar ratio

It was found that the role of catalyst concentration was very important in the formation of silica alcogels for a mixed molar ratio of TEOS/EtOH/H 2 O at 1/7/6 (Figure II.19). In the case of lower catalyst, ( 0.005M) only turbid gels were obtained. This may be due to the formation of silica precipitates. On the other hand, catalyst concentrations 0.001M lead to the formation of transparent alcogels. Figure II.20 shows the gelation time as a function of catalyst concentration. It is clear that a maximum gelation time was obtained for 0.001 M citric acid whereas at lower and higher concentrations of the citric acid the gelation time decreased. Hydrolysis (substitution of OR for OH) or condensation (substitution of OSi for OR or OH) decreases the electron density on silicon (see Figure II.21). This line of reasoning leads to the hypothesis that under acidic conditions, the hydrolysis rates decreases with each subsequent hydrolysis step (electron withdrawing), whereas under basic conditions each subsequent hydrolysis step occurs more quickly as hydrolysis and condensation proceed [ 54]. Then, the decrease of t g at lower concentrations of acid catalyst may be due to the fact that at lower catalyst concentrations the rate of condensation overcompensates the increased surface charge of all ions in the sol and provided for a faster gelation [55].

Chapter II. Synthesis of silica aerogels

64

On the other hand, at higher catalyst concentrations hydrolysis and condensation rates are high which lead to decrease surface charge of all ions in the sol and hence a faster gelation [56]. RO -OSi Si−OH -OR OR -R Increasing acidity (electron withdrawn)

Figure II.20 Inductive effects of substitution attached to silicon, R, OR, OH or OSi [56].

140 120

EtOH/TEOS = 7 acid citric
0.0001M 0.0005M 0.001M 0.003M

Gelation time (hours)

100 80 60 40 20 4,5 5,0 5,5 6,0 6,5 7,0

7,5

8,0

molar ratio water/TEOS

Figure II.21 Gelation time versus water/TEOS molar ratio for several catalyst concentrations. Gels with EtOH/TEOS fixed at 7 and citric acid as catalyst

Influence of the nature of the catalyst Although the hydrolysis and condensation can proceed without the involving catalyst, their use is quite useful. The understanding of catalytic effects is often complicated. There are two interlinked effects that play an important role: the acidity of silanol groups (Si-OH) increases with the extent of the hydrolysis and polymerization, and the effects of reverse reactions that become increasingly important with greater concentration of water and /or base. Hence, to

Chapter II. Synthesis of silica aerogels

65

facilitate the study of the catalyst in the synthesis, sol-gel parameters were kept constant and then the type of catalyst was varied. Previous work indicated that using base-catalyzed in the synthesis with large water ratio (h) produced highly condensed ‘particulate’ aerogels whereas acid catalyzed with low h produced branched ‘polymeric’ sols. Intermediate conditions produce structures intermediate to these extremes. See Figure II.22.

monomer dimer cycle Acid conditions particle Base

conditions . 1 nm 5 nm 10 nm 30 nm 100 nm

Sols Gel: three dimensional network

Figure II.22 Scheme of gel syntheses routes either under basic or acid conditions

The understanding of catalytic effect is complicated because with continue hydrolysis and condensation the acidity of silanol groups (Si-OH) increased, and because the effects of reverse reactions become increasingly important with greater concentrations of water or base. In this section, numerous acid or base catalysts were used. The basic catalysts used were NH4 OH (weak basic catalyst), and NH3 +NH4 F. The acid catalyst used were HF, HCl, HNO3 and C6H 8O7 and the mixture of some of these acids with NH 4 OH, NH4 OH+C2H 2O4 . Their syntheses have been described in the previous sections of this chapter. Table II.18 gathers the gel time (t g) and transparency of the experimental synthesis that resulted in monolithic gels.

Chapter II. Synthesis of silica aerogels

66

Table II.17

Synthesis experimental conditions for TEOS as precursor, ethanol as solvent, and several kind of catalyst, gel time (tg) and transparency of the resulting gels.
Gel label TE99AV (1/5/4) TE99AW (1/5/4)AY(1/5/5) TE99AZ-BA-BB (1/5/5) TE99AZ? TE99AW? 0.03M TE99AG 0.01M TE99AX TE99BL,TE99BJ Catalyst NH4OH 0,01M C2H2O4+NH4OH 0.01M C2H2O4+NH4OH 0.005M NH3+NH4F C2H2O4 HNO3 (1/7/5) CH3COOH (1/5/4) HCl (1/7/5)

tg
2 days 6 days 23 hour 2 days 1 day 19 days 69 hours 12days+2 h

Gel Transparent monolith, opaque gel Transparent, monolith transversal crack. Turbid monolith Transparent monolith, opaque gel Transparent monolith, and opaque gel White gel Monolith, transparent Cracked gel

For all the catalysts when the gels were set with low catalyst concentration (c<10 -4 M), gels were turbid, with c > 1M they were transparent. Turbid alcogels were obtained for the mixtures of acids and bases at lower concentrations (c<10 -2 M). 1. Strong acid + weak basic mixture used as catalysts gives transparent but cracked gels. It is reported that the hydrolysis rate is faster under strongly acidic conditions [ 57]. 2. Weak acid + weak basic mixture gives shrunk and semi-transparent gels. 3. Weak basic gives the best gel.
3.3 ‘TWO-STEP’ SYNTHESIS

This section deals with the achievement in the optimization of the two-steps preparation process roughly corresponding to previous reported recipes [42, 58, 59]. This process was performed using prepolymerized TEOS obtained by the reaction of tetraethoxysilane (TEOS) and sub-stoichiometric amount of water in the presence of acid catalyst. This acid step involves the formation of partially hydrolyzed and partially condensed silica mixture in ethanol, leaving a viscous fluid containing higher molecular weight silicon alkoxy-oxides. In a second part, this viscous mixture is re-dissolved in ethanol with additional water under basic conditions [60]. Gels prepared in this way are known as ‘two-step’ acid-base catalyzed gels. The chemical reactions carried out by this two-step process can be summarized as:

Chapter II. Synthesis of silica aerogels

67

(1) The first step under acid conditions, which operated in concentrated medium, enhanced hydrolysis and formation of dimmers and oligomers. (2) The second step under basic conditions that enhanced polycondensation and allowed dimmers and oligomers to stick in order to form large clusters involving very large pores. This route permitted us to obtain uncracked transparent aerogels with low densities. Specific surface area values were in the range of usual aerogels. (See chapter III, bulk characterization). To establish the effect of several synthesis routes all gels were achieved following the same receipt. The first step was replaced for using the commercially available Prehydrolyzed Ethyl Silicate (H5) as prepolymerized precursor from Silbond Corp. (Silbond, H5). The second step was performed mixing: i) The silica solution containing a variable volume of precondensed silica (v H5 ) diluted in ethanol. ii) With the catalyst solution, that was containing EtOH/H 2O/NH3 or NH4 F+NH3 with variable amounts according to EtOH/H2O ratio. Nevertheless, the volume ratio v NH3 /v H5 was varied from 0.1 to 0.02. Then after gelification, for enhancing the aging process, the gels were soaked in an alcohol/water/catalyst mixture of equal proportions to those of the original sol. The gels were maintained in this solution up to 24 hours.
H2O+EtOH+ NH3 18ml 20ml 0.08ml

Figure II.23 Aging bath including H2 O, EtOH and catalyst

After aging the gels, all water still contained within the pores was removed prior drying by soaking the gels in pure ethanol several times. Effect of precursor concentration The effect of precursor concentrations was examined by keeping the H 2O/H5 volume concentration constant at 1.5 and the catalyst concentration was kept constant at 7.10 -3 M.

Chapter II. Synthesis of silica aerogels

68

In order to study the dependency of the gel time with the volume ratio the v EtOH/ v H5 concentration was changed from 0.8 to 2.5.EtOH/H5. (see Figure II.22). Table II.19 summarizes the two-steps conditions: volume amounts and volume ratios for precursor, ethanol, and NH3

Table II.18

Volume amounts and volume ratios for two-steps aerogels with H5 as precursor, ethanol as solvent, and NH3 as basecatalyst
H5 Volume (ml) Volume ratio 12 1 H2O 18 1.5 EtOH VETOH Variable VETOH/ VTEOS NH3 0.08 7.10-3

Table II.20 gathers the gelation time and transparency of a series of ‘two-steps’ aerogels synthesized at v H5 /v H2O/v NH3 1/1.5/7.10 -3 with a variable amount of ethanol, V ETOH/ VTEOS

Table II.19

Gelation time and transparency of a series of ‘twosteps’ aerogels synthesized at vH5 /vH2O/vNH3 1/1.5/7.10-3 with a variable amount of ethanol, VETOH/ VTEOS
Label H501AF00-05 H501AG00-05 H501AA00-05 H501AH00-05 H501AI00-05 H501AJ00-05 VETOH/VH5 0.8 1.25 1.7 2.1 2.5 3.3 tgel 30’ 1h 1h30’ 2h45’ 4h45’ Observations White precipitate Translucent gels Transparent gels Transparent gels Transparent and very soft gels Transparent gels

The 36 gels (six samples for each molar ratio) were soaked in an aging solution for 24 hours, and after soaked 4 times in pure ethanol for 10 days. It should be pointed out that the washing process increased strongly the quality of the aerogels and decreased the shrinkage during supercritical drying.

Chapter II. Synthesis of silica aerogels

69

Figure II.24 shows the exponential dependency of gelation time versus volume ratio EtOH/H5 for the two-steps gels with EtOH/H5 molar ratio fixed at 1.5 and base-catalyst (NH3 ).
200 180 160

vH2O/vH5= 1.5
y = y0 + A1e y0 A1 t1
x/t1

Gelation time (min)

140 120 100 80 60 40 20

9.12367 6.11881 0.65685 4.9821
-144

1,0

1,5

2,0

2,5

3,0

volume ratio EtOH/H5

Figure II.24 Gel time versus water/H5 volume ratio for gels with EtOH/H5 molar ratio fixed at 1.5 and base-catalyst (NH3 ).

It was observed the same gel time dependency versus EtOH/TEOS volume ratio that onestep gels with TEOS and acid citric as a catalyst. The reaction time increased sharply with the ethanol/H5 volume ratio. For volume ratios lower than one a white precipitate was produced, gels were not formed. Effect of water amount As the same effect that one-step gels, the amount of water used at hydrolysis step was found to have a significant effect on the texture of aerogels. The effect of water concentrations was examined by keeping the catalyst concentration constant at 8.7.10 -5.

Chapter II. Synthesis of silica aerogels

70

Table II.20

Synthesis experimental conditions for precursor, ethanol as solvent, and NH3 catalyst.

H5 as

H5 Volume (ml) Volume ratio molar ratio molar ratio 14 1 -

H2O 32 2.3 1 7.4

EtOH 14 1 0.13 1

NH3 0.01 7x10-4 8.7x10-5 6.5x10-4

The gel time was too short because water was added in excess, then the amount of water was decreased and homogeneous clear and gels were produced. Table II.21
Synthesis experimental conditions for precursor, ethanol as solvent, and NH3 catalyst
H5 Volume (ml) Volume ratio 14 1 H2O 21 1.5 EtOH 24 1.7 NH3 0.01 7.10-4

H5 as

In this synthesis, the gels were not diluted because the quality of the alcogels was very good resulting in non-cracked and transparent samples. Influence of the amount of the catalyst The influence of the amount of the catalyst on the properties of aerogels was studied. The conditions that were considered the optimal concentrations of reagents were for v H5/v EtOH/v H2O 1/1.5/1.7 initial volume concentration of H5 in ethanol with presence of water. Therefore, the influence of the amount of catalyst was studied. The following range of NH3 was tested: 0.002 < xNH3 < 0.1 v H5/v EtOH/v H2O 1/1.5/1.7 Table II.22
Synthesis experimental conditions for H5 as precursor, ethanol as solvent, and a variable amount of NH3 catalyst, c.
H5 Volume(ml) Volume ratio 14 1 H2O 21 1.5 EtOH 24 1.7 NH3 x (volume ratio) c (molar ratio)

Chapter II. Synthesis of silica aerogels

71

Table II.23

H5 aerogels synthesized with vH5 /vEtOH/vH2O fixed at 1/1.7/1.5 and with a variable amount of NH3 catalyst, XNH3 .
Label H501AA00-05 H501AB00-05 H501AC00-05 H501AD00-05 H501AE00-05 XNH3 0.08 0.04 0.06 0.10 0.02 tgel 1h 1h 30’ 1h <1h 12h 10’

All the 30 gels (6 for each catalyst concentration) obtained in the series of two-steps aerogels synthesized with v H5 /v EtOH/v H2O fixed at 1/1.7/1.5 were monolithic and very transparent.

4.

SUMMARY AND CONCLUSIONS

For aerogels using TMOS as alkoxide precursor To obtain transparent aerogels the best synthesis was by using methanol as solvent with the presence of base catalyst at low concentrations. For aerogels using TEOS as alkoxide precursor The best quality TEOS aerogels, in terms of monolithicity and transparency, without much shrinkage were obtained by using weak base or acid catalyst: 1. Tetraethoxysilane concentration in alcohol: 10 ¯40 volume%, 2. Presence of low concentration catalyst. 3. Excess of stoichiometric amount of water (1mol/mol of oxyethylene group). It was found that the gel time varied widely from few minutes to several days, depending on the type of solvent and catalyst combinations, with shortest t g being for methanol solvent and sodium hydroxide catalyst. This effect is a result of the shortest chain length and branching of the solvent, and the effect of the catalyst. Strong acidic catalyst gave transparent but cracked aerogels, whereas weak acids yielded monolithic, transparent aerogels. For all the precursors, it was observed a decrease of gel time either increasing the amount of water or decreasing the concentration of the precursor. With the presence of low concentration of catalyst, the reaction was more easily controlled. The conditions that were considered optimal concentration of reactive were for 1/5/7 and 1/7/5, 6 or 8 with low concentration of acid citric catalyst (0.01<c<0.03). But, summarizing one can state that from the point of view of the texture, the most favorable condition of the preparation were when the ‘two-step’ method was followed and water was removed by

Chapter II. Synthesis of silica aerogels

72

soaking the gels in an ethanol solution. In that case, non-cracked and very transparent aerogels were obtained with a high surface area and a varied density (depends on the v EtOH/v H5 from 0.03 to 0.1).

12 M. Prassar, J. Phalippon, J. Zarzycki,

5.

REFERENCES

Sintering of monolithic silica aerogel, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Processing, vol. 156, Wiley, New York, 1986 13 S.J. Teichner, in: J. Fricke (Ed.), Aerogels, vol. 22, Springer, Berlin, 1986 14 F. Kirkbir, H. Murata, D. Meyers, S. Ray Chaudhuri, in 9th Int. Workshop on Glasses, Ceramics, Hybrids and Nanocomposites from Gels, Sheffield, England (1997) 15 K. Yokota, S. Ohmori and S. Takishima. H. Masuoka, Kagaku Kogaku Symposium Series 35 (1992), p. 149 16 Supercritical drying media modification for silica aerogel preparation Journal of Non-Crystalline Solids Volume 248, Issues 2-3 2 June 1999 Pages 224-234 Satoshi Yoda 17 Ambient-temperature supercritical drying of transparent silica aerogels Tewari, Param H.; Hunt, Arlon J.; Lofftus, Kevin D. Materials Letters Volume 3, Issue 9-10 July 1985 Pages 363-367 18 Drying of silica aerogel with supercritical carbon dioxide M. J. Van Bommela, and A. B. De Haanb,Journal of Non-Crystalline Solids Volume 186 June1995 Pages 78-82 19 Comparison of some physical properties of silica aerogel monoliths synthesized by different precursors Materials Chemistry and Physics Volume 57, Issue 3 25 January 1999 Pages 214218 P. B.Wagh

1. N. Husing, U. Schubert, Aerogels-Airy Materials: Chemistry, Structure, and Properties, Review in Angew. Chem. Int. Ed. (1998), 37, p.22. 2 J. Fricke, R. Caps, D. Buttner, V. Heinemann, E. Himmer, G. Reichenamer, Structural, elastomechanical and thermal properties of silica aerogels, in: K.K. Kruger et al. (Eds.), Characterization of Porous Structure, vol. 629, Elsevier, Amsterdam, 1988 3 T. Woignier, G. Scherer and A. Alaoui. J. Sol¯Gel Sci. Tech. 3 (1994), p. 141. 4 S. Yoda, S. Ohshima and F. Ikazaki. J. NonCryst. Solids 231 (1998), p. 41 5 S.Y. Chang, T.A. Ring, J. Non-Cryst. Solids 147¯ 148, 56 (1992) 6 G.M. Pajonk, M. Repelin-Lacroix, S. Abouarnadasse, J. Chaouki and D. Klvana. J. Non-Cryst. Solids 121 (1990), p. 66. 7 S.S. Kistler. Nature 127 (1931), p. 741. 8 J. Walendziewski, M. Stolarski, M. Steininger and B. Pniak. React. Kinet. Catal. Lett. 58 1 (1996), p. 85. 9 J. Phalippou, T. Woignier and M. Prassas. J. Mater. Sci. 25 (1990), p. 3111. 10 T. Woignier, G. Scherer and A. Alaoui. J. Sol¯Gel Sci. Tech. 3 (1994), p. 141. 11 Transformation of nanostructure of silica gels during drying Journal of Non-Crystalline Solids Volume 262, Issues 1-3 February 2000 Pages 155-161

Chapter II. Synthesis of silica aerogels
20 A.H. Boonstra and C.A.M. Mulder. J. NonCryst. Solids 105 (1988), p. 201. 21 J.G. van Lierop, A. Huizing, W.C.P.M. Meeram and C.A.M. Mulder. J. Non-Cryst. Solids 82 (1986), p. 265. 22 L.C. Klein. Ann. Rev. Mater. Sci. 15 (1985), p. 227. 23 R.A. Laudise and D.W. Johnson, Jr.. J. NonCryst. Solids 79 (1986), p. 155. 24 Physical properties of silica gels and aerogels prepared with new June 1995 Pages 1-8 25 S. Henning and L. Svensson. Phys. Scr. 23 (1981), p. 697. 26 P.H. Tewari, A.J. Hunt, K. Lofftus, in: J. Fricke (Ed.), Aerogels, Springer, Berlin, 1986, p. 31 27 G. Poelz and R. Riethmuller. Nucl. Instrum. Methods 195 (1982), p. 491. 28 R.A. Assink and B.D. Kay. J. Non-Cryst. Solids 99 (1988), p. 359 29 M. Yamane, S. Inove and A. Yasumori. J. Non-Cryst. Solids 63 (1984), p. 12. 30 S.J. Teichner, G.A. Nicolaon, M.A. Vicarini and G.E.E. Gardes. Adv. Coll. Interface Sci. 5 (1976), p. 245. 31 R. Winter, D.W. Hau, D. Thiyagarajan and J. Jonas. J. Non-Cryst. Solids 108 (1989), p. 137. 32 M. Prassas, J. Phalippou and Z. Zarzycki. J. Mater. Sci. 19 (1984), p. 1665 33 Physical properties of silica gels and aerogels prepared with new June 1995 Pages 1-8 34 Ultralow density silica aerogels by alcohol supercritical drying L. Kocon Journal of Nonpolymeric precursors Journal of Non-Crystalline Solids Volume 186 polymeric precursors Journal of Non-Crystalline Solids Volume 186

73
Crystalline Solids Volume 225, Issue 1 April 1998 Pages 96-100 35 T.M. Tillotson and L.W. Hrubesh. J. NonCryst. Solids 186 (1995), p. 209 36 D.J. Stein, A. Maskara, S. Hæreid, J. Anderson, D.M. Smith, in: A.K. Cheetham, C.J. Brinker, M.A. Mecartney, C. Sanchez (Eds.), Better Ceramics Through Chemistry VI, Mater. Res. Soc. Proceed., Vol. 346, Materials Research Society, Pittsburgh, PA, 1994, p. 643. 37 J. Zarzycki, T. Wognier, in: J. Fricke (Ed.), Aerogels, vol. 42, Springer, Berlin, 1986 38 Dependence of monolithicity and physical properties of TMOS silica aerogels on gel aging and drying conditions G. M. Pajonk Journal of Non-Crystalline Solids Volume 209, Issues 1-2 January 1997 Pages 40-50 39 D.R. Uhlmann, B.J. Zeliñski, L. Silverman, S.B. Warner, B.D. Fabes, W.F. Doyle, Kinetic processes in sol¯ gel processing, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Processing, vol. 173, Wiley, New York, 1986 40 G.M. Pajonk. Rev. Phys. Appl. 24 (1989), pp. C4¯ 13. 41 Ultralow density silica aerogels by alcohol supercritical drying L. Kocon Journal of NonCrystalline Solids Volume 225, Issue 1 April 1998 Pages 96-100 42 T.M. Tillotson and L.W. Hrubesh. J. NonCryst. Solids 186 (1995), p. 209. 43. S.S. Kistler. J. Phys. Chem. 36 (1932), p. 52. 44 M. Pauthe and J. Phalippou. Rev. Phys. Appl. C 4 (1989), p. 215. 45 M.G. Vronkov, The siloxane bond (Consultants Bureau, New York, 1978).

Chapter II. Synthesis of silica aerogels
46 Structural development of silica gels aged in TEOS Journal of Non-Crystalline Solids Volume 231, Issues 1-2 1 July 1998 Pages 10-16 47 Transformation of nanostructure of silica gels during drying Journal of Non-Crystalline Solids Volume 262, Issues 1-3 February 2000 Pages 155-161 48. S. Wang, S. Raychaudhuri, A. Sarkar, US patent 5,264,197 (1993). 50 Influence of molar ratios of precursor, solvent and water on physical properties of citric acid catalyzed TEOS silica aerogels. Materials Chemistry and Physics Volume 53, Issue 1 April 1998 Pages 41-47 P. B. Wagha, A. Venkateswara Raoa, and D. Haranatha 51 G.W. Scherer, J. Non-Cryst. Solids 108 (1989), p. 18 and p. 28. 52 C.J. Brinker, G.W. Sherer, Sol¯Gel Science. Physics and Chemistry of Sol¯Gel Processing, Academic Press, New York, 1990 53 Influence of temperature on the physical properties of citric acid catalyzed TEOS silica aerogels P. B. Wagha, D. Haranatha, A. Venkateswara Raoa, and G. M. Pajonkb Materials Chemistry and Physics Volume 50, Issue 1 August 1997 Pages 76-81 54 W. Y. Shih, J, Chem. Phys. 86 (1997), p. 5127 55 C. Okkerse, in: Physical and Chemical Aspects of Adsorbents and Catalyst, edited by B.G. Linsen (Academic Press, 1990), page 214. 56 C.J. Brinker, G.W. Sherer, Sol¯Gel Science. Physics and Chemistry of Sol¯Gel Processing, Academic Press, New York, 1990, page 131. 57 I. A. Aksay, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Processing, vol. 156, Wiley, New York, 1986, pp513-521.

74
58. A.H. Boonstra and T.N.M. Bernards. J. Non-Cryst. Solids 105 (1988), p. 207. 59 Transparent ultralow-density silica aerogels prepared by a two-step sol-gel process Tillotson, T.M.; Hrubesh, L.W. Journal of NonCrystalline Solids Volume 145, Issue 1-3 1 August 1992 Pages 44-50] 60 The dependence of the gelation time on the hydrolysis time in a two-step SiO2 sol-gel process Journal of Non-Crystalline Solids Volume 105, Issue 3 1988 Pages 207-213

Chapter III. Bulk silica aerogel characterization

75

Ch a pt er II I

BULK SILICA AEROGEL CHARACTERIZATION

SECTION OUTLINE
1. MONOLITHICITY, BULK SHRINKAGE, DENSITY AND POROSITY .................................... 75 1.1 TMOS AEROGELS ........................................................................................................................ 76 Skeletal density......................................................................................................................... 76 Bulk density.............................................................................................................................. 76 1.1.1 1.2 1.2.1 1.2.2 1.2.3 Supercritical drying at CO2 conditions ............................................................................ 80 TEOS aerogels synthesized without presence of catalyst ............................................ 82 Base-catalyst .......................................................................................................................... 84 Acid catalyst ........................................................................................................................... 87 Fluorhydric acid ....................................................................................................................... 88 Citric acid ................................................................................................................................. 90 1.3 2. 3. TWO-STEPS SYNTHESIS ........................................................................................................... 91 TEOS A EROGELS ......................................................................................................................... 81

SURFACE AREA MEASUREMENTS BY BET (BRUNAUER, EMMET AND TELLER) ..... 94 INFRARED SPECTROPHOTOMETRY, IR......................................................................................... 99 3.1 3.2 METHANOL SERIES ................................................................................................................. 100 ACETONE SERIES ..................................................................................................................... 102

4.

ULTRAVIOLET-VISIBLE (UV-VIS) SPECTROSCOPY ...................................................................103 4.1 4.2 AEROGEL TRANSPARENCY ................................................................................................. 103 RAYLEIGH SCATTERING ...................................................................................................... 107 4.2.1 A model to interpret the porous aerogel structure using Rayleigh scattering ........ 110

5.

LIGHT SCATTERING MEASUREMENTS OF AEROGELS BY A POLARIZATION-

MODULATED NEPHELOMETER. ................................................................................................................ 113 5.1 5.2 5.3 INTRODUCTION TO LIGHT SCATTERING VS ANGLE EXPERIMENTS .........113 5.1.1 Description of the polarization-modulated nephelometer.......................................... 114 EXPERIMENTAL RESULTS ....................................................................................................115 STRUCTURAL INFORMATION FROM THE LIGHT SCATTERING MEASUREMENTS .......................................................................................................................118 5.3.1 Inhomogeneous media....................................................................................................... 118

Short range correlations: Rayleigh scattering....................................................................... 120 Long range correlations: departures from Rayleigh scattering ........................................... 121 5.4 5.5 6. COMPARATIV E STUDY BETW EEN EXPERIMENTAL M EASUREMENTS AND THEORY ......................................................................................................................................... 122 CONCLUS IONS AND FUTURE W ORK .............................................................................. 125

DIRECT METHODS: ELECTRON MICROSCOPY ........................................................................127 6.1 STRUCTURA L STUDIES BY SCANNING ELECTRON MICROSCOPY .............. .127 6.1.1 6.1.2 6.1.3 6.1.4 6.2 Acetone series .......................................................................................................................127 Effect of the solvent............................................................................................................. 131 Drying procedure.................................................................................................................132 TMOS aerogels in CO2 as solvent....................................................................................133 Sample preparation .................................................................................................................... 134 TEM set-up.............................................................................................................................. 134 6.2.1 Imaging the acetone-series silica aerogels.....................................................................135 Direct visualization .................................................................................................................... 135 6.2.2 Imaging the methanol silica aerogels ........................................................................... .138 Replicas visualization ................................................................................................................. 138

TRANSMISSION ELECTRON MICROSCOPY ................................................................ 134

7.

REFERENCES ............................................................................................................................................. 141

Chapter III. Bulk silica aerogel characterization

75

Previous studies have shown that it is possible to control such physical properties as the porosity and transparency of the aerogels by adjusting the so-called sol-gel parameters. These parameters include the type and concentration of the alkoxide precursor, acid or base catalyst, and water content [1-3]. These parameters affect the structure of the initial gel and, in turn, the properties of the resulting aerogel. In this chapter, it has been taken up a detailed study regarding the comparison of physical properties of silica aerogel monoliths synthesized by different recipes (see chapter II synthesis optimization). Then, each section containing the characterization of a different physical property is arranged in subsections with the different series of silica aerogels. The studied physical properties were: i) ii) iii) iv) v) vi) vii) Monolithicity: monolithic structure or presence of cracks (Section 1), Shrinkage: linear, diametric and volumetric (Section 1) Density of the bulk aerogel (Section 1) and density of the skeleton (Section 1) Volume porosity (Section 1) Specific surface area and pore size distribution (Section 2) Optical transmission and transparency (Section 3) Silica nanoparticle size distribution (Section 6)

It will be shown that all these properties are strongly correlated.

1.

MONOLITHICITY, BULK SHRINKAGE, DENSITY AND POROSITY

Depending on the synthesis and drying conditions of the gels, the aerogels samples were completely cracked, monolith with presences of cracks, or entirely monolithic. Table III.1 summarizes the experimental observations. In order to measure the shrinkage ( V/Vgel) produced during supercritical extraction (see Table III.1) the aerogels and the wet gel dimensions should be compared. Volume shrinkage is defined as:

V Vgel L gel L gel

Vgel L aerogel

Vaerogel Vgel
,

,

(Eq. III.1)

Longitudinal shrinkage:

L L gel

(Eq. III.2)

Diametric shrinkage:
gel

gel gel

aerogel

(Eq. III.3)

Chapter III. Bulk silica aerogel characterization

76

Bulk aerogel density was determined by weighing samples of known dimensions and by dividing the aerogel mass by its volume. A maximum error in the density of about 10% was estimated. The volume porosity was calculated from the density using the equation:
P(%)
SiO2 SiO2 aerogel

*100

(Eq. III.4)

where:

SiO2

= 2.19 g/cm3 is the density of pure silica is the bulk aerogel density was measured by helium pycnometry at room

aerogel

A more accurate value of the aerogel porosity can be obtained using the aerogel skeletal density,
S

, instead of

SiO2

. For few samples,

s

temperature (Micrometrics, AccuyPyc 1330) [4, 5]. For each aerogel, at least four measurements of porosity and aerogel density were carried out.
1.1 TMOS AEROGELS

During gel formation, hydrolyzed TMOS forms the silica gel network and the solvent fills the gel pores. In this section, depending on the solvent used in the gel synthesis, two TMOS routes were characterized: methanol, labeled as M, [6] and acetone [7] labeled as A-series (the corresponding sol-gel syntheses are described in chapter II). The A-series consisted in four aerogels, A1, A2, A3, and A4 with an increasing density. Skeletal density The skeletal density for each of A-series was obtained by helium pycnometry. All the samples showed a similar g/cm3). Bulk density In order to study the batch-to-batch reproducibility a statistical study was performed for a series of aerogels samples obtained using the identical synthesis and drying process for methanol synthesis. Figure III.1 shows the density for each produced M aerogel, mean density value, standard deviation and a density distribution histogram.
s

(around 2.45 g/cm3) slightly larger than that of vitreous silica (

SiO2

=2.19

Chapter III. Bulk silica aerogel characterization

77

0,16 0,15 0,14
0.010

0,16

0,15

0,14

Density (g/cm )

3

0,13 0,12 0,11 0,10 0,09 0.122

0,13

0,12

0,11

0,10

0,09

0

10

20

30

0

2

4

6
3

8

TMOS aerogels, methanol as solvent

Density (g/cm ) Number of samples

Figure III.1 Study of the reproducibility of the aerogel densities obtained using methanol as solvent. Density histogram (left part of the figure) the mean density value was of =0.122 g/cm 3 with a standard deviation of 0.010 g/cm 3.

To study the dispersion of the aerogel density the same reproducibility studies were performed on the acetone series. Figure III.2 shows the densities values for each acetone aerogel sample, the density mean value, the standard deviation and the histogram of the density distribution.

Chapter III. Bulk silica aerogel characterization

78

2

0,35
0

A4 0,0 0,1 0,2 0,3 0,4 A3

A1C

0,06g/cm 0,08g/cm 0,15g/cm 0,24g/cm 0,29g/cm

3

0,007 0,009 0,010

0,30

A1 A2

3 3 3

A4 A2CO2 A3 A2

2

0

0,25

A2CO2 0,25g/cm A3 A4
3 3

0,002 0,017 0,026

0,0
8 6 4 2 0

0,1

0,2

0,3

0,4 A2CO2

density (g/cm )

3

0,20

0,0
2 0

0,1

0,2

0,3

0,4 A2

0,15

0,0

0,1

0,2

0,3

0,4 A1

0,10

A1 A1C

4 2 0

0,0
2

0,1

0,2

0,3

0,4 A4 A1C

0,05 0 10 20 30 40

0

0,0

0,1

0,2

0,3

0,4

50

Acetone series Acetona series

Figure III.2 Aerogel densities for each series obtained when using acetone as gel solvent. 0.06 0.01 g / cm 3 for the A1C series, for the A1 series, 0.08 0.01 g / cm3 3 for the A2 series, 0.15 0.02 g / cm 0.24 0.02 g / cm 3 for 3 the A3 series, 0.25 0.02 g / cm for the A2CO 2 series, and 0.27 0.03 g / cm 3 for the A4 series. For each series, the density histogram is shown at the right of the figure.

It was observed in the Figure III.2 that the samples classified themselves in six different densities groups depending on the different followed synthesis: The first four groups A1, A2, A3 and A4, correspond to the different precursor dilution. The fifth density group is the A2 dried under carbon dioxide supercritical conditions labeled as A2CO 2. It can be observed that A2CO 2 samples have the same density than of A3 aerogels. Finally, the group with the lowest density corresponds to A1C samples that are the A1 samples with added activated carbon. The A-series was chosen to study the dependency of the bulk aerogel density and volume porosity with the concentration of precursor on the initial synthesis solution. As it is shown in Figure III.3, the densities and porosities of the acetone series aerogels presented a linear relationship versus volume concentration of the precursor, v =0.0099 + 0.7229 v
VTMOS . VTMOS Vacetone

(Eq. III.5)

Chapter III. Bulk silica aerogel characterization

79

0,35

100

0,30

Porosity Density

98 96 94

Density (g/cm )

0,25

3

Porosity (%)

0,20

92 90

0,15 88 0,10 86 84 82 0,5

0,05 0,0 0,1 0,2 0,3 0,4

v

Figure III.3 Porosity and apparent silica aerogel density versus v (precursor volume ratio) for the acetone samples. A linear fitting gives, =0.0099 + 0.7229 v.

Varying the TMOS concentration in acetone gels proves to be a very easy way for controlling density and porosity of the resulting aerogels. Following table gathers the mean values of bulk density aerogels, porosity and volume shrinkage of the different TMOS samples.

Table III.1

Volume concentration of TMOS,

v

VTMOS VTMOS Vacetone

,

apparent density, , porosity and volume shrinkage,

V/Vgel, of the

different TMOS aerogels.
Porosity (g/cm3) 0.23 0.10 0.20 0.30 0.40 0.13 0.01 0.08 0.01 0.15 0.02 0.25 0.02 0.27 0.03 (%) 93 96 93 88 86

Sample M A1 A2 A3 A4

V/Vgel 0.27 0.43 0.42 0.47 0.46

It was observed that the methanol-synthesized aerogels, M, presented a smaller shrinkage ( 27 %) than the acetone-series, A, ( 45 %) in which, volume shrinkage was independent on the precursor concentration within the experimental error. Shrinkage differences could be

Chapter III. Bulk silica aerogel characterization

80

related with the use of a basic catalyst for the methanol aerogel while for the acetone series no catalyst was used (sol polymerization conditions of pH between 5 and 6). It is interesting to note that the pH values for both sols are in the acidic side. This is due to the fact that the pH values of TMOS and methanol are on the acidic side (pH 4) and hence the pH of

NH4OH incorporated sol has a value typical of weak-acidic conditions. It is also possible that a number of micro- and/or macropores in the acetone synthesized gels collapsed during supercritical extraction and this resulted in a larger shrinkage. 1.1.1 Supercritical drying at CO 2 conditions To observe the effect of supercritical drying process at low-temperature on the physical properties of the TMOS silica aerogels the acetone gels were used since liquid CO 2 is highly miscible in acetone. The gels used were the A2 synthesis [7, 8] and the resulting aerogels were called A2CO 2. In this first low-temperature drying set, monolithic aerogels free of cracks were obtained. The aerogels obtained had different characteristics that those dried under conventional drying by hypercritical evacuation of the solvent. The main differences between the two drying procedure were: i. The mean aerogel density for the acetone dried gels was CO 2 dried aerogels was aerogels. ii. The mean diametric shrinkage was larger for CO 2 aerogels acetone dried aerogels
/ =0.21. / =0.30 than for = 0.141 g/cm 3 while for the = 0.245 g/cm 3. The aerogels with CO 2 exchange were denser,

then, lower porosity: 85% for aerogels with exchange and 93% for acetone dried

iii. The low- temperature silica aerogels were more opaque. iv. The A2CO 2 aerogels were less fragile. Is important to remark that in the synthesis of the A2CO 2-series the gels were not washed with ethanol after gelation. The soaking solvent was not exchanged, and then, the remaining water and catalyst were still present in the liquid when A2 were supercritcally dried. It may be the main reason for the dramatic shrinkage observed, and consequently the higher density and opacity.

Chapter III. Bulk silica aerogel characterization

81

Previous work [9] reported that the silica aerogels dried at low temperature were hydrophilic while the dried ones at high temperature were hydrophobic. Because the different drying temperatures the composition of the aerogel surface was different. The CO 2 dried aerogels presented OH groups very polar that can react with the water. In the surface of conventional aerogels, there exists alkoxy groups that are not polar and do not react with water. However, in the synthesized aerogels samples presented in this section, the water penetrated in the porous of the aerogels dried conventionally, whiles the CO 2 dried aerogels are hydrophobic. More extended work is necessary to understand this behavior. Conclusions for TMOS aerogels The properties of aerogels are modified according to the conditions of their preparation. i) ii) iii) iv) An easy way for controlling density and porosity of the resulting aerogels is by the variation of TMOS concentration in acetone gels. Methanol aerogels are very transparent while acetone aerogels had a white shading; their opacity decreases with increasing TMOS content. All the aerogels have monolithic structure without cracks. The A1 aerogels were especially fragile. Volume shrinkage for all acetone aerogels is about 45 %, independently of the reactive concentrations. This shrinkage is much larger than that observed for methanol aerogels 27 %. v) Methanol aerogels presented densities and porosities similar to those for A2. For acetone aerogels, it has been observed that density increases, and porosity is reduced, when increasing TMOS content (Figure III.3), the variation could be adjusted to a straight line. This is the behavior that one should expect: denser material needs more precursors, leading to reduced porosities. These results will be supported and discussed by considering the particle and pore sizes observed by scanning electron microscopy (section SEM), by transmission electron microscopy (section TEM) and the optical transmission of aerogels (section UV-VIS-NIR spectroscopy) [10].
1.2 TEOS AEROGELS

A large number of silica aerogels were prepared following, neutral, basic, and acid synthesis. The samples were dried either under ethanol [11-14] or CO 2 supercritical conditions [15, 16].

Chapter III. Bulk silica aerogel characterization

82

The bulk density, porosity and shrinkage of optimized TEOS aerogels (see chapter II for synthesis optimization) are determined in this section. 1.2.1 TEOS aerogels synthesized without presence of catalyst A TEOS-series of aerogels was synthesized without catalyst. Several EtOH/TEOS molar ratio, m, and several H2O/TEOS molar ratio, h, were tested. Two different series of TEOS aerogels were prepared under the same synthesis conditions. After gelling, the gels of the first series were not washed with an ethanol bath, Table III.2, while the gels of the second series were washed and aged in an ethanol soaking (Table III.3). Table III.2 gathers the shrinkages for all the TEOS samples produced without catalyst and at different TEOS/EtOH/H 2O molar ratios. Table III.2
Ethanol/TEOS and water/TEOS molar ratios,
V, V

density, porosity, volume shrinkage, and linear shrinkage, ethanol washing.
EtOH/ TEOS 5 5 5 5 7 7 7 H2O/ TEOS 5 6 7 8 5 6 8 (g/cm3) 0.2515 0.2333 0.1932 0.2215 0.1625 0.1620 0.1645
L L

diametric shrinkage,

for a series of TEOS aerogels without

Porosity (%) 88.5 89.3 91. 2 89.9 92.6 92.6 92.5

V/V 0.545 0.515 0.444 0.535 0.41 0.425 0.480

/ 0.22 0.21 0.18 0.23 0.15 0.16 0.19

L/L 0.26 0.22 0.17 0.23 0.18 0.18 0.21

Observations Cracks Cracks Cracks Cracks Monolithic Monolithic Monolithic

The quality of the set of samples without ethanol exchange was not very good because these aerogels presented some cracks. The shrinkage is similar in all the samples with different TEOS concentration: the volume shrinkage ranged from 0.42 to 0.53, the diametric shrinkage from 0.17 to 0.23, and the linear shrinkage from 0.16 to 0.23. At fixed H2O/TEOS ratio, when increasing the EtOH/TEOS ratio the densities appeared to be smaller.

Chapter III. Bulk silica aerogel characterization

83

Table III.3

EtOH/H2O molar ratio, density, volume shrinkage, and linear shrinkage for a series of TEOS aerogels with ethanol washing.
EtOH/ TEOS 5 H2O/ TEOS 6 (g/cm3) 0.123

V/V

/

L/L

Observations

0.1192

0.365

0.058

Monolithic

5 7 7

7 5 6

0.121 0.116 0.122

0.1481 0.1321 0.1191

0.502 0.360 0.161

0.056 0.0673 0.0826

Monolithic Monolithic Monolithic

7

8

0.113

0.1552

0.530

0.0569

Monolithic

For the washed gels, all the produced silica aerogel were monolithic and with similar smaller volume shrinkage (0.11-0.12). No significant differences of density (0.133 g/cm 3< g/cm3) were obtained when varying the TEOS/EtOH/ H 2O molar ratio. There was a significant difference between the gels not washed and those washed in an ethanol solution [16]. For the same synthesis and drying conditions, gels washed in ethanol exhibited a lower bulk density and the incidence of cracking or fracture of aerogels was significantly lower. This difference in bulk density is attributed to the presence of water during the drying that caused a larger shrinkage giving a denser bulk structure. It was found that the optimum aerogels were produced in the range of 5>h>8, lower (h< 5) and higher (h> 8) values resulted in opaque and cracked aerogels. On the contrary taking the m precursor concentration lower than 5 (m< 5) and higher than 9 (m> 9) values resulted in opaque, high density as well as cracked aerogels. Moreover, the density of aerogels decreases with an increase in m values up to 9. Further increases in m values (m > 9) lead to an increase in the bulk density of the aerogels (because the bad quality of the aerogels). Summarizing, monolithic, low density and transparent TEOS silica aerogels were found for h values between 5 and 8 (5<h<8) and m values between 5 and 9 (5<m<9) when no catalyst was 0.123

Chapter III. Bulk silica aerogel characterization

84

used. As a final point, the effect of washing solution was found to be a very important factor to control the quality of the aerogels. As mentioned before, some of the aerogels dried conventionally were hydrophobic (see Figure III.4), one possible explanation of this effect may be that in the surface of conventional aerogels, there exists alkoxy groups that are not polar and do not react with water. However, in the synthesized aerogels samples presented in this section, the water penetrated in the porous of some aerogels indistinctly of the followed drying process. Figure III.4 shows a picture of a hydrophobic silica aerogel floating on water.

Figure III.4 Photograph of a hydrophobic aerogel produced by using TEOS as metal alkoxide precursor with a molar ratio of TEOS/EtOH/H2O=1/5/6 and dried under ethanol supercritical conditions.

1.2.2 Base-catalyst One-step gels were prepared from TEOS under base-catalyzed conditions. In this case, a small amount of ammonium with ammonium fluoride solution (0.03M NH 3 + 0.5M NH4F) was added as a supplementary catalyst to accelerate the gel formation. Gels were poured in Petri disks ( =30mm, h= 5mm) and dried under CO 2 conditions. Two series of TEOS base-catalyzed aerogels with a variable ethanol concentration were prepared, the first series with H2O/TEOS fixed at 10, and the second series with H2O/TEOS fixed at 25. The obtained samples presented different shrinkage and transparency. The aerogel densities for the two series are gathered in Tables III.4 (h=10) and III.5 (h=25). From the aerogels listed in Table III.4, those ones with highest density presented some cracks and those with lowest density presented an opaque appearance. A

Chapter III. Bulk silica aerogel characterization

85

large variation in aerogel density was produced in that series from 0.0190 g/cm 3 up to 0.124 g/cm3.

Table III.4

Bulk density and porosity of TEOS aerogels with base-catalyst (NH3+NH4F) and H2O/catalyst/TEOS fixed at 10/3.3.10-3/1.
Porosity (g/cm3) 0.1244 0.0602 0.0408 0.0295 0.0190 (%) 94.3 97.2 98.1 98.6 99.1

EtOH/TEOS 16.82 24.73 66.29 91.27 115.75

The most important factor to obtain more transparent aerogels in the base-catalyzed aerogels is to increases the H2O/TEOS molar ratio [17]. Then, in order to improve the transparency of the base silica aerogels the H2O/TEOS molar ratio was increased at 25.

Table III.5

Bulk density and porosity of TEOS aerogels with base-catalyst (NH3+NH4F) and H2O/catalyst/TEOS =25/3.3.10-3/1.
Porosity (g/cm3) 0.053 0.047 0.037 0.036 (%) 97.6 97.8 98.3 98.4

EtOH/TEOS 12.23 18.85 26.25 33.65

When H2O/TEOS molar ratio was fixed at 25 (Table III.5) all the aerogel samples were monolithic without presence of cracks and more transparent than when H 2O/TEOS molar ratio was fixed at 10. In this series, the dependency of density and porosity versus EtOH/TEOS molar ratio was studied. Figure III.4 shows the linear dependency of density and porosity versus EtOH/TEOS molar ratio when H 2O/TEOS=25.

Chapter III. Bulk silica aerogel characterization

86

0,055

98,6

Porosity
0,050

Density

98,4

density (g/cm )

3

98,2

Porosity (%)

0,045

98,0

0,040

97,8

0,035

water/TEOS = 25 base-catalyst (NH3+NH4F)
10 15 20 25 30 35 40

97,6

97,4

EtOH/TEOS

Figure III.5 Porosity and apparent silica aerogel density versus molar EtOH/TEOS ratio for the TEOS aerogels with base-catalyst 3.3.10-3 (NH3+NH4F) and TEOS/H2O fixed at 25. Solid lines are the linear fitting.

If the two density-molar ratio dependencies are compared, one can observe that for larger H2O/TEOS the linear variation of the density versus the EtOH/TEOS was faster. See Figure III.6.

Chapter III. Bulk silica aerogel characterization

87

0,07

0,06 water/TEOS = 10 base-catalyst (NH3+NH4F)

0,05

density (g/cm )

3

0,04

0,03 water/TEOS = 25 base-catalyst (NH3+NH4F)

0,02

0,01 20 40 60 80 100 120

molar concentration EtOH/TEOS

Figure III.6 Comparison of the dependency of density versus EtOH/TEOS ratio for two different samples, one with H2O/TEOS fixed at 10 at the other fixed at 25. Linear fittings.

It should be pointed out that the gels with base-catalyst were soaked in water, catalyst, and ethanol solution in the same proportions than the initial sol in order to accelerate the aging of the gels. There was a significant difference between the gels soaked only in ethanol and those soaked in an aging solution. Gels washed only in ethanol exhibit a more fragile skeleton. This difference is attributed to the presence of water during the aging solution. The presence of water causes solution/reprecipitation giving a smoother network. In addition, and probably more important, continued hydrolysis and condensation reactions occur giving a stronger network [18, 19]. 1.2.3 Acid catalyst The influence of two acid-catalysts (acid fluorhydric and acid citric) on the density, porosity, and shrinkage is studied in this section. All samples were dried under CO 2 supercritical conditions. Several EtOH/H2O/TEOS ratios were used in order to optimize the quality of the acid-catalyzed aerogels.

Chapter III. Bulk silica aerogel characterization

88

Fluorhydric acid The acid catalyst used was 52%HF. The recipe followed was fixing the H 2O/TEOS ratio at 10 and then varying EtOH/TEOS concentration from 12 to 42. Gels were washed with ethanol for several days; Table III.6 shows some of the obtained aerogel densities.

Table III.6

Density and porosity of TEOS aerogels with acidcatalyst (52%HF) and H2O/TEOS fixed at 25.
Density g/cm3 0.102 0.068 0.043 0.024 0.018 Porosity (%) 95.3 96.9 98.0 98.9 99. 2

EtOH/TEOS 12.23 18.85 26.25 33.65 41.05

In that case, the produced TEOS aerogels with HF catalyst were very transparent samples. Figure III.7 shows a linear decrease in the bulk density and linear increase in the bulk porosity with an increase of EtOH/TEOS ratio, which is due to the smaller SiO 2 concentration in the gels when larger ethanol concentrations.

0,07

Porosity Density

99,5

0,06

99,0

density (g/cm )

3

0,05

98,5

Porosity (%)

0,04

98,0

0,03

97,5

0,02

97,0

0,01 15 20 25 30 35 40 45

96,5

EtOH/TEOS
Figure III.7 Porosity and apparent silica aerogel density versus EtOH/TEOS ratio for the TEOS aerogels acid-catalyst (HF) and H2O/TEOS fixed at 25. Linear fitting Porosity(%)=95.1+0.1m with R=0.993.

Chapter III. Bulk silica aerogel characterization

89

Another synthesis using HF was tried with a lower H2O/TEOS molar ratio (fixed at 12) and with a variable EtOH/TEOS molar ratio (in polystyrene tubes of =16mm). Table III.7 gathers the densities obtained. Table III.7
TEOS aerogel densities and porosities of acid series with a variable EtOH/TEOS molar ratio. Acid-catalyst (52% HF) and H2O/TEOS fixed at 12.
Density (g/cm3) 0.0192 0.0294 0.0410 0.0602 0.1244 Porosity (%) 99.1 98.7 98.2 97.2 94.3

EtOH/TEOS 8.55 6.67 6.71 5.43 4.52

Transparency Most opaque Opaque Translucent Most transparent Transparent but opaque inside

In that case, it was found that EtOH/TEOS molar ratio strongly affects the transparency due to the structural change of pore and particle size of the aerogel. A larger density results in more transparent aerogel. Next photography compares a TEOS silica aerogel with an ambient evaporated gel (xerogel). In the case of xerogel sample, it was observed a transparent sample but with a very large shrinkage.

Figure III.8 Photograph comparing two citric acid TEOS silica dried gels samples, on the top a CO 2 supercritically dried sample, and on the bottom, an ambient evaporated gel.

Chapter III. Bulk silica aerogel characterization

90

Citric acid As a comparison, gels were prepared from TEOS under acid-catalyzed conditions at molar ratios of the starting components of the sol: TEOS/EtOH/H 2O=1/7/5. In this case, a variable amount of acid citric (from 0.0005 to 0.1) was added as a supplementary catalyst to speed up the gel formation. The gels were dried under ethanol supercritical conditions. Table III.8
TEOS aerogel, density, shrinkage, and monolicithy of acid series with a variable H 2O/EtOH/TEOS molar ratio. Acidcatalyst (0,0001M acid citric).
Porosity (g/cm3) 0,160 0,162 0,164 0,249 0,233 0,189 0,222 (%) 92,7 92,6 92,5 88,6 89,4 91,4 89,9 d/d (%) 14,52 16,94 19,2 21,77 21,77 16,94 22,58

Label TE98X01-02b TE98X03-04b TE98X05-06b TE98X07-08b TE98X09-12b TE98X13-18b TE98X19-20b

m 7 7 7 5 5 5 5

h 5 6 8 5 6 7 8

V/V 0,40 0,43 0,48 0,54 0,52 0,43 0,54

L/L 0,18 0,18 0,21 0,23 0,22 0,18 0,23

Monolithicity Monolithic Monolithic Monolithic Monolithic with crack Monolithic with crack Monolithic Monolithic with crack

At fixed water concentration, the bulk density is larger when larger TEOS concentrations. The gels experienced a typical linear shrinkage of 0.18-0.23 during the supercritical drying. The density as a function of water molar ratio is shown in Figure III.9.

Chapter III. Bulk silica aerogel characterization

91

0,26

0,24

density (g/cm )

3

0,22

0,20

0,18 4,5 5,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5

H2O/TEOS
Figure III.9 Variation of density from silica aerogel versus H2O/TEOS molar ratio of acid series at fixed concentration of citric acid (0,0001M).

It was found that for h values lower than seven an increase in h value leads to a decrease of the density of the aerogels. Moreover, for higher h values, h>7, the density increases with h. Lowest (h<5) and highest values (h<8) lead to the cracking due to the high shrinkage.
1.3 TWO-STEPS SYNTHESIS

As described in chapter II, in this thesis the two-steps synthesis was achieved by replacing the first acid-step for the commercially partially hydrolyzed silica precursor, H5 obtained by Silbond corp. Then, it will be necessary to identify the desirable processing conditions in the second step. In that second step, the prepared precursor, mixed with appropriate amounts of H2O, EtOH and NH4OH underwent further hydrolysis and condensation reactions formed a clear gel usually within few hours. Then after aging for 24 h in a solution with the same amount of water and catalyst, they were soaked for several days in a pure ethanol bath for removing the interstitial water. They were dried using the CO 2 substitution method. All of the aerogels obtained were hydrophobic.

Chapter III. Bulk silica aerogel characterization

92

Figure III.10 Photograph comparing the quality of two silica aerogel samples obtained with TEOS as alkoxide precursor. The aerogel on the top is a one-step silica aerogel and on the bottom a two-step aerogel. The two-step aerogel shows a higher transparency and lower density.

A first series of two-steps silica aerogels were prepared with different amounts of water and ethanol. A second series was prepared to show the effect of the amount of catalyst used in the gel preparation [20]. Table III.9 gathers some of the densities and transparencies of the two-step series obtained by changing the H5 dilution and the catalyst amount.

Table III.9

Density and transparency of the two-step aerogel series obtained with NH3 catalyst in the second step.
Catalyst amount 0.02 0.04 0.06 0.08 0.1 0.1 0.08 0.08 0.08 0.08 VETOH/ VH5 1.7 1.7 1.7 1.7 1.7 1.7 2.1 1.25 2.5 3.3 VH2O/ VH5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Density (g/cm3) 0.0299 0.0330 0.0466 0.0550 0.0823 0.0800 0.0734 0.0841 0.0748 0.0672 Porosity (%) 98.6 98.5 97.9 97.5 96.2 96.3 96.6 96.2 96.6 96.9

Label H501AE H501AB H501AC H501AA H501AD00 H501AD01 H501AH01 H501AG01 H501AI01 H501AJ01

Transparency Opaque Opaque Opaque Transparent Translucent Translucent Translucent Translucent Translucent Translucent

The two-step aerogel densities ranged from 0.03 to 0.08 g/cm3. For samples with the same water and catalyst concentration increasing EtOH/H5 ratio from 1 to 1.7, the aerogel density

Chapter III. Bulk silica aerogel characterization

93

decreases from 0.0786 to 0.0550 g/cm3. In addition, it was observed that the most transparent and with low-density samples were produced when a catalyst amount of 0.08 and water/EtOH/H5=1.5/1.7/1. The dependence of silica aerogel density on the base-catalyst amount for a fixed molar ratio of TEOS/EtOH/H 2O is plotted in Figure III.11.
0,08

0,07

density (g/cm )

0,06

3

0,05

0,04

0,03

0,02 10
-2

log10(concentration of the catalyst (NH3))

10

-1

Figure III.11 Density of two-step silica aerogel versus the concentration of base catalyst

It is seen from the Figure III.11 that the aerogel density increases as the concentration of catalyst increases. This is due to the fact that at higher concentrations the colloidal particles and pores are smaller and therefore the gels tends to shrink and become denser [23, 24]. It was observed that a very important factor to produce non-cracked two-step aerogels is to soak the gels in a solution with water and basic catalyst dissolved in ethanol. This solution enhances the aging of the gels. When skipping this step, highly cracked aerogels were obtained. In conclusion, two-step process appears to be the best synthesis method to obtain low-density, non-cracked, and transparent aerogels.

Figure III.12 Transparent ‘two-step’ silica aerogels.

Chapter III. Bulk silica aerogel characterization

94

2.

SURFACE AREA MEASUREMENTS BY BET (BRUNAUER, EMMET AND TELLER)

One important aspect of the aerogel pore network is its open nature. In a closed-pore material, gases or liquids cannot enter the pore without breaking the pore walls. Instead, with an open-pore structure, gases or liquids flow through the entire material. The IUPAC classification for the pore size is given by: Macropores, when pore diameter, 50 nm (0.05 m). Mesopores: when 2 nm than 2 nm. Silica aerogels possess a distribution of pores sizes in the micro, meso and macropores regimes. However, the majority of the pores fall in the mesopore range, with relatively few micropores. To get an inside knowledge of the pore structure of aerogels several techniques are used: Small angle X-ray scattering, SAXS, maybe the most useful one for such characteristics and a lot of articles deal with it [25, 26]. Unfortunately, we were not able to have access to this technique. BET (Brunauer, Emmet and Teller) is the most widely available and utilized method for determining aerogel porosity [27]. A detailed description of this method can be found in annex III. This technique successfully accounts for pores below about 100 nm. Thus, in aerogels with typical pore sizes in the 1-1000 nm range, only a fraction of the total available pore space is detected. However, microporosity information can be obtained through mathematical analyses of BET technique such as t-plots or the Dubinin-Radushevich method (Annex III). Gas adsorption can not effectively determines macroporosity. In this technique, nitrogen at its boiling point is adsorbed on the solid sample. The amount of gas adsorbed depends of the size of the pores within the sample and on the partial pressure of the gas relative to its saturation pressure. By measuring the volume of gas adsorbed at a particular partial pressure, the Brunauer, Emmet and Teller equation gives the specific surface area of the material and the pore size distribution of the sample. The pore size distribution used in this work was determined using the Kelvin equation in the analysis of the nitrogen adsorption/desorption curves and the parameter C is obtained by analyzing the standard 2 parameter BET isotherm gives the amount of gas adsorbed as a function of the relative pressure of the adsorbing gas:
pore pore

, is larger than
pore

50 nm, and Micropores when

is smaller

Chapter III. Bulk silica aerogel characterization

95

V Vm

c ( P / P0 ) (1 P / P0 ) 1 ( c 1) ( P / P0 )

(Eq. III.6)

where: V = Volume of gas adsorbed at pressure P, V m = Volume of gas covering the surface with a monomolecular layer, n/nmono is the ratio of the moles adsorbed to the moles adsorbed in a single monolayer. Po = Saturation pressure of the gas (vapor pressure), i.e. the pressure of the gas in equilibrium with bulk liquid at the temperature of the measurement and C is a constant for the gas/solid combination, C=(slope+Y intercept )/Y intercept. The isotherm can be converted to a linear form for ease of extracting the values of V m and C. The constant C represents the relative strengths of adsorption to the surface and condensation of the pure adsorbate (see annex III). BET porosity characterization of the aerogel samples was performed with a Micromeritics ASAP 2000 instrument. The BET surface area, SBET, pore volume, VBET, mean pore diameter,
<
pore >BET

, and C parameter were obtained from the adsorption isotherm of N2 at 77K. The

samples were outgassed overnight at 300 C. The porosity of several TMOS aerogels, A1, A2, A2CO 2, A3, A4, M, and M+2%C was characterized by BET method following the protocol described in Annex III. Surface area, SBET, total pore volume, VBET, and mean pore diameter, < and 630 m2g-1.
pore>BET

, measured by BET, are

presented in Table III.10. It can be observed that all samples show surface area between 410

Table III.10

BET measurements of A-series and M aerogels. Apparent density, porosity, BET surface area, SBET, total volume of pores, VBET, mean pore diameter measured by BET, < pore>BET = 4VBET / SBET, and C parameter.
Porosity (g/cm3) 0.08 0.01 0.15 0.02 0.24 0.02 0.25 0.02 0.27 0.03 0.13 0.01 0.12 0.01 (%) 96 93 89 88 86 93 94 S BET [m2/g] 470 420 551 560 414 589 632 VBET [cm3/g] 1.0 2.7 2.3 2.1 3.2 5.7 5.7 <
pore> BET

Sample A1 A2 A2CO2 A3 A4 M M+2%C

C
57 46 113 51/58 56 37 40

(nm) 10 30 17 20 20 50 34

Chapter III. Bulk silica aerogel characterization

96

The C value showed in Table III.10 gives a quantitative method to evaluate the hydrophobicity of the aerogel samples, smaller C values means larger hydrophobicity. The pore size distributions of the aerogels are estimated by applying the Pierce method [32] to the measured absorption isotherms. Some examples of the pore size distributions obtained by BET are shown in Figure III.13.

A1

Incremental Pore Volume (cm3/g)

A2

A3

A4

M

0 10 100 1000

Mean Pore Diameter (Å)

Figure III.13 Incremental pore volume for A-series, A1, A2, A3, A4 and M aerogels obtained by BET.

From the pore size distribution of Figure III.13 it was observed that for the samples A1 (lowest density, largest opacity), no peak was observed in the mesopore region. In the aerogel prepared at the composition of A4 (largest density, most transparent from A-series), a large fraction of pores has a size in the range of 10 - 100 nm. A2 and A3 aerogels shows that only a fraction of the pores is accounted by BET. For the methanol aerogels, a strong and narrow increment in the range of 40 - 90 nm was observed. It should be noticed that the mean pore diameter values shown in Table III.10 were calculated using de VBET, which only measures

Chapter III. Bulk silica aerogel characterization

97

the pores in the mesopore range, so in the case of BET measurements the mean value
<
pore >BET

will be working successfully only for aerogels with a porosity included exclusively

below 100nm [34, 35]. By plotting the incremental surface area versus pores diameter, we can obtain more information about microporosity. A clear presence of micropores is shown in the incremental surface area plot (Figure III.14). For example, in A1 aerogel surface area are slightly increases when we are close to the micropore range. In this sample, there was no presence of peak in the mesopore range and increased very quickly when close to micropore range, meaning that some pores are out of the measurable BET range.
Incremental surface area (m2/g)

250 200 150 100 50 0 100 1000

Mean Pore Diameter (A)

Figure III.14 Surface area increases for A1 aerogel. The value when close to micropore range was increasing.

If the pore volume is calculated based in the silica aerogel density:
Vpore 1
Aerogel

1
SiO2

(Eq. III.6)

Most of the aerogels showed larger pore volume values than that obtained by BET. Then the V= Vpore -VBET will indicate approximately the volume of porous not measured by BET (pores diameter smaller than 2 nm and larger than 50nm), as well as the percentage of micro and/or macropores. The obtained results are also shown in Table III.11. In addition, using the pore volume obtained by density, the mean pore diameter can be calculated by:
4 Vpore
pore density

S BET

(Eq. III.7)

Chapter III. Bulk silica aerogel characterization

98

Table III.11

Comparison of pore volume and mean pore diameter obtained by BET analysis and by density measurements for the A-series silica aerogels (TMOS).
Sample Vpores [cm3/g] A1 A2 A3 A4 M 12.0 6.2 3.5 3.2 7.2 VBET [cm3/g] 1.0 2.7 2.1 3.2 5.7 Volume of micro+macropores* 90% 60% 40% 0% 20% <
pore> density

<

pore> BET

(nm) 110 60 30 20 60

(nm) 10 30 20 20 50

* Excluding mesopores, pore range being measured by the BET method.

Main discrepancies were observed when the obtained mean pore diameters are compared with the real one obtained from the own density of each sample. For A1 and A2 aerogels the differences are associated at the presence of macropore because the opaque aspect of the samples (Rayleigh effect). This phenomenon appears when the scattering center, the pore, has a diameter close to the visible wavelength, around 500nm. From these data, one might conclude the following: i) The opacity in A1 could be explained by the large value of V which would correspond approximately to the macropores not measured by BET (~90%). ii) A2 and A3 have a pore size distribution with an important number of micropores and/or macropores, but the mean pore diameter obtained is within the mesopore range. iii) A4 presents a mesopores distribution, which is totally accounted by the BET technique, and agrees with the mean pore value obtained by optical measurements. vi) M have a pore size distribution that is mostly accounted by BET (~80%). On the other hand, the clear transparency of monolithic aerogels gives an upper limit for their pore size of about 100 nm [33]. The translucence of some aerogel samples indicates the presence of macropores, although they are not accounted by the BET technique. In order to evaluate the effect of the macropores on the transparency, light transmission (LT) experiments were performed (see section Rayleigh scattering). The porosity of several silica aerogels produced with TEOS as metal alkoxide precursor, by one and two-step synthesis was characterized by BET method following the protocol

Chapter III. Bulk silica aerogel characterization

99

described in Annex III. Next Table gathers the surface area; total pore volume, and mean pore diameter measured by BET. It can be observed that all samples show larger surface area than TMOS aerogels, between 700 and 1012 m2g-1. These differences can be originated by the addition of the washing step in those TEOS aerogels.

Table III.12

BET measurements of TEOS aerogels by one and two-step synthesis. Apparent density, porosity, BET surface area, SBET, volume of pores, VBET, means pore diameter and C parameter measured by BET.
Porosity (g/cm3) 0.115 0.107 0.075 0.080 (%) 94.7 95.1 96.9 96.2 SBET [m2/g] 780 812 946 899 VBET [cm3/g] 4.8 4.8 5.7 4.9 <
pore> BET

Sample TE00AA (1/7/5) TE00AF (1/7/5) H501AI (0.08) H501AD (0.1)

(nm) 22 18 24 21

C
48 60 90.8 95.2

It is observed that two-step aerogels shows a larger surface area (between 890 and 950 m 2g-1) than one-step aerogels. 3. INFRARED SPECTROPHOTOMETRY, IR

The infrared spectroscopy is generally used for the characterization and identification of organic compounds or functional groups of those. Infrared spectroscopic methods have provided considerable information about the surface and structure of silica [36-39]. In this section, the acetone series (A1, A2, A3 and A4) and the methanol aerogel series (M synthesis) were characterized using IR spectrophotometry, a Fourier Transform Infrared Spectrometer Nicolet 710 was used. The IR spectrometer settings were 50 scans, 16.0 cm-1 resolution, and ratio mode. The spectra were registered in a wavelength range of 400 -4000 cm-1. A beam path background spectrum was recorded without sample. Then, the background was subtracted for each IR spectrum to eliminate the vibrations due to air. The IR samples were prepared by making a KBr tablet, approximately 1% weight mass of aerogel mixed with KBr powder were placed inside a cylindrical stainless steel die. The tablet (wafer) was compacted with a pressure of 1000 Kg/cm2, for 20 s in a Carver press. The wafer was inspected for cracks or holes before fit the tablet in the IR holder.

Chapter III. Bulk silica aerogel characterization

100

Figures III.15, III.17 and III.18 show the IR spectra of M, A1 and A2 aerogels. The main common features of these spectra are: two bands around 3500 cm -1 and 1600 cm-1 representing adsorbed water, and the bands around 2950 cm-1 associated to C-H groups. The 1080, 800, and 460 cm-1 bands are attributed to different modes of Si-O or O-Si-O vibrations and the band around 960 cm-1 correspond to stretching vibrations of Si-OH.
3.1 METHANOL SERIES

Figure III.15 shows IR spectrum for the methanol aerogels, M, synthesized using TMOS, Si (OCH2)4, water and base-catalyst (NH4OH).

C-O CH- from methanol Si-OH

Si-O-Si symmetric

60 %T 40

2854.4 2950.9
M

1633.6 958.6
atmospheric H2O

559.3 808.1
atmospheric CO2

3438.8
OHfrom H2O

Si-O-Si bending

20

464.8
O-Si-O asymmetric

1091.6 1000 500 1/cm

4000

3000

2000

1500

Figure III.15 IR spectrum of methanol aerogel (M).

The curve in Figure III.15 is the infrared spectrum of aerogel M. Several important bands were observed. The adsorption bands identified characterizing the SiO 2 aerogel were: 1200-1000 (1092) cm-1 : O-Si-O asymmetric stretching mode. 808 cm-1 :Si-O-Si symmetric stretching mode. 465 cm-1 : Si-O-Si bending mode. These three IR adsorption peaks correspond to the different modes of silica [40]. 959 cm-1 : Si-OH: stretching mode. Si-OH is a quite visible peak, indicating the hydrophilic nature of the M silica aerogel. This result can be confirmed by the C value obtained for this sample by BET. Other identified adsorption bands are:

Chapter III. Bulk silica aerogel characterization

101

3439 cm-1: A broad band appears corresponding to water 1634 cm-1: Atmospheric H2O band that overlaps with the SiO-H band. Both of these bands are related to adsorbed molecular water, indicating again the hydrophilic nature of the sample. 2850 -2950 cm-1: C-H (O-CH2) methanol bonds. The bands of adsorbed methanol are assigned to the symmetric and antisymmetric stretching vibrations of the C-H bonds of residual methanol. An IR spectrum complement is obtained using UV-VIS- near IR spectroscopy technique. In a similar way of IR spectroscopy, absorption bands were obtained in the range of visible, ultraviolet and near infrared. Figure III.16 shows a complete UV-VIS- near IR spectrum from M aerogel.

100

Transmission (%)

80

60

40

20

UV
0

VIS
1000

Near-IR
1500 2000 2500

IR
3000

500

Wavelength (nm)
Figure III.16 UV – VIS - Near IR Transmission spectrum of base-catalyzed TMOS aerogel M (sample 1 cm thick)

The intrinsic absorbance of silica is low in the visible region. It can be observed the low intrinsic adsorption in the visible range (300-900 nm) resulting in a 100% of transmission in the visible range. As wavelengths become progressively shorter, scattering increased, eventually cutting off transmission near 300 nm. Weak absorbance begins to appear in the near infrared, and again cut off transmission around 2700-3200 nm. There is then a "visible

Chapter III. Bulk silica aerogel characterization

102

window" of transmission through silica aerogel that is an attractive feature of this material for day lighting applications. As the spectrum moves into the infrared, scattering becomes less important, and standard molecular vibrations account for the spectral structure. The observed bands in the frequency range of the infrared and near infrared were: vibrations of the ‘stretching’ modes of the SiO-H bonds at 7390 cm-1 (27003200 nm). hydrogen bond of the water at 5476 cm-1 SiO-H stretching and bending modes 4598 cm-1. The analysis of the UV-VIS spectrum shows that the formation of SiO 2 is not completed because the presence of SiO-H groups. C-H stretching and bending modes at 4233 cm-1 There is a region of high infrared transparency between 3300 and 2000 cm -1. This allows a certain amount of thermal radiation to pass through silica aerogel and lower its thermal insulative performance. Addition of additives that absorb radiation in this region can remedy this problem

3.2

ACETONE SERIES

Figure III.17 shows IR spectrum of the A2 aerogel:

100 %T 75 2358.8 contamination 50 3425.3 OH- from H2O 25 1639.4 C-O atmospheric H 2O 804.3 968.2 Si-OH 470.6 Si-O-Si bending 1103.2 O-Si-O asymmetric 0 4000 3000 2000 1500 1000 500 1/ cm

A2

Si-O-Si symmetric

atmospheric CO 2

Figure III.17 IR spectrum of A2 acetone aerogel.

Chapter III. Bulk silica aerogel characterization

103

No large differences were observed compared to M aerogels meaning that the A-series silica skeleton composition is not much different from that one from M aerogels. The C-H peak at 2950 cm-1for A2 sample, present at M samples, did not appear indicating that no acetone remains in the A2 aerogels. Figure III.18 compares the spectrum for each of the acetone-series aerogel.

100 %T 75 A2 A1

A3 A4

50

25

0 4000 3000 2000 1500 1000 500 1/cm

Figure III.18 IR spectra for all the aerogels from the acetoneseries, A1, A2, A3 and A4.

The four spectra did not present remarkable qualitative differences. The analysis shows that the formation of SiO 2 is not completed because the presence of SiO-H groups at 3820 cm-1. The CO 2 atmospheric band at 2360cm-1 (A2 and A4) depends on the quality of the background extraction. 4. ULTRAVIOLET-VISIBLE (UV-VIS) SPECTROSCOPY
4.1 AEROGEL TRANSPARENCY

Depending on the preparation conditions silica aerogels may appear transparent, translucent and opaque. They are transparent when the sizes of pore and particle are smaller than the wavelength of light, and they are homogeneously distributed. The key to control the inhomogenities (implying pore and particle size) of the aerogels lies in the sol-gel stage and in the supercritical extraction process. The amount of light scattered from an aerogel depends mainly on structural inhomogeneities smaller than the wavelength of visible light [41]. Therefore, transparent aerogel transmits rather than scatter light.

Chapter III. Bulk silica aerogel characterization

104

Figure III.19 shows a photograph of the aerogels produced in our laboratory, ordered from the most opaque to the most transparent ones depending on the different sol compositions. These aerogels have been optically characterized in this section by using UV-VIS spectroscopy.

Figure III.19 Photograph of silica aerogels obtained under different sol-gel conditions. The acetone series from A1 to A4, and the methanol sample, M. Its degree of transparency is usually related with the presence of inhomogeneities, amount and size of macropores (section Rayleigh scattering).

In this section, with a view to understand the opacity and transparency of the aerogels, the light transmission in the ultraviolet-visible (UV-VIS) wavelength was measured using a Shimadzu UV/VIS UV-2102 spectrometer. The apparatus was equipped with light sources covering the ultraviolet-visible wavelength range from 300-900 nm. The light transmission (LT) is the amount of light with a fixed wavelength that is transmitted through the aerogel without being scattered in other directions. Then, the maximum of LT corresponds to a completely transparent aerogel where all the incident light is transmitted in the same direction that was incidented. See Figure III.20

Ligth source
Lens Sample Lens

Detector

Figure III.20 UV/VIS spectrometer scheme used to measure light transmittance.

Chapter III. Bulk silica aerogel characterization

105

Aerogel tiles were carefully cut into samples with thickness of 1 cm, and with parallel sides. Then, the incident, Ii, and transmitted, It, intensity of a monochromatic beam with a fixed wavelength were measured. The optical transmittance, T, is defined as the ratio between transmitted and incident intensities (with a fixed wavelength): T = It/ Ii The transmittance, T, is related to the aerogel thickness, x, as:
T e kx ( Eq.III.9 ) Where the constant k is related to the sample structure. Therefore, from the k value obtained

(Eq. III.8)

it may be possible to extract some structural information. The optical absorbance, A, is defined as:
A ln T kx ( Eq.III.10 )

Figure III.21 shows the experimental absorbance obtained for different synthesized samples.
5

A1
4

A2
Absorbance (a.u) Absorvance
3

A3
2

A4
1

M
0

375

475

575

675

775

875

wavelength (nm)

Figure III.21 Absorbance versus wavelength at UV-VIS range for four acetone aerogels, A-series, and a methanol aerogel, M.

Chapter III. Bulk silica aerogel characterization

106

For all aerogel samples it was observed that the absorbance was larger at blue wavelength (358nm) than at red (635nm). It may be used to quantify the red shading of aerogels as the transmitted light is passed through a silica aerogel and the slight bluish haze when an illuminated piece is viewed against a dark background. The optical transmission of the aerogels was measured at a wavelength of 900 nm in order to compare quantitatively the degree of transparency of the samples at the visible range. The results are presented in Table III.13.

Table III.13
aerogels.

Optical transmission at 900nm for 1 cm thick

Sample A1 A2 A3 A4 M

Transmission at 900nm [%] 23 28 30 40 70

Transparency Opaque Translucent Translucent Transparent Very transparent

It was observed that the aerogels prepared using methanol as a solvent and under basic conditions are more transparent than other solvents. This may be due to the fact that as size of the alkoxy group increases, steric hindrance occurs, then when acetone was used as a solvent instead of methanol leaded to larger pores, less homogeneity and hence a decrease in transparency of the aerogels. In Figure III.22 was observed that the amount of precursor strongly affects the optical transmission due to the structural change of pore and particles of the aerogel. The lowest transmission was obtained when more diluted sol conditions (A1), the percentage of transmission was of 23% for a sample with a thickness of 1 cm. In this plot the thickness of the aerogels are not normalized. A1 (x=0.75cm) thickness is smaller than A2, A3, A4 and M (x=1cm). The large size pores may be responsible for the opaque nature of A1 aerogel.

Chapter III. Bulk silica aerogel characterization

107

40

A4

Transmission at 900nm [%]

35

A3
30

A2 A1

25

20 0,1 0,2 0,3 0,4

vTMOS/vTMOS+acetone
Figure III.22 Percentage of optical transmission (at 900 nm) vs. TMOS volume ratio, v, for the acetone series with H2O/TMOS ratio fixed at 4.

In next section, the percentage of transmitted light will be related to the diameter size of the porous, larger porous leads to lower transmission.
4.2 RAYLEIGH SCATTERING

Most of the light that our eyes receive comes not directly from the light source but comes through the scattered light (light that reaches our eyes in an indirect way). The phenomenon of scattering leads to several well-known natural effects, such as blue skies, red sunsets, the white (or gray) color of clouds, and poor visibility on foggy days [42, 43]. Mie developed a very complete theory for scattering spheres of arbitrary size using electromagnetic theory [44]. As mentioned before, in silica aerogels the Rayleigh effect is observe by the reddening of transmitted light (red light has a longer wavelength, and is scattered less by the fine structure of aerogels) and the blue appearance of the reflected light of silica aerogels. Scattering results from the interaction of light with inhomogeneities in aerogel structure. The actual entity that causes scattering, called the scattering center, can be as small as a single large molecule (with an inherent inhomogeneity) or clusters of small molecules arranged in a nonuniform way. However, scattering becomes more effective when the size of the scattering center is similar to the wavelength of the incident light. This occurs in small particles (~400-

Chapter III. Bulk silica aerogel characterization

108

700 nm in diameter for visible light) that are separated from another, or by larger, macroscopic, particles with inherent irregularities. When scattering centers are smaller in size than the wavelength of the incident light, scattering is much less effective. In silica aerogels, the primary particles have a diameter of ~2-5 nm, and do not contribute significantly to the observed scattering. However, scattering does not necessarily arise from solid structures. There is in silica aerogels, a network of pores, which can act, themselves, as scattering centers. The majority of these are much smaller (~20 nm) than the wavelength of visible light (see section 1 on Porosity). There are, however, invariably a certain number of larger pores that scatter visible light. Control of the number and size of these larger pores is, to a certain degree, possible by modifying the sol-gel chemistry used to prepare the aerogel. As scattering efficiency is dependent on the size of the scattering center, different wavelengths will scatter with varying magnitudes. In this section, a method is proposed to quantitatively measure the relative contributions of Rayleigh scattering (21-23) and the wavelength-independent transmission factor (due to surface damage and imperfections) for silica aerogels prepared with different recipes and/or drying procedures. The transmission spectrum of an aerogel slab of known thickness is given by:
Cx 4

T

Ae

(Eq. III.11)

Where: T = transmittance A = wavelength independent transmission factor, C = intensity of Rayleigh scattering, x =sample thickness, = wavelength of the incident light Then, the transmission is plotted against the inverse fourth power of the wavelength and A and C parameters can be determined by fitting to the equation III.11. Aerogels with a high value of A and a low value of C will be the most transparent.

Chapter III. Bulk silica aerogel characterization

109

4

M A2

ln (Transmission)

2

A3
A1 A2 A3 A4 M

A4

A1
0

1,0x10

-11

2,0x10

-11

3,0x10

-11

4,0x10

-11

Figure III.23 Light UV/VIS wavelength transmission and Rayleigh scattering fitting. The data are fitted by lnT=lnAC.x/ 4.

Table III.14 lists A and C values of A-series and M aerogels obtained from the optic transmission at ultraviolet-visible range, wavelength between 300 and 900 nm.

Table III.14
transmission

A and C parameters from the analysis of light Sample A1 A2 A3 A4 M A 3.62 3.81 3.96 3.67 4.17 C (nm-3) 1.70 1011 4.41 1010 3.73 1010 3.51 1010 1.27 1010

Chapter III. Bulk silica aerogel characterization

110

The fit of the absorbance data in Figure III.23 confirms that Rayleigh scattering contributes to the extinction of the light through an aerogel. The fitting parameter C is a measure of the transparency of the aerogel, for lower values of C, more transparent are the aerogels. The most transparent aerogel, M, has a C value of 1.27 1010 while the most opaque aerogel, A1, has a C
value of 1.7 1011. A is the wavelength-independent transmission factor that gives the

contribution of the surface effects on the optical transmission of visible light (due to surface damage and imperfections). Besides the wavelength factor, the scattering intensity depends of the pore size distribution. It is the absence of macropores, which is primarily responsible for the lower light scattering and therefore higher visible transmission for M sample. However, the light scattering measurements do not provide much information about the size of primary particles, which are too small compared to the light wavelength. Section 5 will use the dependency of visible light versus scattering angle to get further structural information. 4.2.1 A model to interpret the porous aerogel structure using Rayleigh scattering In this section, the correlation of scattering measurements with other structural investigations (BET) has been attempted. The principal idea is to correlate the pore information obtained by using the BJH pore size distribution (that determines the mesoporosity), with the Rayleigh scattering measurements (that determines the macroporosity). Making use of both results, one can obtain information on a wider range of pore sizes. Silica absorbs only slightly in the visible and near ultraviolet, so most of the optical attenuation results from Rayleigh scattering. For a material with pore structures in the 1 to 100nm size range, the strong Rayleigh scattering is expected towards the blue and ultraviolet spectral region. The amount of scattered light in aerogels mainly depends on the number and size of the pores. Thus, the optical transmission curve (see Figure III.21) is analyzed for Rayleigh scattering and the data are fitted to the equation:

T

A e

( ). x

(Eq. III.12)

Where: T = transmittance at the wavelength , A = wavelength independent transmission factor, = wavelength of the incident light ( ) is the volumetric coefficient of scattering.

Chapter III. Bulk silica aerogel characterization

111

One might assume independent Rayleigh scattering from spheres with index of refraction n. A characteristic size for the scatter centers (porous) can be derived from the C value using the expression for the volumetric coefficient of scattering valid for an isolated spherical scatter center with diameter <
( ) (1 ) 8(
Rayleigh 4

pore

>Rayleigh :
2

)3

4

n2 1 n2 2

(Eq. III.13)

where is the volume fraction of air. The index of refraction for low-density aerogels is close to one and was estimated with [22]:
n 1 0.21 ( g / cm3 )

(Eq. III.14)
>Rayleigh , for the different samples

Mean porous diameter derived from this calculation, <

pore

are shown in Table III.15. In order to show the discrepancies between mean pore diameters obtained by the different analysis, the obtained mean pore diameters obtained by Rayleigh scattering (Eq. III.13) were compared with the one obtained from the density of each sample and from the BET analysis.

Table III.15
analysis, < Sample

Mean pore values evaluated by three different methods are compared, by BET, < pore>BET , by Rayleigh scattering
pore > Rayleigh, and

by bulk aerogel density, < <
pore> Rayleigh

pore>density.

<

pore> BET

<

pore> density

(nm) A1 A2 A3 A4 M 10 30 20 20 50

(nm) 150 50 15 20 40

(nm) 110 60 30 20 60

The most astonishing feature is the difference between the mean pore diameters for the A1 sample as being determined by BET and LT techniques. For the most opaque sample, A1, the mean pore diameter, <
pore

>Rayleigh , derived from this calculation was of 150 nm. This
pore

value was very different of that obtained by BET, <

>BET =10 nm. The reason of these

discrepancies may be due that BET accounts only in mesopore range, and A1 aerogel have most of their pores in the macropore range (calculated by Rayleigh scattering). From

Chapter III. Bulk silica aerogel characterization

112

analyzing the differences in the data obtained using the different techniques one might obtain the mean pore size distribution proposed in Figure III.24.

Mesopore range BET range

A1 A2 A3

A4

M

1

10

100

1000

Pore size (nm)

Figure III.24 Proposed pore size distribution for A1, A2, A3, A4 and M aerogels obtained by BET, Rayleigh scattering and density analysis.

The model accounts for the observed differences in the optical transparency of the aerogels: the opacity in A1 is explained by the pore size distribution at macropore range (confirmed by UV-VIS measurements). In addition, that clarifies why the A1 porosity was not measured by BET. A2 and A3 have a bimodal pore size distribution with an important number of micropores and/or macropores, but the mean pore diameter obtained is within the mesopore range. That explains that BET measures only a part of the porosity. A4 presents a mesopores distribution, which is totally accounted by the BET technique, and agrees with the mean pore value obtained by optical measurements. M, completely transparent, have a pore size

Chapter III. Bulk silica aerogel characterization

113

distribution that is mostly accounted by BET (~80%). Its mean value is similar for both techniques, BET and optical measurements.

5.

LIGHT SCATTERING MEASUREMENTS OF AEROGELS BY A POLARIZATION-MODULATED NEPHELOMETER.
5.1 INTRODUCTION EXPERIMENTS TO LIGHT SCATTERING VS ANGLE

Light scattering is a noninvasive and remote indirect method to derive structural information. The experimental and theoretical development was carried out at the ‘Microstructured Materials Group’ of the Lawrence Berkeley National Laboratory under the supervision of Prof. Arlon Hunt and Dr. Michel Ayers. The objective of this work was to find the correlation of the angular dependence of light scattering at visible regions with the structural nature of the silica aerogel medium. In the previous section (Rayleigh scattering), it has been proved that intensity of light measurements at fixed angle provide information about the size of scattering centers. Few previous works on angular measurements at different wavelength have been carried out for aerogels characterization. This section will demonstrate the necessity of performing light scattering vs. angle measurements to obtain information outside of the Rayleigh regime and to extract information about the inhomogeneities of the aerogel microstructure. Since the nephelometer set up was not prepared to measure aerogels, and very few articles about this field are published, the work in this section presented on nephelometer characterization shows preliminary results indicating the advantage of using this technique on supplementary structural information. Further studies should be undertaken in order to optimize the use of this technique. This section was structured in four sections: 1. Synthesis and drying of several transparent aerogel samples by the two-steps method (explained in detail in chapter I and II). 2. Light scattering measurements of synthesized aerogels by a polarization-modulated nephelometer (section 5.2) 3. Development of a model that gives structural information from the dependency of the scattered light versus angle and wavelength (section 5.3). 4. And, finally the comparatives study between experimental measurements and theoretical model (section 5.4).

Chapter III. Bulk silica aerogel characterization

114

Optical characterization of the aerogels was performed using scattering apparatus in which a laser beam interacts with the specimen and a detector is rotated around the irradiated volume section. Structural units comparable to the wavelength of the laser light cause a strong isotropic scattering, and entities, which are smaller than the wavelength, cause more or less isotropic scattering depending of the homogeneity of the microstructure. 5.1.1 Description of the polarization-modulated nephelometer The polarization-modulated angle-scanning nephelometer apparatus, illustrated in Figure III.25, was constructed to measure the wavelength, angular, and polarization dependence of the scattered light intensity at visible regions. Three lasers were used, a first one was tunable from 450 to 540 nm (from green to violet), a second one provides a fixed 635 nm red beam, and the last one a ultra-violet beam at 355 nm. The wavelengths used for the scattering measurements were of 355 nm, 458 nm, 488 nm, 514 nm and 635 nm provided the source of light. laser beam laser aerogel sample polarizer Photomultiplier tube

Figure III.25 Photograph of the nephelometer apparatus when silica aerogel light scattering is measured at blue wavelength

It was critical for correct measurements, the alignment of the detection optics and to ensure that the scattering volume seen by the detector was at the center of rotation. A cylindrical aerogel sample was correctly placed in the nephelometer taken attention to the correct alignment with the incoming laser beam in order to diminish the shape and geometrical effects on the detected light scatter intensity. Then, the incoming beam polarized at an angle of 45 to the scattering plane, was focused into the aerogel, with plano-convex

Chapter III. Bulk silica aerogel characterization

115

lens. A rotatory detector was used to pick up the intensity of the scattered light at each angle from 10 to 170 . The rotating arm carries collimation optics, a photomultimeter, and polarizers oriented either parallel or perpendicular to the scattering plane. The rotating stage is controlled by a personal computer. A scheme of the experimental apparatus of this set-up is shown in Figure III.26.

Figure III.26 Schematic diagram of the angle-scanning nephelometer.

The formalism used to describe the polarization states of scattered light is based on the Stokes vector [48]. The Stokes vectors describing incident and scattered light are connected by a 4x4-element Mueller matrix, Si,j [48, 49]. I’=MI where the M is a 16-element Mueller matrix, I is the Stokes vector of the incident light and I’ is the Stokes vector of the scattered light. The information that can be gleaned from each element is dependent on the scattering system. Depending on the polarizer’s configuration different elements of the Mueller matrix can be obtained. In our experiments only S11 were analyzed because are those related with the scattering intensity [48].
5.2 EXPERIMENTAL RESULTS

Scattering measurements were performed on aerogels following the above-described conditions. In this section, it is proposed that a fraction of the aerogel scattering might be due to the density fluctuations in the material on a scale range larger than the pore size [50, 51]. The predicted scattering from inhomogeneous two-phase materials will be described by following the proposed hypothesis. Next figure shows the intensity of scattered light versus scattering angle from a methanol aerogel sample, M, at different wavelength.

Chapter III. Bulk silica aerogel characterization

116

M aerogel
10000

nm514 nm488 nm635 nm458

s11/(1+cos )

2

1000

100 0 20 40 60 80 100 120 140 160 180

Figure III.27 The total intensity S11 on a log10 scale as a function of scattering angle for M aerogels at 4 different wavelengths. In each measure, the scattering angle varies from 10 to 170 . Intensity was arbitrary normalized at =90 and the geometrical factor for horizontally polarized incident light was subtracted,
s11 1 cos
2

, for each

intensity.

The results given in Figure III.27 are the experimental results of the dependency of scattered intensity versus scattering angle, , for a M aerogel. Each curve is the average of three reproducible experimental data. The laser beam have different incident intensity for each different wavelength, in the case of methanol sample was arbitrary normalized at 90 . The angular dependence of the scattered intensity varied when using different wavelength. This dependency is the most fundamental measurement for sizing and will be used in section 5.3 to obtain structural information of the aerogels. The measurements of intensity versus h, h 4 sin( / 2 ) , are called optical structure factor measurement and leads to remark the variations in scattered intensity and quantify the analysis. Figure III.28 shows the experimental s 11 data for M aerogel plotted as a function of h.

Chapter III. Bulk silica aerogel characterization

117

10000

M aerogel

nm458 nm488 nm514 nm635

s11

1000

100 0,0000

0,0005

0,0010

0,0015

0,0020

0,0025

0,0030

h=4 sin( /2)

Figure III.28 Scattered intensity versus h, h 4 sin( / 2 ) , from M silica aerogel for four different wavelength.

This experimental dependency will be used in next sections to calculate the density-density correlation function. The intensity versus angle was also studied in samples with different density and porosity using a fixed wavelength. Figure III.29 shows the dependency of the scattered light for M, A4 and A3 for 635 nm wavelengths. The intensity of the scattered light for A1, A2 aerogels was too large to get any useful data.

0,1

M A3 A4

s11
0,01 1E-3 0,0000

0,0005

0,0010

0,0015

0,0020

0,0025

h

Figure III.29 Scattered intensity versus h for M, A3, and A4 silica aerogels at fixed wavelength: 635 nm. The intensities are not normalized.

Chapter III. Bulk silica aerogel characterization

118

As treated in the Rayleigh scattering section, the intensity versus wavelength gave us some information about pore size distribution, but if we want to get additional characterization of the density inhomogeneities in the aerogels, the angular Rayleigh effect caused by the scatter centers should be normalized,
1 sin

.

5.3

STRUCTURAL INFORMATION FROM THE LIGHT SCATTERING MEASUREMENTS

A model to interpret the experimental results may allow extracting structural information of the aerogels. 5.3.1 Inhomogeneous media In treating the scattering by a particle, it is assumed that the medium where the particle is comprised is optically homogeneous. However, extended continuous media scatters light, indicating that the solid material contains inhomogeneities. The problem of characterizing inhomogeneities in solids and of relating these to the scattered intensity has been treated by Debye using the Rayleigh-Debye theory [52]. In this section, the Rayleigh effect caused by the presence of ‘discrete’ scatter centers will be normalized. By the scattering, we will obtain information about the inhomogeneities of the aerogel media by treating the case assuming that the inhomogeneity of the medium is due to a continuous variation of the dielectric constant. The macroscopic property of the solids appears to be uniform. However, the dielectric constant varies from point to point, then the dielectric constant at point A is given by [53]:
A A

(Eq. III.15)
A

Where

is the average values and
A

a local variation at the point A.

The study of the local variation

is related to the determination of the inhomogeneities of
A B

the media. The correlation distance,

, is the average extension of the inhomogeneities.

In order to visualize the correlation distance, one can consider the product of the fluctuations
A

and

B

at two points A and B separated by a distance r. The average of this product for all
A B

points of the solid will depend upon the distance r. For r=0, mean square value of the fluctuation
2

is obviously equal to the

. If the scattering medium is statistically uniform and

Chapter III. Bulk silica aerogel characterization

119

isotropic, the correlation function will depend only upon the magnitude r, and will vanish for sufficiently large r,
A B

0.

The correlation function is defined by:
(r)
A 2 B

(Eq. III.16)

Figure III.30 shows a scheme that may help to understand the behavior of the correlation function in a two-different medium as aerogels are. Aerogels can be considered a physical mixture of two media: the silica solid skeleton, medium A, and the pore network: medium B.
Medium B: Pore

Medium A: Silica skeleton

r

r '

Figure III.30 Sketch describing the two aerogels media: the silica solid skeleton, medium A, and the pore network: medium B. To understand the variation on density-density correlation function the two figures may be progressively superposed, then density-density correlation function may account for the ‘self-similitude’ of the aerogel microstructure.

The density-density correlation function can be visualized with the aid of Figure III.30 that represents the variations in density when left and right figures were superposed giving a scheme about the ‘self-similitude’ of the microstructure. Then, an idea of the average extension of the inhomogeneities is the steepness of the correlation function from 1 (r=0) to 0 (large r). A narrow shape (continuous line in Figure III.32) means short correlations: large porous and more irregular structure. A broad shape (discontinuous line in Figure III.31) means long correlation: smaller pores and structure that is more regular. If the pore size distribution is very wide, then, the correlation density of the pore structure is too small to contribute.

Chapter III. Bulk silica aerogel characterization

120

5nm

200nm

r

Figure III.31 Density-density correlation function for two types of aerogel microstructure: the discontinuous line means long correlation (smaller pores and regular structure) and the continuous line means short correlations (large porous and more irregular structure).

The presence of the correlation function (r) in the scattered intensity equations permits one to use the angular distribution of the scattered light to determine density-density correlation in the aerogels medium and then, when analyzing this correlation function, allows to obtain structural information. Following the Rayleigh-Debye mode the scattered light is defined by [52]:

I

4
0

r

2

( r)

sin ( h r) hr

dr

sin h 4

2

(Eq. III.16)

Where: is the scattering angle. is the wavelength of the laser beam. (r) is the density-density correlation function. Short range correlations: Rayleigh scattering If the medium contains only short-range correlations in comparison with the wavelength of the light (discrete scatter centers with a size similar of the wavelength). Then (r) vanishes as r increases, in this case, the angular and wavelength dependence of the scatter intensity is the described for the Rayleigh scattering (section 4), symmetrical about 90 and proportional to
-4

.

Chapter III. Bulk silica aerogel characterization

121

Long range correlations: departures from Rayleigh scattering When correlation (r) does not vanish for values of r comparable to the wavelength then, if the correlation function (r) is known, the scattering can be predicted. For example, P. Berdhald and A. Hunt assumed that the correlation function consists of a short-range exponential part, 1(r), and a long-range gaussian part, 2(r):
r r2

(r)

1( r )

2( r )

(1 w )e a 1

we a 2

2

(Eq. III.17)

1.1

1
r r2

(r)
( r)

(1 w )e a 1
4000 500

we a 2
a1 part icle radius a2 porous radius

2

a1 a2

0.0

0 0 0 1 10

4

r

2 10

4

3 10 30000

4

Figure III.32 Density-density correlation used in the predictions for silica aerogels, consisting of a short-range exponential and a long-range gaussian part function

In aerogels, it can be assumed that short-range correlations will be related to the silica nanoparticles, a1, and large-range correlation to the pore structure, a2. The parameter w is the fraction of short to range correlation. Substitution of the proposed correlation function (Eq. III.16) into the intensity equation (Eq. III.17) and performing the Fourier transform of the intensity dependency on intensity resulted in the two components:
i i1 i2

and , the

(Eq. III.17)
3 2 2 2

Where:
i1 8 (1 w) sin a1 1 2
2

1

16

2

a1

Chapter III. Bulk silica aerogel characterization

122

3

i2

2

w a2 a2 exp

2

4

2

sin

1 2
2

2

a2

2

Figure III.33 illustrates the dependency of the predicted scattered intensity for the proposed model versus the scattering angle for each of the used laser. Various wavelengths will cause different scattering intensity in the same aerogel.

i( 30 4580) 1.2 i( i( i( i( i( 2 10 4880) 5145) 6350) 10 1 10 4580) 3550)
10

1 2 3 4

5

0 0

0

0

50

100

150 180

Figure III.33 Theoretical angle dependency of the scattered light intensity, i( , ), for each of the 5 laser wavelength. Where: 1 = 355 nm ultraviolet wavelength, 2 = 458 nm violet wavelength, 3 = 488 nm purple wavelength, 4 = 514 nm green wavelength, and 5 = 635 nm red wavelength. 5.4 COMPARATIVE STUDY BETWEEN EXPERIMENTAL

MEASUREMENTS AND THEORY

The experimental measurements of the angular distribution of the scattered light compared with the theoretically predicted values of intensity. The experimental data have been fitted to the obtained theoretical intensity function, i( , ), by the variation of the parameters a1, a2 and w. Rayleigh angular dependence and a wavelength-dependent intensity have already been removed from both the experimental and theoretical expressions. The following procedure was used to fit the proposed model to the experimental data:

Chapter III. Bulk silica aerogel characterization

123

i) The experimental intensity/angle output file was appended into a matrix for posterior fitting process. In the fitting process, the function readprint reads a data matrix into the document from i( , ) file for each of the aerogel samples measured.

.051

int

Scattered intensity

0.04

1

0.02

1.61 10

3

0 0

60 ( int )
0

120

180 180

Figure III.34 Experimental data file for =514.5 nm of a M aerogel sample.

ii) Then, The MathCAD program has been used to find a linear combination of i1 and i2 functions that best fits to the experimental data. The proposed functions i1 and i2 were entered in the vector F ion order to be fitted:
3 2

w a2 a2 exp

2

4

2

sind

1 2
2

2

a2

2

F

(1

w)

8 sind

a1 1 2
2

3 2 2 2

1

16

2

a1

iii) For each wavelength, an independent file is obtained, so the same procedure to fit a1, a2, and w parameters was repeated in for each of the wavelength experimentally used. Figure III.35 compares the experimental curve with the curves fitted from the model proposed for a M silica aerogel at 635 nm with a final values of a 1=50 nm, and a 2 =400 nm. The measured scattered intensity is fairy well predicted by the calculations, even is incorrectly predicted for angles close to 10º. This disagreement cannot be remedied by calculations

Chapter III. Bulk silica aerogel characterization

124

assuming any reasonable a1, a2 and w values. A "better" fit could be obtained ignoring several of the data points near = 0º and 180º. Further measurements of s11 may be

performed in order to diminish this effect.

7 Aerogel H5 red 5 green Serie1 purple Serie2 Serie3

6

M

i/

4

3

2

1

0 0 20 40 60 80 100 120 140 160 180

Figure III.35 Intensity of scattered light versus angle for a M sample with red wavelength. Solid line shows fitted curve and cross curve gives experimental measurements. The correlation parameters obtained were: a1=50nm, a2=400nm, w=310 -6

For the same aerogel sample, the intensity function was fitted for each of the wavelength resulting in a similar a 1, a 2, and w values for the different wavelength. The fitted values are in agreement with those values obtained by TEM (for particle size) and pore size (150 nm by the model presented in previous section). Figure III.36 compares the experimental curve with the curves fitted from the model proposed for a two-step silica aerogel at 635 nm with a final values of a 1=150 nm, and a 2 =2000 nm. The residual plot,
q
j

min( X)

j

( max X) (

min( X) )

npoint s

, shows the differences

between theoretical and measured angle distribution of the scattering.

Chapter III. Bulk silica aerogel characterization

125

.051 0.04 Yi fit q j

Residual Plot
0.02

i

qj
0

0.001

0 min( X) 1

50

100 Xi q j

150 max( X) 1

50

100

150

X-Y dat a Least -squares fit

Figure III.36 Intensity of scattered light versus angle for a H5 sample with red wavelength. Solid line shows fitted curve and cross curve gives experimental measurements. The residual plot, qj, shows the differences between theoretical and measured angle distribution of the scattering. The correlation parameters obtained were: a1=50nm, a2=400nm, w=310 -6

The total intensity results of Figure III.36 shows that the predicted calculations are quite good approximations to the experimentally measured data. Moreover, the fitted parameters: a1=50nm, a2=400nm shows poor agreement with the pore and particle values obtained by other techniques. A possible reason is that the two-step analyzed sample was extremely transparent so the effects that caused scattering are exclusively the surface damage (microcracks in the range of 2 microns, a2 value). In this case, the nephelometer technique does not give any further information. Further studies may be developed in order to improve the fitting of the data with the aim of extract more accurate structural information from the scattered intensity. Also to normalize the intensity for each laser beam.
5.5 CONCLUSIONS AND FUTURE WORK

The nephelometer has been used to measure the angular and polarization dependence of light scattered at visible regions. It has been proved that intensity measurements at variable angle provide structural information outside the Rayleigh scattering regime. The model proposed for a correlation function ( r ) (1 w )e
r a1 r2

we

a2 2

has fitted the experimental data

Chapter III. Bulk silica aerogel characterization

126

by the variation of the a1, a2 and w parameters. The model has also been fitted with five or four different wavelengths. New correlation functions should be proposed trying to provide a more accurate fits to the experimental scattering data. The normalization of the experimental curves should be changed from 90º to 20º. Further studies may find a better physical interpretation. The useful part of the curves should be normalized with different scale factors because the incident intensity was different for each wavelength. For the short range e -r/a1 correlation function, since a1<<1/h, the Fourier transform can be taken independent of h. In addition, in some places it may be possible to ignore w as small compared to one. Assuming that the present correlation function (r) could be improved to fit the data well, we should plot i( , ) as a function of h alone. It should be possible to get the data for all three wavelengths to plot on the same curve, by adjusting the normalization. Having constructed such a function, it will be needed to extrapolate it to h = infinity (there may be more than one way to do this). Attention should be taken in the interpretation of the analyzed curves. Strong backscattering was observed for values close to 10º, this should account the strong inhomogeneities of the surface. Therefore, when these curves were fitted large a2 values were obtained explaining the larger pores of the surface.

Chapter III Bulk silica aerogel characterization

127

6

DIRECT METHODS: ELECTRON MICROSCOPY

Scanning and Electron microscopy (SEM and TEM) techniques yield direct images of the aerogel structure. Thus, morphological features, such as particle shapes and particle arrangements, can be recognized. An estimation of the particle size can also be obtained, although the acquisition of enough data as to evaluate the particle size distribution is rather tedious.
6.1 STRUCTURAL STUDIES BY SCANNING ELECTRON MICROSCOPY

A microstructural investigation has been taken up using scanning electron microscopy (Leica 360 scanning electron microscope). Preparation of the samples A special problem with the aerogels is the image degradation due to the charging of the samples during the sample exposure to the electron beam. This charge is caused by the strong electrical isolating nature of the silica aerogels. This problem is solved by depositing a thin, conductive 20 nm gold coating by sputtering, thus apparently the gold penetrates in the pores, making the aerogel more conductive avoiding electrostatic charge during the SEM observations. In such case, the tenuous aerogel skeleton may be slightly distorted by the gold coating. A second coating with silver contacts was done to facility the electrical contact between sample and holder. Thus, SEM pictures must be interpreted with caution [54]. 6.1.1 Acetone series When silica aerogel samples were observed by SEM at low amplification, a porous structure was observed. Figure III.37 compare, at the same scale, the morphology of two different types of aerogels, A3 and A4. In both cases, it was observed a cracked surface, probably caused by the preparation process of the samples: samples were carefully cut but it did not avoid the formation of some cracks of some microns in size.

Chapter III Bulk silica aerogel characterization

128

A3

A4

5.0m

5.0m

Figure III.37 Morphology of A3, and A4 silica aerogels imaged by SEM.

SEM micrographs of A-series aerogels were compared at the same enlargement in order to know the effect of TMOS/acetone molar ratio (directly related with the aerogel density) on the microstructures of silica aerogels. Figure III.38 shows the A1, A2 microstructure, and Figure III.39 the A3 and A4 microstructure at the same magnification.

A1
 pore  particle

A2
 particle  pore

1.0m

1.0m

Figure III.38 SEM micrograph of A1, the lowest density aerogel from A-series, and A2 silica aerogel. Parallel arrows mark the constituting particles,  particle, and pores,  pore.

Chapter III Bulk silica aerogel characterization

129

A3
 particle  pore

A4
 pore

 particle

1 m
Figure III.39 SEM micrograph of A3, and A4 silica aerogels. Parallel arrows mark the constituting particles,  particle, and the pores,  pore.

1 m

In all the SEM images at 1-micron range, the aerogels had a granular appearance composed by spherical particles and some pores. SEM images show that the A1 sample is built by smaller interconnected particles than the denser A4 sample. The A4 particles showed the smallest pores, although particles were larger than those of A1. The constituting particle size distributions of 300 particles for each of the aerogel samples calculated from the corresponding micrographs are shown in Figures III.40, III.41, III.42 and III.43, corresponding to A1, A2, A3 and A4, respectively. The slash indicates the corresponding magnification. SEM images show that A1 sample is built by smaller interconnected particles (with a mean size of 48 nm) than the denser A4 sample (with a mean particle size around 90 nm).
Øp=48 nm σ=8 nm

500 nm 500 nm
20

Particle size (nm)

40

60

80

Figure III.40 SEM micrographs of A1 silica aerogel and particle-size distribution of 300 particles seen in micrographs.

Chapter III Bulk silica aerogel characterization

130

Øp =88 nm Mean 88,1 sd 11,4 σ=11 nm

A4
500 nm
20 40

Particle size (nm)

60

80

100

120

Figure III.41 SEM micrographs of A4 silica aerogel and particle-size distribution of 300 particles seen in micrographs.

Ø=55 nm σ=8 nm

500 nm

0

20

40 Particle 60 μm) size 80

Particle size (nm)

(
Figure III.42 SEM micrographs of A2 silica aerogel and particle-size distribution of 300 particles seen in micrographs.

Chapter III Bulk silica aerogel characterization

131

Øp=62 nm σ=11 nm

200 nm
20 40

Particle size (nm)

60

80

100

Figure III.43 SEM micrographs of A3 silica aerogel and particle-size distribution of 300 particles seen in micrographs: samples.

The average diameter for 300 particles calculated from a similar SEM micrograph is summarized in Table III.16. The A1 sample showed the smallest particle size. Considering mean particle size and density, one could assume that in A1 aerogel there are more particles per unit volume and a larger number of contacts among them. Section 2.3 of chapter IV shows a model that correlates mechanical properties and microstructure. 6.1.2 Effect of the solvent To investigate the effect of the solvent; SEM measurements have also been performed on two samples with similar density but different solvent, acetone (A2) and methanol (M). Figure III.45 compares the SEM micrographs from A2 and M aerogels. A variation of particle size is observed; the more opaque aerogel (A2) contains closely bound spherical particles of 30-80 nm in diameter and larger interstitial pores whilst the particle size of the transparent aerogel (M) is smaller. M aerogel shows an interconnected band structure with smaller particle size (less than 50 nm). These microstructures are consistent with the observed differences in optical transparency of the obtained samples.

Chapter III Bulk silica aerogel characterization

132

Figure III.44 SEM micrograph of interconnected band microstructure.

M

aerogel shows

A2

M

500 nm

500 nm

Figure III.45 SEM micrographs comparing microstructures of a) A2, and b) M silica aerogels.

6.1.3 Drying procedure A2 has been dried in two different manners. First, by a supercritical extraction of the solvent and secondly by exchanging the acetone by liquid carbon dioxide, samples are labeled as A2 and A2CO 2 respectively. The resulting aerogel microstructures have been compared. Figures III.46a) and III.46b) compare the morphology of A2 and A2CO 2 aerogels.

A2

A2CO2

1 m

1 m

Figure III.46 SEM micrographs comparing microstructures from A2, and A2CO 2 aerogels.

Chapter III Bulk silica aerogel characterization

133

A2CO 2 presents a slightly more cracked structure and larger particles. See TableIII.16. Shrinkage during drying is larger in A2CO 2 than in A2 samples and their final density is similar to A3 sample. 6.1.4 TMOS aerogels in carbon dioxide as solvent The microstructure of the aerogels obtained at low temperature using supercritical carbon dioxide as solvent was compared to the aerogel obtained by the classical method.

Figure III.47 SEM of HCOOH aerogel obtained at low temperature.

The aerogel microstructure for samples obtained without presence of water was more polymeric than a sample with similar density obtained by one –step method. Moreover, the presence of porous was hardly detected in HCOOH aerogels compare to one-step aerogels.

Table III.16 Mean constituting particle diameter,  p  of silica aerogels measured by SEM .

Sample A1 A2 A3 A4 M A1 + C A2CO2

 (g/cm3) 0.080.01 0.150.02 0.230.02 0.260.03 0.140.01 0.060.01 0.240.03

 p (nm) 483 554 622 886 401 463 604

Chapter III Bulk silica aerogel characterization

134

It should be pointed at that this values are slightly larger than those expected for constituting particles. Probably, this effect is caused by the agglomeration of the nanoparticles by the gold treatment. Although this coating distortion, this technique was useful in order to account for the differences in microstructure, i.e. in A-series increasing density implies increasing particle size. Further studies may be done in order to study the dependency of the microstructure with the variation of the so-called sol-gel parameters.
6.2 TRANSMISSION ELECTRON MICROSCOPY

In general, the counting of particles for obtaining a distribution of particle sizes is tedious and, usually only two-dimensional projections are available. In this section, some threedimensional images were obtained by the acquisition of stereographic micrographs. The main effect of the electron beam is to charge the small particles because are made of so strong insulating material. Therefore, some instability occurred (spatial drift) which affect the resolution. Other effect of the radiation was an overall deformation of the structure after long irradiation time so special attention was taken to control this effect. Sample preparation: The specimen preparation is important if one wants to preserve initial structure of the dried aerogels. Small pieces of material were directly produced by crushing the solid in the agate mortar with the presence of some small pieces of glass to improve the crushing effect. The fine powder was directly deposited on the grid. In the aerogels with replicas visualization, the replicas were obtained loading the aerogels specimens onto the stage of a freezing microtome, evacuated to 1.10 -6 Pa, and cooled to –185C. The aerogels were platinumcarbon replicated at an almost vertical angle (80) and backed with a rotary deposited carbon film at a 100 angle. The silica replica was removed from the aerogel with diluted acid. The replicas were deposed on copper grids. It should be account that the Pt-C film increases the average of particle size (approx. 0.5nm). TEM set-up Electron microscope observations were performed either, directly on the aerogel samples at 100kV, 200 kV or 400 kV, or imaging the aerogel replicas at 20k -80k magnifications. All replicas samples were examined in stereo. Low voltages give high contrast, but the resolution is limited to 5 Å. High voltage gives low contrast but very good resolution (aprox. 2 Å at 400kV). However, this theoretical resolution level has never been obtained due to the charging effect. Practically the best resolution at

Chapter III Bulk silica aerogel characterization

135

400kV was of the order of 4 to 5 Å. Stereopairs were taken to study and visualize the three dimensional arrangement: a tilt angle of ±5º is usually sufficient. Stereopairs were examined to give an idea about the three-dimensional arrangement and the number of chains at the crossing points. The effect of radiation damage by the electron beam was studied in some aerogel samples. 6.2.1 Direct visualization The structure of A-series was confirmed to be a three-dimensional network with an open structure of small chains of diameter a, interconnected at average distances, d. Figure III.48 shows an example of A4 microstructure. The structure is defined by chains with connecting points with a number of departing branches (either 2 or 3). The optical diffractographs exhibit the usual rings due to an amorphous phase indicating no sign of crystallinity. Imaging the acetone-series silica aerogels

A46

60

Gaussian fit Mean SD -------------14,0 3,1

d
40

a

20

0

0

5

10

15

20

25

30

a
Figure III.48 TEM image of A4 silica aerogel shows length chains of 70nm, marked with arrows, with average particle diameter of a=14.0 3.19nm, marked with parallel arrows, and distance of d=30.8 3.9nm.

Chapter III Bulk silica aerogel characterization

136

A4151 (A4+15%C)
20 Gaussian fit Mean SD -----------16,8 2,9

10

0

8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

Figure III.49 TEM image of a detail of the particles of A4 silica aerogel showing a mean particle diameter of 16.8 2.9nm.

The comparison of several aerogels with different densities, A1 and A4 from series-A, (Figures III.50-53) indicated that the basic elements of the 3D network are dependent on the aerogel density.

80

Øp =10.1nm Mean 2,10109 σ=0.6nm SD 0,59944

60

40

20

0

5

1,0

7.5

1,5

10 12.5 15 17.5 Particle size (nm) Particle size (nm)

2,0

2,5

3,0

3,5

20

4,0

Figure III.50 TEM image of A4 silica aerogel shows length chains of 70 nm with average particle diameter of 2.1 0.6 nm and distance of 30.8 3.9 nm

Chapter III Bulk silica aerogel characterization

137

Figure III.51 TEM image of A4 81K zoom silica aerogel.

60

Mean 0,00104 Øp = =nm 8.0 σ= nm 0.1 SD = 1,61623

40

20

0

2.5

0,5

5

1,0

7.5 10 size12.5 14.5 Particle (nm) Particle size (nm)

1,5

2,0

2,5

3,0

3,5

4,0

Figure III.52 TEM image (x160K) of a detail of the particles of A1 silica aerogel showing a mean particle diameter of 8 nm.

Figure III.53 Zoom of A1 silica aerogel TEM image.

Chapter III Bulk silica aerogel characterization

138

The chain diameter is smaller by 30% for a density variation of 30% and the average distance increased of 15%. At very low magnification, the organization of the different densities was hardly observed. The structure of A4 was shown more compact. The chain diameter is smaller and the network was much tighter. 6.2.2 Imaging the methanol silica aerogels Transmission electron microscopy was used to study the morphology of the most transparent one-step silica aerogel. The samples were fractured, vertically replicated with 0.95 nm Pt-C and backed with approximately 12 nm of rotary evaporated carbon. The silica aerogel was then removed from the replica with dilute acid and the replicas were studied by TEM. The stereoscopic TEM images reveal that particles in methanol aerogels are slightly smaller than acetone aerogels and that their structure is markedly more polymeric. This morphology results from side-chain formation on a nearly linear structure. For M, the particles have diameters ranging from 1.7 to 14.2 nm with an average of 6.4 ± 0.5 nm and the chains lengths averaged 62 ± 21 nm with some as long as 132 nm. Pore sizes ranged from 12 to 277 nm with an averaged 61 ± 56 nm. The pores were slightly larger than pores in Aseries, which ranged from 13 to 240 nm with an average of 74 ± 43 nm. Replicas visualization In Figure III.54, the surface of a M silica aerogel with TMOS/acetone/water 1/12.25/4 is shown at 80k magnification. If this image is visualized with a 10x magnifier, the silica chains can be observed. In Figure III.55, it is possible to observe Figure III.54 in three dimensions using stereo glasses. This aerogel, when viewed in stereo, demonstrates that the „airy‟ appearance of the aerogel structure. It can be observed that the chains contain many small spherical particles. The range in size is from 5 to 15 nm with an average diameter of 10±1nm.

Chapter III Bulk silica aerogel characterization

139

Figure III.54 TEM micrograph of base-catalyzed silica aerogel. 50z M-aerogel: low temperature replica. In order to see the detail of the structure of the aerogel it should be viewed with an eye loop (x10)

Figure III.55 Stereoscopic images (tilt angle of 10 ). Aerogel skeleton is formed by interconnected particles in a three-

Chapter III Bulk silica aerogel characterization

140

dimensional structure (average diameter of 6.4±1nm). Low temperature M-aerogel replica.

Figure III.56 Stereoscopic image of detail M-aerogel replicas at low temperature.

Figure III.57 Stereoscopic image of M-aerogel replicas. On the right, a stereoscopic image of M replicas is shown.

Summarizing TEM was used to examine a series of acetone silica aerogel (A-series) and a base catalyzed aerogel with methanol as solvent (M). This technique provided molecular information about the aerogels and enables to distinguish the different parts of the structure of the aerogel: individual chains and crosslinking junctions were visualized. TEM microscopy was used to examine either directly the silica aerogel or the surface replicas. The stereoscopic images with a tilt series at 20k-80k magnifications have made possible a three-dimensional visualization of the aerogel structure.

Chapter III Bulk silica aerogel characterization

141

7

REFERENCES
1. Schmidt, H., and Scholze, H., 9. Fikret Kirkbir Journal of Non"Aerogels" edited by J.Fricke SpringerVerlag (1986), p.49. 2. Brinker, C.J., and Scherer, G.W., "Solgel science: the physics and chemistry of sol-gel processing" Academic Press, N.Y; (1990). 3. M. Prassar, J. Phalippou, J. Zarzycki, Sintering of monolithic silica aerogel, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Processing, vol. 156, Wiley, New York, 1986 4. Skeletal density of silica aerogels T. Woignier, J. Phalippou, Journal of Non-Crystalline Solids 93, 1987, 17-21 5. A. Ayral, J. Phalippou, T. Woignier J. Mater. Sci. 27 (1992), p. 1166 6. Dependence of monolithicity and physical properties of TMOS silica aerogels on gel aging and drying conditions G. M. Pajonk Journal of Non-Crystalline Solids Volume 209, Issues 1-2 January 1997 Pages 40-50 7. Comparison of some physical properties of silica aerogel monoliths synthesized by different precursors Materials Chemistry and Physics Volume 57, Issue 3 25 January 1999 Pages 214-218 P. B.Wagh 8. Drying of aerogels in different solvents between atmospheric and supercritical pressures Crystalline Solids Volume 225, Issue 1 April 1998 Pages 14-18 10. S.S. Kistler. J. Phys. Chem. 36 (1928), p. 52. 11. J. Phalippou, T. Woignier and M. Prassas. J. Mater. Sci. 25 (1990), p. 3111 12. G.M. Pajonk, A.V. Rao, B.M. Sawant and N.N. Paravathy. J. Non-Cryst. Solids 209 (1997), p. 40 13. K. Tajiri, K. Igarashi and T. Nishio. J. Non-Cryst. Solids 186 (1995), p. 83 14. A. Emmerling and J. Fricke. J. NonCryst. Solids 145 (1992), p. 113 15. Supercritical drying media modification for silica aerogel preparation. Satoshi Yoda Journal of Non-Crystalline Solids Volume 248, Issues 2-3 2 June 1999 Pages 224-234 16. Influence of molar ratios of precursor, solvent and water on physical properties of citric acid catalyzed TEOS silica aerogels. P. B. Wagha, A. Venkateswara Rao, and D. Haranatha Materials 41-47 17. Structural development of silica gels aged in TEOS Journal of NonCrystalline Solids Volume 231, Issues 1-2 1 July 1998 Pages 10-16 Chemistry and Physics Volume 53, Issue 1 April 1998 Pages

Chapter III Bulk silica aerogel characterization
18. W,. Cao, and A.. J. Hunt, J. Non-Cryst. Solids 176 (1994) 18 19. Physical properties of silica gels and aerogels prepared with new polymeric precursors Journal of Non-Crystalline Solids Volume 186 June 1995 1-8 20. G.M. Pajonk, A.V. Rao, B.M. Sawant and N.N. Paravathy. J. Non-Cryst. Solids 209 (1997), p. 40 21. G.W. Scherer, J. Non-Cryst. Solids 145, 33 (1992). 22. J.D. Mackenzie, Applications of the sol¯ gel method: some aspects of initial processing, in: L.L. Hench, D.R. Ulrich (Eds.), Science of Ceramic Processing, vol. 113, Wiley, New York, 1986 23. Smith D.M, Hua D.W. and EarlW.L., MRS Bulletin, 44 - 48 (1994). 24. S. Lowell, J.E. Shields, Powder Surface Area and Porosity, Chapman and Hall, London, 1984. 25. J. Fricke, R. Caps, D. Buttner, V. Heinemann, Reichenamer, E. Himmer, G. elastoStructural,

142
Christelle Alié, René Pirard and JeanPaul Pirard 28. C. Pierce , J. Phys. Chem. 57 (1953) 149. 29. G.W. Scherer, S. Haereid, E. Nilsen, M.A. Einarsrud, J. Non-Cryst. Solids, 202 (1996) 42-52. 30. S. Yoda, S. Ohshima and F. Ikazaki. J. Non-Cryst. Solids 231 (1998), p. 41 31. Pierce C., J. Phys. Chem. 57 (1953) 149 32. Fricke J., and Reichenaver G., in "Better ceramics through chemistry II" Ed. Brinker, C.J., Clark, D.E., and Ulrich, D.R., MRS, 1986 , p775. 33. Nitrogen sorption in aerogels, Journal of Non-Crystalline Solids, Volume 285, Issues 1-3, June 2001, Pages 167-174 G. Reichenauer and G. W. Scherer 34. Extracting the pore size distribution of compliant materials from nitrogen adsorption, Colloids and Surfaces A: Physicochemical 2001, Pages 41-50 35. J.B. Peri, J. Phys. Chem. 70 (1966) 2937. 36. J. Kratochvila and M. Gheirghiu, J. Non-Cryst. Solids, 116 (1990) 93. 37. B.A. Morrow and A.J. Mc Farlan , J. Non-Cryst. Solids, 120 (1990) 61. 38. M.L. Hair J. Phys. Chem. 73 (1969) 2372 39. B.E. Yoldas, J. Non-Cryst. Solids 63 (1984), 145. 40. . Fricke and T. Tillotson, Thin Solid Films 297 (1997) 212-223. 41. H. C. Van de Hulst, Light scattering by small particles, Wiley, New York, 1957. and Engineering Aspects, Volumes 187-188, 31 August

mechanical and thermal properties of silica aerogels, in: K.K. Kruger et al. (Eds.), Characterization of Porous Structure, vol. 629, Elsevier, Amsterdam, 1988 ll 26. S. Brunauer, P.H. Emmet and E. Teller. J. Am. Chem. Soc. 60 (1938), p. 309. 27. Mercury porosimetry: applicability of the buckling intrusion mechanism to low-density xerogels, Journal of NonCrystalline Solids, Volume 292, Issues 1-3, November 2001, Pages 138-149

Chapter III Bulk silica aerogel characterization
42. M. Kerker, The scattering of the light and other electromagnetic radiation, Academic Press, New York, 1969. 43. G. Mie, Ann. Physik 25 (1908) 377. 44. Rubin M. and Lampert C.M., Solar Energy Materials 7 (1983) 393-400. 45. Born M. and Wolf E., “Principles of optics” 6th ed. 46. Kistler S.S and Caldwell A.G., Ind. Eng. Chem., 26 (1953) 658. 47. H. Mueller J.Opt. Soc. Am. 38 661 (1948). 48. A.J. Hunt, Proceedings of the intern. conf. on ultrastructure processing of ceramics, glasses, and composites, (1983) 54. 55. 53. 52. 50. 51. 49.

143
A. J. Hunt and P. Berdahl Mat. Res. Soc. Symp. Proc. 32 (1984), 275 P. Debye, Ann. Phys. 30, 59 (1909). Sorense C.M., Aerosol Science and technology 35 (2001) 648-687. A M. Kerker, The scattering of light, Acacemic Press, New York, 1969 Bourret, A. Europhys. Lett. 6, 731 (1988) Schaefer, D. MRS Bulletin, 49 (1994) G. C. Ruben J. of Non-Crystalline Solids 186, 209 (1995)

0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 0Particle size (nm) 20 40 60 = = 0,00104 Mean SD 1,61623

Chapter III Bulk silica aerogel characterization

144

Chap te r IV

MECHANICAL CHARACTERIZATION OF SILICA AEROGELS

SECTION OUTLINE
1. INTRODUCTION ............................................................................................................................... 146 1.1 1.2 2. MICROINDENTER DESCRIPTION.................................................................................................147 MECHANICAL CHARACTERIZATION ...........................................................................................149

MECHANICAL PROPERTIES OF SILICA AEROGELS AS A FUNCTION OF

DENSITY ............................................................................................................................................................ 151 2.1 2.2 SAMPLE PREPARATION ................................................................................................................151 E FFECT OF THE ALKOXIDE CONCENTRATION..........................................................................152 2.2.1 Relationship between silica aerogel microstructure and mechanical properties ....................................................................................................................................... 154 3. INFLUENCE OF S OLVENT AND SUPERCRITICAL DRYING METHOD ON THE

MECHANICAL PROPERTIES .................................................................................................................... 156 3.1 3.2 4. E FFECT OF THE DRYING PROCEDURE........................................................................................156 E FFECT OF THE SOLVENT IN MECHANICAL PROPERTIES .........................................................158 PROPERTIES OF CARBON-SILICA AEROGEL

MICROMECHANICAL

COMPOSITES ................................................................................................................................................... 159 4.1 4.2 5. I NTRODUCTION............................................................................................................................159 E FFECT OF THE CARBON ADDITION ..........................................................................................160

VISCOELASTICITY OF SILICA AEROGELS AT ULTRASONIC FREQUENCIES ...... 166 5.1 5.2 5.3 INTRODUCTION .....................................................................................................................166 E XPERIMENTAL SET-UP: AIR-COUPLED BROAD-BAND PIEZOELECTRIC TRANSDUCERS ........167
DETERMINATION OF THE VISCOELASTICITY OF SILICA AEROGELS AT ULTRASONIC FREQUENCIES. ..............................................................................................................................169

5.3.1 5.3.2 6. 7.

Normal incidence ...................................................................................................... 169 Oblique incidence ..................................................................................................... 171

MECHANICAL CHARACTERIZATION CONCLUSIONS ................................................... 173 REFERENCES...................................................................................................................................... 175

Chapter IV Mechanical characterization of silica aerogels

146

1.

INTRODUCTION

The mechanical properties of the aerogels are crucial for almost any application because the need of handling and machining the material, as well as its durability in rough environments. In addition, there is fundamental interest in understanding the variation in elastic properties with density, and to compare experimental results with theoretical models. The aim of this chapter is to present a description of the mechanical characterization of the silica aerogels which were prepared through out the thesis (chapter II). The mechanical measurements of such samples were carried out by Elena Martínez at the „Departament de Física Aplicada i Òptica‟ of the Universitat de Barcelona. The mechanical characterization of silica aerogels presents some difficulties. Aerogel is a fragile material, difficult to handle and brittle (very small loads are sufficient to crack them). Efforts are being made on improving their mechanical properties and on overcoming the difficulty of measuring such properties. Several testing methods for mechanical characterization have been previously reported, namely; Young‟s modulus and toughness are usually obtained by using ultrasonic sound velocity, [1-2-3], direct longitudinal compression methods, [2, 4], and measurements by the three-point bending beam technique [5,6]. It has been reported that tensile and bend specimens can give extraneous deformations under estimating of the true modulus [7]. AFM in contact mode has also been used to measure Young‟s modulus of aerogels [8]. Mechanical studies of reinforced aerogels using Vickers and Knoop indentation techniques have also been published [1, 9] but are not sensitive enough to measure the mechanical response of such materials. On the other hand, the Young‟s modulus of aerogels is a factor 10 2 to 10 4 smaller than that of silica glass [10] and, therefore, they can be easily compressed. It is a major challenge to improve the mechanical properties of such materials without sacrificing others and also, to find a suitable non-destructive method for their mechanical characterization. Dynamical microindentation is a powerful technique, initially developed for thin film mechanical characterization, where low applied loads and small penetration depths are required [11-12-13]. When it is applied to aerogels, it presents the added advantage of recording the continuous measurement of load-penetration curves, which makes the direct observation of the indentation marks unnecessary. An asset of this technique is that the specimens do not need any

Chapter IV Mechanical characterization of silica aerogels

147

machining for the test to be performed, since the machining process may alter the sample microstructure. Young‟s modulus (E), elastic parameter (EP) and indentation hardness (H) can be measured by applying very small loads (~1mN), small enough to slightly deform the composite aerogels while preventing crack formation in these brittle materials. This technique allows elastic and plastic behavior to be differentiated. The results are presented in five different sections corresponding to the mechanical characterization of different aerogel series that were synthesized by a variety of the sol-gel processes previously described in chapter II. i) ii) First section is an introduction to the mechanical characterization of silica aerogels and a description of the microindenter. Second section shows the results obtained in a series of samples with different densities. Results were analyzed as functions of density, , morphology and pore size distribution. A relation of the type, E with ~2.9 was found for the acetone-

synthesized series. As a function of aerogel density, two different regimes of mechanical behavior were observed. The lowest density aerogels are elastic but the denser aerogels are elasto-plastic materials. iii) iv) Third section presents the mechanical characterization of different series of silica aerogels using different supercritical drying procedure and different synthesis solvent. Fourth section presents the results obtained in a series of silica-carbon composite aerogel obtained with a variable amount of activated carbon (Annex articles: article III). v) Fifth section reports the relationship between mechanical properties and the microstructure of the silica aerogels and carbon-silica aerogel composites. 1.1 MICROINDENTER DESCRIPTION

The microindentation measurements were carried out on a Nanotest 550 (Micro Materials Ltd., U.K.) provided with a Berkovich diamond indentation tip [14].

Chapter IV Mechanical characterization of silica aerogels

148

(1)

(2) (3)

(4)

Figure IV.1 Photography of Nanotest 550 (Micro Materials Ldt.)

The Nanotest apparatus consists in two pendulums (1), and (2), and an indenter (3) integrated in one platform (on the right of the photo). A second platform integrates the motor (4), which allowed moving the sample (on the left of the photo). This system is placed in an isolating chamber. The measured signal (load and penetration depth) is processed by a control unit connected to a computer. The computer allows to control the process of indentation, order the displacement of the motors and record the data. Figure IV.2 shows a schematic design of the system.

Scheme of Nanotest 550

•Non-destructive technique • Doesn’t need sample preparation• Dynamic microindentation • Extremely small applied loads • Diamond Berkovich tip • Maximum loads up to 500 mN • Maximum penetration up to 10 mm • Resolution: 0.1 nm, 0.1 mN

weight to balance the pendulum

Figure IV.2 Schematic design of Nanotest 550 system

Chapter IV Mechanical characterization of silica aerogels

149

The Nanotest consists in a diamond tip attached to a ceramic pendulum. When a current is applied along the coil, it is attracted towards the magnet moving the arm until the diamond tip penetrates on the sample surface. The displacement of the tip is measured using a variable capacitor. The limit stop defines which will be the maximum penetration for each type of sample. Continuous loads and penetrations are automatically recorded. 1.2 MECHANICAL CHARACTERIZATION

The microindentation system allows load and depth resolutions better than 1 N and 1 nm, respectively [11]. The maximum applied load was 1 mN or 0.5mN for the most elastic aerogels. These maximum loads led to maximum penetration depth in the range of 2 -7 m. Each loading-unloading cycle was repeated at least 10 times at different points in each sample to check the consistency of the results. Before measuring the unloading branch of the cycle, the hold time at maximum load was varied between 0 to 600 seconds to determine if aerogels were prone to stress relaxation or creep. Figure IV.3 illustrates a typical behavior for the sample A2. It can be seen from Figure IV.3 that there is creep penetration when the diamond tip is being held during some time at the maximum load.

8

Creep penetration ( m)

6

4

2

0

200

400

600

Creep time (s)

Figure IV.3 Penetration creep as a function of time for the A2 sample under maximum indentation load.

Chapter IV Mechanical characterization of silica aerogels

150

The creep rate strongly increases for creep times less than 200 s and becomes almost constant for longer creep times. This feature, if not considered, could lead to apparent higher hardness values [15].

P
hp he

h t: depth

total

penetration

hp: plastic depth he: elastic d epth Pmax: maximum load

P=0 Pmax

ht

Figure IV.4 Scheme of penetration of the Berkovich indenter in the sample surface.

Hardness values, H, were obtained from: H = Pmax/A (Eq. IV. 1) where Pmax is the maximum load and A is the projected indentation area for the maximum penetration depth. For a Berkovich diamond tip, A is given by the expression A=24.5h t2, where ht is the maximum penetration depth measured from the load-penetration curves (see Figure IV.4). Hardness values calculated by this method correspond to the total elasto-plastic deformation. It should be pointed out that this is not the most usual hardness definition, although is convenient in the case of very elastic materials, as aerogels are. Young‟s modulus, E, is obtained from the analysis of the unloading branch of the penetration vs. load curve by applying the method proposed by Oliver and Pharr [16] and using Sneddon‟s relationship:
dP dh 2E 1
2

A,

(Eq. IV. 2)

where is the Poisson‟s ratio ( =0.2 for a silica aerogel) [17,18] and dP/dh is obtained from a polynomial fit of the unloading curve (see Figure IV.5).

Chapter IV Mechanical characterization of silica aerogels

151

h
Unloading he ht hp Loading

Pmax

P

Figure IV.5 Hysteresis curve penetration depth versus load

Another interesting parameter that can be derived from these measurements is the elastic parameter, EP, which is similar to the one previously defined [19]. EP allows quantitative comparison of the elastic behavior of the samples. EP [15], is defined as:

EP

ht ht

hp

(Eq. IV. 3)

where ht is the total penetration depth during the indentation process and hp is the non-recovery depth (plastic depth) of the diamond tip inside the aerogel sample. 2. MECHANICAL PROPERTIES OF SILICA AEROGELS AS A FUNCTION OF DENSITY 2.1 SAMPLE PREPARATION In order to investigate the changes in the mechanical properties of the aerogels when varying the concentration of the silicon alkoxide in the initial sol a series of acetone aerogels (samples A1 to A4) was synthesized and characterized. Aerogels with different density, particle and pore size were obtained using different molar ratio of TMOS/acetone. The molar ratio of TMOS to water was always kept to four. Several volume ratios, v, defined as v

VTMOS , VTMOS Vacetone

were used. For v = 0.1, 0.2, 0.3 and 0.4, samples were labeled as A1, A2, A3 and A4 (chapter II). All the obtained aerogels were monolithic, in the form of cylindrical rods of 1cm diameter and lengths from 5 to 12 cm.

Chapter IV Mechanical characterization of silica aerogels

152

2.2

EFFECT OF THE ALKOXIDE CONCENTRATION

Figure IV.6 shows the load-penetration hysteresis curves for each sample „as measured‟ without any data smoothing or averaging.

7
Penetration depth( m)

6 5 4 3 2. 1 0 .2

A1
A1

A2 A3 A4

.4 .6 Load (mN )

.8

1

Figure IV.6 Hysteresis loading-unloading curve penetration depth versus load for the samples: A1 (+), A2 (∆), A3 (○) and A4 (□).

From those curves, we have obtained the three characteristic mechanical parameters, Hardness, H, Young‟s modulus, E, and elastic parameter, EP. The results are shown in Table IV.1, which also includes dilution and density for each sample preparation.

Table IV.1 Several volume ratios, v, were used to prepare the aerogel samples, their densities, , mean particle diameter, p , and mean pore diameter, 0 , are listed below together with their mechanical properties: Hardness, H, Young‟s modulus, E, and elastic parameter, EP. Standard deviations are shown in parenthesis and refer to the last digit. is related with Young‟s p / 0 modulus (see text). Sample label A1
p 0 p 0

v
0.1

H (MPa) 0.5 (1)

E 7.0 (9)

EP 78 (1)

(g/cm3) 0.08 (1)

(nm) 48 (7)

(nm) 110

(MPa) (%)

0.44

Chapter IV Mechanical characterization of silica aerogels

153

A2 A3 A4

0.2 0.3 0.4

0.15 (2) 0.23 (2) 0.26 (3)

55 (8) 70 (9) 88 (11)

60 30 20

0.92 2.3 4.4

2.4 (3) 4.8 (3) 5.7 (3)

50 (2) 153 (3) 346 (6)

30 (1) 10 (2) 6 (2)

It can be observed that as the dilution of the sol changes from 0.1 to 0.4, the density of the aerogels increases, so it does the hardness and Young‟s modulus. The EP values show a decrease, as the samples become more plastic. In order to analyze the evolution of Young‟s modulus, hardness and elastic parame ter as a function of the aerogel densities, the experimental points were fitted to power law functions. The resulting scaling exponent for the Young‟s modulus is agreement with other previous results reporting The scaling exponents for hardness, 0,4 respectively.
2
H

= 3.0

0.2 (E

). This is in

values within 2.5 and 3.8 [20, 21, 22, 23].
EP,

, and elastic parameter,

were 2.0

0.1 and -1.7

log(H (MPa))

1 0 -1 -3.0 6

H

-2.5

-2.0

-1.5
-3

-1.0

log(density (g/cm ))
log (E (MPa))

4 2 0 -3.0

E

-2.5

-2.0

-1.5

-1.0

log(density (g/cm-3))
1.0

EP

0.5

EP

0.0 0.05 0.10 0.15 0.20
-3

0.25

0.30

density (g/cm ))

Figure IV.7 Plots of Young‟s modulus (a), hardness (b) and EP (c) as a function of the aerogels density. Fittings are show n as solid

Chapter IV Mechanical characterization of silica aerogels

154

lines. The graphs of H and E are presented with the logarithm values of the data.

From the load-displacement curves of Figure IV.6 and the results given on Table IV.1 it can be observed that the aerogel samples investigated cover a wide range of mechanical responses. In particular, lowest density samples are almost completely elastic materials, this is seen because the loading and unloading branches do not show hysteresis, and they have a very low Young‟s modulus and high EP value. While for larger density aerogels deformation is almost entirely plastic and presents a much higher Young‟s modulus value, high modulus values could be expected in a plastic material because Young‟s modulus accounts solely for the elastic behavior of materials. Hardness and Young‟s modulus increase and EP decrease when increasing the density of the samples. Notice that hardness, as defined in Equation IV.1, is derived from the total elastoplastic penetration depth. If we had used the more common hardness definition, which involves only the plastic penetration depth, then we would have obtained an unrealistically high hardness value for the very elastic samples such as A1. 2.2.1 Relationship between silica aerogel microstructure and

mechanical properties

Chapter IV Mechanical characterization of silica aerogels

155

Microstructural observations were performed with a Leica 360 scanning electron microscope. The analysis of such micrographs allowed us to assess the particle size distribution for all the samples. Brunauer-Emmet-Teller (BET) porosity characterization of the aerogel samples was performed with a Micrometrics ASAP 2000 instrument. The BET surface area, SBET, was obtained from the adsorption isotherm of N2 at 77K. The mean pore diameter was calculated by in Table IV.3. a)
500 nm
0

= 4Vpore / SBET

where Vpore = (1/

aerogel

- 1/

Si lica

). The results are shown

Ø 48.5 nm =48nm
7.6 nm σ=7.6nm
p

20

40

60

80

100

b)

Mean sd

Ø 88,1 =88nm 11,4 σ=11nm

20

40

60

80

100

120

Figure IV.8 Scanning Electron Micrographs and particle size histograms for (a) A1 and (b) A4 aerogels. < p> mean particle diameter, and σ standard deviation, calculated by SEM histogram analysis.

SEM images (see Figures IV.8a) and b)), show that the A1 sample is built by smaller interconnected particles than the denser A4 sample. The mean particle diameter obtained,
p

,

for all samples were shown in Table IV.1. Assuming a similar fractal dimension between the sample series [24] Young‟s modulus is related to the degree of necking among contiguous particles. Necking contact increases with increasing particle size, with pore size, following E=k
0 p

, but its density decreases
p

. In fact, Young‟s modulus behaves linearly with the /
0

/

0

quotient,

p

, where

k=3.4MPa.

Chapter IV Mechanical characterization of silica aerogels

156

3.

INFLUENCE

OF

SOLVENT

AND

SUPERCRITICAL

DRYING

METHOD ON THE MECHANICAL PROPERTIES Silica gels were prepared by hydrolysis of TMOS under different conditions to evaluate the different responses of the aerogels to indentation. The A2 sample ( 0.15 g/cm3) was used as reference to compare the different syntheses conditions. A2 was compared in the previous section to an aerogel series with different densities (A1, A3, and A4). In this section, A2 sample will be compared with different drying procedure, A2 CO2, and with a sample with the similar density but different solvent, M. The solvent and the drying procedure used may cause variations in the aerogel hardness and Young‟s modulus. 3.1 EFFECT OF THE DRYING PROCEDURE

The first sample was dry with a conventional high temperature supercritical extraction of acetone while the second sample by exchanging the acetone for liquid carbon dioxide. The corresponding samples were labeled as A2 and A2 CO2 respectively. The microindentation responses of both aerogels can be compared in Figure IV.9.

Chapter IV Mechanical characterization of silica aerogels

157

6

Label

Penetration depth( m)

5

(g/cm3) (MPa) (MPa)

H

E

EP
(% )

A2

0.15

2.4 4.9

50 197

30 8

4

A2CO2 0.24

A2

3

A2 + CO2

2

1

0

0

.2

.4

.6

.8

1.0

Load (mN) Figure IV.9 Penetration depth versus load loading and unloading

curves for A2 (∆) and A2CO2 (●) samples.

In the case of differently dried samples, differences can be due to sample shrinkage during drying, which is more important in A2 CO2 samples than in A2 samples. It may be remarked that A2 CO2 gels were not washed in an ethanol bath and then the presence of remaining water in the gel solvent causes the noticeable shrinkage. As a result, the density of the A2 CO2 samples is higher and similar to that of A3 samples. Therefore, the A2 CO2 samples show a mechanical behavior similar to A3 samples. This shrinkage might have shortened the length of the bonding necks and increased connectivity between the primary silica particles, resulting in a slight increase in the density of the silica aerogels, and consequently an increase in hardness and Young‟s Modulus. It can be pointed out that A2 CO2 stills follow the scaling laws mentioned earlier in the previous section. It is found that the A2 sample presents a much more plastic response than the A2 CO2 sample, as it can be observed from the elastic recovery in Figure IV.9. Moreover, the A2CO2 is harder than A2 and presents a much higher Young‟s modulus (values are shown in Table IV.2).

Chapter IV Mechanical characterization of silica aerogels

158

Table IV.2 Several solvent volume ratios, v, and different solvent and drying procedures were used to prepare the aerogel samples, their densities are listed below together with their mechanical properties: Hardness, H, Young‟s modulus, E, and elastic parameter, EP. Standard deviations are shown in parenthesis and refer to the last digit. Sample A2 A3 M A2CO2 v 0.2 0.3 0.23 0.2 H (MPa) 2.4 (3) 4.8 (3) 1.4 (1) 4.9 (3) E (MPa) 50 (2) 153 (3) 29 (2) 197 (3) EP (%) 30 (1) 10 (2) 49 (1) 8 (1)

(g/cm3) 0.15 (2) 0.23 (2) 0.14 (1) 0.24 (3)

v = VTMOS / (VTMOS + Vsolvent) 3.2 EFFECT OF THE SOLVENT IN MECHANICAL PROPERTIES

To investigate the effect of the solvent, measurements were performed on two different solvent samples of similar density, acetone (A2) and methanol (M), see Table IV.2. When using methanol as a solvent, samples labeled as M, the molar ratio of the reactives we re: TMOS:CH3OH:H2O:NH4OH = 1:12.25:4:6.5·10-2 [25]. For the syntheses with acetone [26], no catalyst was used. Figure IV.10 shows the load-penetration curves obtained from A2 and M aerogels.
6

Penetration depth( m)

M
5

A2
4

3

2
Label
(g/cm3) (MPa) (MPa)

H

E

EP
(%)

1

M A2

0.14 0.15

1.4 2.4

29 50

49 30

0

0

.2

.4

.6

.8

1.0

Load (mN)

Figure IV.10 Penetration depth versus load loading and unloading curves for A2 (∆) and M (●) samples.

Chapter IV Mechanical characterization of silica aerogels

159

It can be observed that at equal maximum load, the maximum penetration depth is lower for A2 than for M aerogel. However, both samples show similar residual penetration depths after indenter unloading, so the M sample has a higher elasticity than the A2 sample while exhibiting the same density. Consequently, the elastic parameter values increase and the Young‟s modulus values decrease for the M sample. Thus, the A2 sample is harder than the M sample as can be seen Table IV.2. It is known that initial conditions for the TMOS sol-gel polymerization process, such as the solvent, have a pronounced influence on the microstructure of the aerogels [18]. The differences between elastic and plastic behavior in M and R samples must have their origin in the differences in the aerogel microstructure. Base catalysts such as NH 4OH, as in the M sample, lead to polymeric samples with high cross-linking therefore increasing the elasticity of the sample. Nevertheless, further structural and modeling efforts are needed for a complete understanding of these dependencies. In conclusion, the effects of the solvent, being methanol or acetone, on the silica aerogels have been studied. It was found that for samples with similar density values, the ones obtained using acetone have higher hardness and Young‟s modulus values than those obtained from methanol, but with less elastic recovery. Moreover, the effect of the drying process has been studied. It has been shown that the process with CO 2-acetone exchange causes a slight improvement in hardness and a relevant increase in the elastic modulus, mostly due to larger shrinking effects. This shrinkage might have shortened the length of the bonding necks and increased connectivity between the primary silica particles, resulting in a slight increase in the density, and consequently an increase in hardness and Young‟s Modulus.

4.

MICROMECHANICAL PROPERTIES OF CARBON-SILICA AEROGEL COMPOSITES 4.1 INTRODUCTION

To fit engineering needs, some potential aerogel applications may require materials with a higher elastic recovery than that inherent to pure silica aerogels. As will be shown, this can be done by incorporating activated carbon particles within the silica framework. Contrary to

Chapter IV Mechanical characterization of silica aerogels

160

conventional composites, in the resulting carbon-silica aerogel the most rigid phase corresponds to the silica aerogel matrix. Such systems are called inverted composites [7]. Carbon-silica aerogel composites may have a broad range of applications [27]. For instance, the thermal conductivity of silica aerogels can be reduced by absorbing infrared radiative component of the heat transfer. Carbon-loaded silica aerogels increase the thermal resistance due to carbon broad-band absorption. [28, 29].Another possible application for carbon-silica aerogel composites is as low temperature-black materials, for example, as opaque or lowreflectivity monoliths and coatings. Sometimes, the addition of carbon creates an electronic path through the aerogel network [30].Carbon-silica aerogel composites can be used as a catalyst support, which facilitates access of reagents to the electrocatalyst. 12 These examples illustrate the versatility of carbon-silica aerogel composites in a wide range of applications where their unique combination of mechanical, thermal, electrical, microstructural, and chemical properties have opened up new possibilities. 4.2 EFFECT OF THE CARBON ADDITION

It has been previously reported that by incorporating active carbon powder in the silica network, the aerogel elasticity increases [[31]. Carbon-silica aerogel composites were obtained by adding powdered activated carbon (supplied by Norit, Darco KB) to the sol in some A1 and A4 samples just before gelation. The colloidal mixture was stirred for some minutes, poured into cylindrical molds and covered with Parafilm. Activated carbon powders are produced from carbonized graphite-like plates, followed by the steam activation process where the carbonized material is reacted with steam at 1000 C. The carbon particle aggregates have a diameter ranging from 10 to 45 m. This carbon shows a tamped bulk density of 0.45g/cm3, high specific surface area (1500m2/g), and large elastic recovery. The mass fraction of carbon in the aerogel, x

mcarbon , was varied from 0 to 0.5. The A1 mcomposite
aerogel

carbon-silica samples were labeled as A1 c. In the composite A4 samples, the mass fraction of carbon, x

mcarbon , was 0.02, 0.15 and 0.5. Samples were accordingly labeled as C2, C15 and mcomposite
aerogel

C50, respectively. Supercritical extraction of the solvent took place in a high-temperature process. All aerogel samples obtained were monolithic, in the shape of 5 - to 12-cm-long cylindrical rods and 1cm in diameter. The apparent density was determined by accura tely weighing samples of well-defined dimensions. The final densities of carbon-silica aerogel

Chapter IV Mechanical characterization of silica aerogels

161

composites are significantly lower than those corresponding to conventional silica aerogels. The volume shrinkage,
V V gel Vaerogel V gel V gel

, produced during supercritical extraction was

determined by comparing the dimensions of the dry aerogels and the dimensions of the original gel. Shrinkage during drying decreases dramatically as the mass fraction of carbon increases. The cause of the lower densities is a consequence of the lower shrinkage observed for the aerogel composites with high carbon content.

Figure IV.11 Photography comparing a silica aerogel sample with a carbon-silica aerogel composite sample.

The most plastic aerogel sample (A4) and the most elastic sample (A1) have been used to analyze this effect. In both cases, identical samples but with added carbon showed a much more indentation elastic response than pure silica samples. This feature is illustrated in Figure IV.12, which shows the load vs. penetration depth curves for the A4 sample and for samples with carbon mass fractions of 0.02, 0.15 and 0.5. It can be seen that the addition of small amounts of activated carbon to pure silica aerogel induces great changes in the shape of the indentation curves. They change from curves characteristic of elastoplastic materials to those corresponding to highly elastic materials, as reported in [31]. This increase in elasticity results, in higher EP values of the composite aerogel samples, as it can be observed from the values listed in Table IV.3, which also includes the carbon mass fraction, the density and the shrinkage corresponding to all the listed samples. In particular, A1 and A1C are almost totally elastic materials, so they have a very low Young‟s modulus and a high EP value. It should also be noticed that experimental values of Young‟s modulus strongly decrease with slightly increasing carbon mass fraction (Table IV.3).

Chapter IV Mechanical characterization of silica aerogels

162

Table IV.3 Several carbon mass fractions were used to prepare the composite aerogel samples. Their densities, , and shrinkage, V/V are listed below together with their mechanical properties: Hardness, H, Young‟s modulus, E, and elastic parameter, EP. Standard deviations are shown in parenthesis and refer to the last digit. Sample label A4 C 02 C 15 C 50 A1 A1C Carbon percentage (mass %) 0 2 15 50 0 V/V (%) 34.3 29.8 19.8 7.2 H (MPa) 5.1 (2) 3.4 (2) 2.1 (2) 1.7 (2) 0.5 (1) 0.4(1) E (MPa) 190 (5) 52 (3) 28 (2) 23 (2) 7.0 (9) 9.0(8) EP (%) 6 (1) 29 (1) 45 (2) 54 (2) 78 (1) 89(1)

(g/cm3) 0.24 (1) 0.21 (2) 0.17 (2) 0.15 (3) 0.08 (1) 0.06(1)

The maximum applied load was 1 mN. For the A1 and A1 C samples, the maximum load was lowered to 0.5 mN due to the materials extreme softness. Figure IV.12 shows applied load vs. penetration depth indentation curves „as measured‟ for each sample for a loading–unloading cycle.

Chapter IV Mechanical characterization of silica aerogels

163

5

AC50 AC15

4

Penetration depth (m)

AC2
3

AC0

2

1

0 0,0 0,2 0,4 0,6 0,8 1,0

Load (mN)

Figure IV.12 Penetration depth versus load indentation curves for a pure SiO2 sample AC0 (▲) and composite aerogels with 2% of carbon, AC2 (●), 15% of carbon AC15 (◊), and 50% of carbon AC50 (□). The edge values are indicated for the non-recovery penetration depth, hp, the elastic penetration depth, he, and the total penetration depth, ht for the pure SiO2 sample (AC0).

It can be seen that the addition of small amounts of activated carbon to pure silica aerogel induces great changes in the shape of the indentation curves. They change from those characteristics of elastoplastic materials to those corresponding to highly elastic materials. From these curves we have calculated three mechanical parameters; Young‟s modulus, E, the elastic parameter, EP, and the hardness, H. Results are listed in Table IV.3, which also includes the carbon mass fraction, the density and the shrinkage corresponding to all the studied samples. Experimental values of Young‟s modulus strongly decrease with slightly increasing carbon mass fraction (Table IV.3). The dependence of the experimental Young‟s modulus on the carbon content of our aerogel composites will be discussed by using the regular model for composite materials [32, 33]. The mechanical properties of composite materials depend on the mechanical properties of the components, on the morphology of the phases and on the nature of the interface

Chapter IV Mechanical characterization of silica aerogels

164

between the phases. Figure IV.13 shows a schematic picture that illustrates two extreme phase distribution models that can be considered to estimate Young‟s modulus of composite materials.

200 180 160 140
(a) rigid phase elastic phase

E (MPa)

120 100 80 60 40 20 0 0,0 0.0 0,1 0.1 0,2 0.2 0,3 0.3 0,4 0.4 0,5 0.5 0,6 0.6 0,7 0.7 0,8 0.8 0,9 0.9 1,0 1.0
(b)

x

Figure IV.13 Composite Young‟s modulus values obtained for various mass fractions of silica, showing the upper and lower limits for the two extreme layered ideal composites. Hollow arrows indicate the direction of the external stress

The maximum possible value for the composite modulus is described by a linear combination of the Young‟s modulus for the filler, E filler, and the matrix, E matrix. This is expected when the two components of the composite are distributed in parallel, E ‖, in the way schematically shown in Figure IV.13(a). In this case, the Young‟s modulus value, E ‖, is described by equation (4) as a function of the carbon mass fraction, x, see Figure IV.13 [31].
E xE filler (1 x) Ematrix

(Eq. IV.4)

The lowest possible modulus for a composite material results when the two phases of the composite are connected in series Figure IV.13 (b). Then, the Young‟s modulus E described by equation (5). is

1 E

x E filler

1 x E matrix

(Eq. IV.5)

This model also predicts that when the composite is particulate, then the expected values for the Young‟s modulus will be close to the equation IV.5, but do not follow the exact

Chapter IV Mechanical characterization of silica aerogels

165

hyperbolic function. Experimental Young‟s modulus values listed in Table IV.3 are also included in Figure IV.12. It is found that the incorporation of small amounts of carbon into the silica aerogels causes a large decrease in the modulus of the composite. Modulus values for higher concentrations of carbon do not follow Equation IV.5, but lie between equations IV.4 and IV.5 as predicted for a particulate composite. The measured modulus values are closer to the lowest curve of Figure IV.12. We understand it in the following way: for low carbon concentration, the carbon particles could act as anchorage centers for silica branches and then be incorporated within the silica network. This may be the cause of the strong diminution in Young‟s modulus when a small amount of carbon is added. When the carbon mass fraction increases, the percentage of the carbon particles not incorporated into the silica network rises, forming a particulate composite with Young‟s modulus values that differ from the hyperbolic behavior of equation IV.5. The elastic parameter values listed in Table IV.3 allow us to quantify the improvement in the elastic response to indentation previously illustrated in Figure IV.11. In particular, the EP values are dramatically increased by incorporating low carbon amounts in the silica aerogel and they become saturated for higher carbon concentrations. A possible explanation for the important changes observed in the elastic behavior of the carbon silica aerogel composites is that the filler can also disrupt the cross-linking of the silica aerogel network and lead to a less rigid structure. This consequently reduces the brittle failure typical of fragile materials such as silica aerogels and thus, the indentation plastic deformation. The measured hardness values of carbon-silica composites show a slight decrease when carbon content increases (Table IV.3). These experimental hardness values are close to those previously reported for silica aerogels [15]. Hardness as a function of aerogel density can be fitted to a power law function: H with a scaling exponent = 2.3 0.1, very similar to the one expected for pure silica aerogels [15]. Therefore, hardness of the composite is mainly due to the silica phase and is much less affected by the addition of carbon than the elastic parameter or Young‟s modulus values are.

Chapter IV Mechanical characterization of silica aerogels

166

5.

VISCOELASTICITY FREQUENCIES

OF

SILICA

AEROGELS

AT

ULTRASONIC

This section is included for completeness and shows the measurements of viscoelastic properties using a technique based on the analysis of thickness resonance of air-surrounded aerogel plates at ultrasonic frequencies. The measurements and analysis of the results were performed by T. E. Gómez Álvarez-Arenas and F. R. Montero de Espinosa from the „Instituto de Acústica-CSIC‟ [34]. The aerogels samples were prepared at the ‟Institut de Ciència dels Materials de Barcelona‟. This technique allow us to measure the density, Young Modulus and Poisson ratio of the samples, these results can be compared to those ones obtained by microindentation. 5.1 INTRODUCTION

Specially designed air-coupled, high-sensitivity and broad-band piezoelectric transducers [35, 36, 37], operating in the frequency range of 0.3-2 MHz, were used in order to excite and sense the resonance by airborne ultrasonic waves. This technique allows us to obtain precise and simultaneous measurements of velocity and attenuation of longitudinal and shear waves in silica aerogels at different frequencies as well as aerogel density. From these results, it has been achieved a full characterization of the viscoelastic properties of silica aerogels [38,15], over a significant frequency range, i.e. to obtain complex-valued and frequency-dependent data for all the elastic constants. Piezoelectric transducers Aerogel plate air

Figure IV.14 Specially designed air-coupled, high-sensitivity and broad-band piezoelectric transducers.

The technique is based on a silica aerogel plate embedded in a continuum medium (air), which is insonificated by a broad-band airborne ultrasonic pulse. The frequency spectrum of the ultrasonic pulse comprises several eigenfrequencies of the plate [39]. Eigenvibrations of the aerogel plate excited by the incident wave are recorded and analyzed. The theoretical

Chapter IV Mechanical characterization of silica aerogels

167

approaches to this problem is to impose boundary conditions to stress and strains fields at the surfaces of the aerogel plate and solve the system of equations for field amplitudes [40]. By this procedure, overlapping resonance can be discerned. The viscoelastic nature of the silica aerogel plate is introduced into the theoretical analysis by means of the correspondence principle (i.e. introducing complex and frequency dependent elastic constants) [41]. The use of aerogels as acoustic impedance matching layers for air-coupled piezoelectric transducers in the kilohertz frequency range has previously been reported [42, 43, 44]. Operating over 0.5 MHz, air-coupled transducers could be used for particular applications that require airborne signals and high spatial resolution: non-destructive testing [45], medical applications [46], surface characterization [47], etc. Therefore, new techniques for generation and detection of airborne ultrasonic signals are under very active research (e.g. micromachined capacitive transducers) [48]. Recently, it has been analyzed the possibility of using aerogel matching layers for the frequency range of 0.5-2 MHz. [49]. The use of piezoceramics together with a stack of matching layers where the outer layer is made of aerogel may give rise to a transducer whose performance may be better to that achieved from other techniques. [50]. For this purpose, velocity and attenuation of ultrasonic waves in the aerogel must be accurately measured. While methods to determine ultrasonic longitudinal velocity are well established, attenuation data are limited. Attenuation was measured by Debye-Sears diffraction for the frequency range of 0.8-8 MHz [51]. At lower frequencies (20200 kHz) a reverberation method was used [52]. Experimental data about shear wave propagation are very limited. 5.2 EXPERIMENTAL SET-UP: AIR-COUPLED BROAD-BAND

PIEZOELECTRIC TRANSDUCERS The synthesis of the aerogel used in this work was described in more detail in chapter II (TE00AT page 49, 60, and 62.). The molar ratios between reagents were TEOS/EtOH/H 2O = 1/7/5 and 0.003M citric acid. The gel was washed several times in pure ethanol. The silica aerogel slab (2.4 cm diameter and 0.3 cm height) had a density of 0.160 g/cm3. Before the measurements the sample was placed in a vacuum chamber and heated to 100 ºC to remove any absorbed moisture A pair of specially designed air-coupled piezoelectric transducers facing each other was used for the experimental set-up. The Insertion Loss (IL) for the aerogel plate is defined as:
IL 20 log 10 Asample Aref

(Eq. IV.6)

Chapter IV Mechanical characterization of silica aerogels

168

where:
A sample is the amplitude of the FFT (Fast Fourier Transform) of recorded ultrasonic

waves with aerogel plate in between the transducers

A ref is the amplitude of the FFT of recorded ultrasonic waves without the aerogel.
In addition, the transmission coefficient, T, is defined by the ratio transmitted to incident energy fluxes:
T
12

A sample A ref

(Eq. IV.7)

Details of the technique can be found elsewhere [53, 54]. Two cases were analyzed: normal and oblique incidence. At normal incidence (angle of 19 ), shear waves are not generated in the aerogel. In this particular case, and following the quantum-mechanical theory of resonance scattering [55], a simple analytical expression for T can be derived:

T

1

1 4

~ 2 m 1 m sin 2 k l t

1

(Eq. IV.8)

where: m is the ratio between complex acoustic impedances of aerogel and air complex acoustic impedance. t is the thickness of the plate. ~ ~ k l is defined as kl kl i l aerogel, where:
k l is the wave vector,
l

cl

i

l

~ cl , the complex wave vector in the

the longitudinal wave attenuation,

c l the longitudinal phase-velocity

is the angular frequency
~ c l the complex longitudinal velocity of sound.

Resonance of the plate appear at maximum values of transmission coefficient, T, which take place at kt

n , n = 0, 1, 2… On the contrary, no simple analytical expression for T can be

derived for oblique incidence.

Chapter IV Mechanical characterization of silica aerogels

169

5.3

DETERMINATION OF THE VISCOELASTICITY OF SILICA AEROGELS AT ULTRASONIC FREQUENCIES. 5.3.1 Normal incidence

Figure IV.15 shows the measured insertion loss, IL (dots), for normal incidence in a frequency range from 0.3 to 1.3 MHz. Separation between resonance is almost constant and equal to 59 1 kHz. First order resonance might be located at 59 kHz and the first peak in Figure IV.15 (354.5 kHz) should then correspond to the sixth order peak (n=6).
-15
insertion loss (dB)

n=6
(a)

-25

59 KHz

-35

-45 0.3 0.5 0.7 0.9 frequency (MHz) 1.1 1.3

Figure IV.15 Insertion loss versus frequency for a silica aerogel plate. Dots: experimental measurements. Solid line: theoretical results. Normal incidence.

Longitudinal velocity, c l , longitudinal attenuation,

l

, and density,

are used as fitting

parameters to match the theoretical calculations of IL to the measured values. The results for the fitted IL (solid line) are compared with experimental values (dots) in Figure IV.16). Figure IV.16 shows the obtained values of c l and
l

at different resonance.

Chapter IV Mechanical characterization of silica aerogels

170

375
Longitudinal

335
wave Shear wave

attenuation (Np/m)

300 225 150 75 0 0.0 0.4

310

velocity (m/s)

285 260 235
Shear wave

210 185

0.8 1.2 frequency (MHz)

1.6

Figure IV.16 Attenuation versus frequency of longitudinal ( ) and shear () waves. Solid lines: power fitting. Velocity versus frequency of longitudinal () and shear (▲) waves. (50‟).

The density,

, obtained by IL fitting is 0.220 0.020 g/cm3. While longitudinal phase
l

velocity, c l , is rather constant (324 m/s), longitudinal attenuation, power law:
αl f αl 1 f y ,

follows a frequency (f)

(Eq. IV.9)
3.16 10 5 Np /(m.Hz y )

where: y = 1.1 0.05 and α l 1 techniques. Up to now, c l and

It is of interest to compare these measurements with results obtained from different
l

were also measured following a conventional “through

transmission” technique. High-frequency (1.4 MHz) and broad-band transducers were employed in order to be able to separate, in the time domain, the different echoes due to multiple reverberations within the sample [56]. Measured values at transducer center frequency (1.4 MHz) are: c l = (325 3) m/s and
l

= (210

20) Np/m. These results are

consistent with those obtained from the resonance technique. In addition, results obtained here are consistent with data reported by other authors. Attenuation data shown in References 10 and 11 for the frequency range 0-200 kHz and 2.58 MHz follow a linear frequency law with: 2.1 10
5

Np m.Hz

l1

1.2 10

4

Np . m.Hz

Chapter IV Mechanical characterization of silica aerogels

171

Measurements for different aerogel samples having density values close to 0.2 g/cm 3 provide values of c l in the range 200-500 m/s [57, 58]. 5.3.2 Oblique incidence Figure IV.17 shows the measured IL (dots) for oblique incidence (19º). Interferences due to the overlap of longitudinal and shear resonance are clearly appreciated.
-15

insertion loss (dB)

Interaction longitudinal share (b) waves

-25

-35

-45 0.3 0.5 0.7 0.9 frequency (MHz) 1.1 1.3

Figure IV.17 Insertion loss versus frequency for a silica aerogel plate. Dots: experimental measurements. Solid line: theoretical results for incidence angle of 19º.

Using the values of cl and

l

obtained in the analysis of IL for normal incidence, shear
t

wave phase-velocity ( c t ) and shear wave attenuation (

) were used as fitting parameters to

match theoretical calculations of IL to experimental values. The higher accuracy for
ct and
t

are obtained at frequencies were interferences between longitudinal and shear

resonance appear. The result for IL is shown in Figure IV.17 (solid line). Obtained results for ct and
t t

are shown in Figure IV.17. While c t is rather constant (197 m/s), results for

can be adjusted by a power law:
αt f
t1

fy,

where y

0.5 0.15,

t1

0.226 Np / m / Hz 0.5

(Eq. IV.10)
t

For frequencies higher than 0.9 MHz, the uncertainty in the determination of

becomes

very high. Therefore, the error in the determination of the y exponent is also very high. Using thinner samples and/or larger incidence angles might solve this problem.

Chapter IV Mechanical characterization of silica aerogels

172

Complex elastic constants and related viscoelastic parameters can be calculated from the analysis of the exponential curves. Results are gathered in Table IV.4. The complex shear modulus G is obtained from: G
~ ct 2 . The complex elastic modulus M

~ ~ is defined as: M=K+4/3G cl 2 , where K is the bulk modulus, and c t is the complex shear

wave velocity. E is the Young Modulus defined by E

9GK , with real values of the 3K G

same order as the ones found using microindentation [15]. Poisson coefficient, which is difficult to obtain from other techniques, is calculated from:
2r 1 , where r 2r 1

c t2 . c2 l

Table IV.4 Poisson coefficient, , and the three complex elastic modulus: complex shear modulus, G, shear loss, tan G , complex elastic modulus, M, and Young Modulus E are measured at different frequencies, f, from 0.44 MHz to 1.2 MHz.

f
(MHz) 0.44 0.63 0.82 1.0 1.2 0.214 0.209 0.207 0.208 0.204

G (MPa) 8.36+0.18i 8.49+0.15i 8.54+0.14i 8.54+0.14i 8.58+0.13i

ta n 1δG imag(G) real(G)

M (MPa) 22.98+0.32i 23.01+0.28i 23.01+0.31i 23.16+0.36i 23.09+0.38i

ta n 1δM imag(M ) real(M )

E (MPa) 20.30+0.38i 20.53+0.32i 20.60+0.31i 20.62+0.33i 20.67+0.32i

ta n 1δE imag(E) real(E)

0.0212 0.0179 0.0164 0.0166 0.0151

0.0140 0.0124 0.0132 0.0155 0.0165

0.0185 0.0158 0.0151 0.0162 0.0156

A detailed analysis of data shown in Table IV.4 reveals that none of the calculated elastic moduli follows the frequency dependence predicted by any of the simple and basic viscoelastic single relaxation models (Voigt and Maxwell). On the contrary, bearing in mind that attenuations follow a frequency power laws (Equations. IV.9 and IV.10), a possible alternative to single relaxation models could be a time causal model [59, 60]. The real value of E ranged from 20.3 to 20.7 Mpa, this values are of the same order as the ones found using microindentation where a sample with a density similar to that one (0.23g/cm3) was of 30Mpa (M aerogel). Moreover, Poisson ratio ranged from 0.204 to 2.214, this values confirms that one used in microindentation, =0.2. In some aspects, the behavior of the aerogel observed here resembles that of some well investigated materials. These similarities permit to gain an insight into the underlying physics. For example, the shear

Chapter IV Mechanical characterization of silica aerogels

173

modulus (G) and shear loss ( tan

G

) exhibit a similar behavior to those reported for some

kind of polymers. For such polymers, the interpretation given is based on non-local cooperative interactions of large molecules, which could also be applied for aerogels [60, 61]. Another interesting feature is provided by the fact that Q M

tan

1 M

cte

l

f .

This relationship has also been observed, for some kind of aerogels, at higher and lower frequencies [51, 52]. A similar behavior has been found in marine sediments (water-saturated and dry sediments). Theoretical predictions of
l

in fluid-filled porous media (as sediments)

are based on the interaction between the fluid in the pores and the solid skeleton. This provides a dependence of the attenuation with the frequency that varies at
f 2 , f or f 1 2 depending on the frequency range involved [62]. On the contrary,

experimental measurements over a wide frequency range suggest a linear frequency dependence for
l

. This is the object of a long lasting argument between experimentalists

and theoreticians [62]. To explain this experimental behavior, different sources of dissipation leading to an attenuation proportional to ƒ (e.g. friction at the contact area between particles of the frame) were introduced into the theoretical modeling. The understanding of sound attenuation in aerogels may benefit from this. In its turn, low-density aerogels exhibit
l

f 2 , and some authors consider that this behavior is due to the influence of the fluid in

the pores [51, 63].

6.

MECHANICAL CHARACTERIZATION CONCLUSIONS

In conclusion, the microindentation technique has proved to be a non-destructive, suitable method to assess the parameters that characterize the mechanical behavior of extremely porous materials such as aerogels, despite their brittleness and softness. Silica aerogels of different mechanical responses have been obtained by varying the initial parameters in the TMOS sol-gel polymerization process, such as alkoxide concentration, solvent, drying process, as well as the carbon addition. Creep effects are very important for these samples and should be taken into account during measurements and in the interpretation of the microindentation results. Initial conditions have a pronounced influence on the density of the aerogels and also on their microstructure, which is reflected by their mechanical behavior. The A-series samples show two different types of mechanical behaviors; the low-density aerogels are elastic, while the denser aerogels behave as elasto-plastic materials. Young‟s

Chapter IV Mechanical characterization of silica aerogels

174

modulus, hardness and the elastic parameter have been evaluated for these aerogel samples. It is shown that the evolution of the parameters describing the mechanical behavior as a function of the bulk density follows power-scaling laws. The evaluated exponents are 3.0, 2.0 and -3.2 for Young‟s modulus, hardness, and Elastic Parameter, respectively. The large dependency of Young‟s modulus on the density as well as the change from elastic to plastic behavior has its origin on the aerogel microstructure. Further structural and modelization efforts are needed to a deeper understanding of these dependencies. The effects of the solvent, being methanol or acetone, on the silica aerogels have also been studied. It was found that for samples with similar density values, the ones obtained using acetone have higher hardness and Young‟s modulus values than those obtained from methanol, but with less elastic recovery. Moreover, the effect of the drying process has been studied. It has been shown that the process with CO 2-acetone exchange causes a slight improvement in hardness and a relevant increase in the elastic modulus, mostly due to larger shrinking effects. From the results presented in the previous section, we conclude that the addition of small amounts of powdered carbon as filler in silica aerogels increases the elasticity of the composite and keeps the hardness similar to silica matrix values. It has been found that including small amounts of activated carbon inside the fragile silica network dramatically increases its elastic indentation recovery. This is reflected in the shape of the indentation curves as well as in the increase of the elastic parameter value, which evaluates the percentage of elasticity versus plasticity. Young‟s modulus values obtained for carbonreinforced aerogels show a similar variation to the carbon mass fraction as that predicted by a commonly used model for composite materials. The measured hardness values corresponding to the total elastoplastic deformation do not show such a prominent dependency on the carbon mass fraction as the elastic parameter and Young‟s modulus do and they are similar to those measured for the pure silica aerogel. Moreover, we present an experimental technique that do not require any sample machining to simultaneously measure velocity and attenuation of longitudinal and shear waves in aerogels. A fully viscoelastic characterization of the aerogel is obtained and a deeper insight on aerogel basic properties is gained.

Chapter IV Mechanical characterization of silica aerogels

175

7.

REFERENCES

13 M. F. Doerner, and W.D. Nix, „A method for interprating the data from depth-sensing indentation instruments‟, J. Mater. Res 1, 601 (1986). 14 J. Loubet, G. Georges, „Vickers indentation curves of elastoplastic materials‟ Microindentation Techniques in Material Science, P.J Blau and B. Lawn (Eds.) ASTM Philadelphia (1986) 72-89. 15 M. Moner-Girona, A. Roig, E. Molins, E. Martínez, and J. Esteve, Appl. Phys. Let. 75, 653 (1999) 16 W.C. Oliver, and G.M. Pharr, J. Mater. Res. 7, 1564 (1992). 17 Gross, G. Reichenauer, J. Fricke, J. Phys. D: Appl. Phys 21 (1988) 1447. 18 A.V. Rao, G.M. Pajonk, N.N. Parvathy,, J. Mat. Sci 29 (1994) 1807. 19 M. F. Doerner, and W.D. Nix, J. Mater. Res 1, 601 (1986). 20 R.W. Pekala, L.W.Hrubesh, T.M. Tillotson, C.T. Alviso, J.F. Poco, and J.D. Le May, Mat. Res. Soc. Symp. Proc. 207, 197 (1991). 21 T. Woignier, J. Phalippou, H. Hdach, and G.W. Scherer, Mat. Res. Soc. Symp. Proc. 180, 1087 (1990). 22 T. Woignier, and J. Phalippou, Rev. Phys. App 24, C4 179 (1989). 23 J. Gross, and J. Fricke, J. Non-Cryst. Solids 95/96,1197 (1987). 24 W. Schaefer, and K.D. Keefer, Phys. Rev. Lett. 56, 2199 (1986). 25 G.M. Pajonk, A.V. Rao, N.N. Parvathy, E. Elaloui , J. Mat. Sci 31 (1996) 5683 26 M. Pauthe, J. Phalippou J. Rev. Phys. App. 24 (1989) 215

1 K. Parmenter, and F. Milstein, J. Non-Cryst. Solids 223, 179 (1998). 2 J. Gross, G. Reichenauer, and J. Fricke, J. Phys. D 21, 1447 (1988). 3 M. Gronauer, A. Kadur, and J. Fricke in: J.Fricke (Ed), Aerogels, Springer, Berlin 167 (1986). 4 R.W. Pekala, L.W.Hrubesh, T.M. Tillotson, C.T. Alviso, J.F. Poco, and J.D. Le May, Mat. Res. Soc. Symp. Proc. 207, 197 (1991). 5 T. Woignier, J. Phalippou, H. Hdach, and G.W. Scherer, Mat. Res. Soc. Symp. Proc. 180, 1087 (1990). 6 T. Woignier, and J. Phalippou, Rev. Phys. App 24, C4 179 (1989). 7 L.E. Nielsen, and R.F. Landel, Mechanical properties of polymers and composite, (Marcel Decker Inc., New York, 1994), p. 392. 8 C.A. Rutiser, S. Komarneni, and R. Roy, Mat. Res. Soc. Symp. Proc. 371, 223 (1995). 9 A.Venkateswara Rao, G.M. Pajonk, B. Haranath, and P.B. Wagh, Microporous Materials 12, 63, (1997). 10 M. Gronauer, and J. Fricke, Acustica 59, 177 (1986). 11 J. Pethica, R. Hutching, and W.C. Oliver, „Hardness measurements at penetration depths as small as 20nm‟ Philos. Mag. A48, 593 (1983). 12 W.C. Oliver, R. Hutching and J. Pethica, „Measurements of hardness at indentation depths as low as 20nanomters‟ Microindentation Techniques in Material Science, P.J Blau and B. Lawn (Eds.) ASTM Philadelphia (1986) 90-108.

Chapter IV Mechanical characterization of silica aerogels

176

27 C.A. Morris, M.L. Anderson, R.M. Stroud, C.I. Merzbacher, and D.R. Rolison, Science 284, 622 (1999). 28 X. Lu, P. Wang, D. Büttner, U. Heinemann, O. Nilsson, J. Kuhn, and J. Fricke, High Temp. - High Press. 23, 431 (1991). 29 D. Lee, P. Stevens, S. Q. Zeng, and A. Hunt, J. Non-Cryst. Solids 186, 285 (1995). 30 Th. Rettelbach, J. Säuberlich, S. Koreder, and J. Fricke, J. Non-Cryst. Solids 186, 278 (1995). 31 M. F. Ashby, and D.R.H. Jones, Engineering Materials (Butterworth Heinemann, London, 1996), Vol 1, p. 63. 32 Z. Hashing, S. Shtrikman; J. Mech. Phys. Solids 10, 335 (1962). 33 Z. Hashing, S. Shtrikman; J. Mech. Phys. Solids 11, 127 (1963). 34 T. E. Gómez Álvarez, F. R. Montero, M. Moner-Girona, E. Rodríguez, A. Roig and E. MolinsViscoelasticity of silica aerogels at ultrasonic frequencies, Applied Physics Letters (accepted for publication). 35 . T.E. Gómez Álvarez-Arenas and F. Montero de Espinosa. Bol. Soc. Esp. Cerám. Vidrio 41(1), 16 (2002). 36 F. Montero, T. E. Gómez, A. Albareda, R. Pérez, J. A. Casals. 2000 IEEE Ultrasonics Symp. Proceedings, 1073, (2000). 37 S. P. Kelly, G. Hayward and T.E. Gómez. 2001 IEEE Ultrasonics Symp. Proceedings (2001). 38 Y. Xie, J. R. Beamish. Phys. Rev. B 57(6), 3406, (1998). 39 L. Flax, G. C. Gaunaurd and H. Überall. in Physical Acoustics vol. XV, edited by W. P.

Mason and R. N. Thurston (Academic Press, 1981). 40 L. M. Brekhovskikh. Waves in layered media (Academic Press, New York, 1960) 41 . D.R. Bland. The Theory of linear viscoelasticity (Pergamon Press, 1960). 42 R. Gerlach, O. Kraus, J. Fricke. J. of NonCryst. Solids 145, 227 (1992). 43 O. Kraus, R. Gerlach and J. Fricke, Ultrasonics 32 (3), 217 (1994). 44 V. Gibbiat, O. Lefeuvre, T. Woignier, J. Pelous, J. Phalippou. J. of Non-Cryst. Solids 186, 244 (1995). 45 S. P. Kelly, R. Farlow, G. Hayward. IEEE Trans. Ultrason., Ferroelect., Freq. Contr., 43(4), 581. (1996). 46 . J. P. Jones, D. Lee, M. Bardwaj, V. Vanderkam, B. Achauer. Acoustical Imaging. 23, 89, (1997). 47 T. E. Gómez y F. Montero. 2001 IEEE Ultrasonics Symposium Proceedings, (2001). 48 I. Ladabaum, B. T. Khuri-Yakub, D. Spoliansky, (1995). 49 T. E. Gómez, F. Montero, M. MonerGirona, E. Rodriguez, A. Roig, E. Molins, J.R. Rodríguez, S. Vargas, M. Esteves. 2001 IEEE Ultrasonics Symp Proceedings (Atlanta 7-10), (2001). 50 T.E. Gómez Álvarez-Arenas and F. Montero de Espinosa. Bol. Soc. Esp. Cerám. Vidrio 41(1), 16 (2002). 51 T. Schlief, J. Gross and J. Fricke J. NonCrys. Solids 145, 223, (1992). 52 A. Zimmerman, J. Gross and J. Fricke. J. Non-Cryst. Solids 186, 238 (1995). M.I. Haller. 1995 IEEE Ultrasonics Symposium Proceedings, 501

Chapter IV Mechanical characterization of silica aerogels

177

53 S. P. Kelly, G. Hayward and T.E. Gómez. 2001 IEEE Ultrasonics Symp. Proceedings (2001). 54 . T. E. Gómez, F. Montero, 2000 IEEE Ultrasonics Symp. Proceedings,1069 (2000). 55 L. Flax, G. C. Gaunaurd and H. Überall. in Physical Acoustics vol. XV, edited by W. P. Mason and R. N. Thurston (Academic Press, 1981). 56 W. Sachse and H. Y. Pao. J. Appl. Phys. 49 (8), 4320, (1978). 57 . J. Gross, J. Fricke J. Acoust. Soc. AM. 91(4), 2004, (1992). 58 J. Gross, G. Reichenauer and J. Fricke, J. Phys. D 21, 1447 (1988). 59 T. L. Szabo and J. Wu. J. Acoust. Soc. Am. 107 (5), 2437, (2000). 60 T. L. Szabo. J. Acoust. Soc. Am. 97 (1), 14, (1995). 61 J. D. Ferry. Viscoelastic properties of polymers (John Wiley & Sons, 1980). 62 A. C. Kibblewhite. J. Acoust. Soc. Am. 86 (2), 716, (1989). 63 J. Fricke and T. Tillotson. Thin Solid Films 297, 212 (1997).

Ch a pt er V

SILICA AEROGEL MICROPARTICLES

SECTION OUTLINE

1.

SOL-GEL 1.1. 1.2.

ROUTE

TO

DIRECT

FORMATION

OF

SILICA

AEROGEL

MICROPARTICLES USING SUPERCRITICAL ETHANOL/ACETONE........................ 181 ‘IN SITU’ PARTICLE PROCESSING .................................................................................. 182 AEROGEL MICROPARTICLE CHARACTERIZATION ................................................ 184 1.2.1 1.2.2 1.2.3 2. SOL-GEL 2.1. 2.2. Scanning Electron Microscopy ............................................................................185 Independent solutions .................................................................................. 189 Transmission Electron Microscopy ....................................................................190 Atomic Force Microscopy ..................................................................................... 191 ROUTE TO DIRECT FORMATION OF SILICA AEROGEL

MICROPARTICLES USING SUPERCRITICAL CARBON DIOXIDE ...............................195 ‘IN SITU’ LOW-TEMPERATURE MICROPARTICLES: TEOS, HCOOH, AND SUPERCRITICAL CO2 AS SOLVENT.................................................................................. 196 PRECURSOR DIRECTLY INJECTED IN CO2 SUPERCRITICAL CONDITIONS AT LOW TEMPERATURE ..................................................................................................... 198 2.2.1 2.2.2 2.3. 2.4. 3. 4. Injection of hydrolysis and precursor solution independently ......................199 Injection of sol ........................................................................................................ 203

IN SITU’ INJECTION IN LIQUID CO2............................................................................... 203 INJECTION OF PREPOLYMERIZED PRECURSOR IN SUPERCRITICAL CO2 ..... 205 CONCLUSIONS ...................................................................................................................... 208 REFERENCES ........................................................................................................................ 208

Chapter V Silica aerogel microparticles

180

This chapter focuses on the preparation of silica porous microspheres directly in the highpressure reactor. This process allows the use of supercritical fluids in manufacturing fine particles with high porosity. Different approaches were undertaken to obtain silica aerogel microparticles by this method and two routes were used depending on the supercritical fluid chosen. High temperature method when acetone or ethanol were used as solvents, and low temperature method if using carbon dioxide. Silica in the form of microspheres is a material of interest in several fields. The Stöber [1] method for the synthesis of nonporous silica spheres via the hydrolysis and condensation of tetralkoxysilane has been well recognized for producing particles with very narrow distributions. Moreover, several methods have been attempted for obtaining silica microparticles. These include nozzle-reactor systems (spray drying or pyrolysis) [2-4], and emulsion/phase separation techniques with sol-gel processing [1-2, 5-10]. Aerogel microspheres offer an attractive alternative for microparticle applications. In general, porous microparticles provides an advantage over nonporous materials when large surface areas can be an advantage. The resulting silica aerogel particles would exhibit much of the surface area characteristic of a silica particle, while maintaining the narrow size distribution of Stöber-type particles. Silica aerogel microparticles can be used for a range of applications, including: as additives for conventional foaming operations, controlled release agents, encapsulation of products, gas separations, advanced thermal and acoustic insulation, microelectronics, optics, catalysis, high surface-area adsorbents [2], and chromatography materials. The use of small (i.e., <5.0 μm) diameter particles in ultra -high pressure liquid chromatography provides both an increase in resolution and a decrease in analysis time over more traditional column packing materials [11-12]. Supercritical fluids have received considerable attention as solvents or reaction media for the processing of powders, particles, fibers and coatings [13-17], since they offer a combination of gas like properties (viscosity, diffusion coefficient) and liquid like properties (density). Moreover, the synthesis of aerogel microparticle process at low temperature uses supercritical carbon dioxide. CO 2 is an attractive medium because, is a non-toxic, non-flammable and

Chapter V Silica aerogel microparticles

181

inexpensive fluid with a low critical temperature. A simple and versatile method to obtain silica aerogel particles based on the hydrolysis and subsequent condensation of silicon alkoxides in several supercritical fluids is developed in this chapter. This microparticle production route reduces the number of steps of traditional microparticle sol-gel processing. The proposed method is based on two factors: the solvent power of the supercritical fluid and the sol-gel reaction under these specific conditions. Finally, efforts were aimed on understanding the relationship between the structure and the synthesis conditions of these types of materials, the particle formation mechanisms and on the conditions to tailor the particle morphology, size and porosity.

1.

SOL-GEL ROUTE TO DIRECT FORMATION OF SILICA AEROGEL MICROPARTICLES USING SUPERCRITICAL ETHANOL/ACETONE

In this section monodisperse, microspherical aerogel and fiber silica morphologies powders were produced inside an autoclave by sol-gel process by using supercritical ethanol or acetone as solvent. The influence of different synthesis parameters and the conditions of the synthesis media on the structure and morphology of the obtained aerogel silica particles were investigated.
Sol in process of gelification
Solvent at supercritical conditions Colloidal particles

Figure IV.1 Scheme of the silica aerogel particle production by performing the sol-gel process under supercritical conditions.

Particle size was mainly controlled by varying the relative amounts of alkoxysilane, water and acetone. Other important parameters in order to control the particle size are the relative time, t/tgelification, and the order of introducing the reactants in the autoclave. It has been observed that a relevant factor to control the particle morphology is the venting rate of the supercritical

Chapter V Silica aerogel microparticles

182

fluid. The morphology of the particles was characterized by electron microscopy (SEM and TEM) and Atomic Force Microscopy (AFM). Coulter technique was also used to account for the particle size distribution. In addition, BET surface area, pore volume and mean pore diameter, <
pore >BET

, of the particles were obtained from nitrogen sorption isotherms.

Reagent grade alkoxides and solvents were used without further purification. Reactions were carried out either in a specially designed high-pressure 300-ml cell or in a 2000-ml reactor. (See annex II: Facilities). The basic component of the system is a syringe pump that is able of pumping fluids inside the autoclave through a nozzle.
1.1 ‘IN SITU’ PARTICLE PROCESSING

The ‘in situ’ process consisted in the following steps: i) ii) iii) iv) A sol in a colloidal initial stage (containing acetone as a solvent, tetramethoxysilane as a precursor and water) was placed inside the reactor. The reactor was then driven above supercritical values of the acetone, P c = 47 Bar, Tc = 235 . The sol was solubilized in the supercritical acetone distributing it over the entire reactor leading to the formation of gel particles. Finally, after a remaining time the solvent was extracted from the pores of the gel particles at supercritical conditions. Two different experiments were tested: in the first experiment, a sol (formed by acetone as a solvent, tetramethoxysilane (TMOS) as a precursor and water) was placed inside the reactor: Samples A, B, and C, (See Table IV.1). In the second experiment, the alkoxide precursor, the solvent and water were introduced in two independent vessels. One with the hydrolysis solution (water dissolved in acetone) and the precursor solution (TMOS dissolved in acetone) in the other vessel: Sample D (See Table IV.2). Figure IV.2 shows a simplified scheme of the ‘in situ’ process for the two set-ups either as single vessel with containing the sol (1a path in Figure IV.2) or two independent solutions (1b path in Figure IV.2).

Chapter V Silica aerogel microparticles

183

autoclave

1a)
TM OS + acetone H2O + acetone

3)

Venting the autoclave

sol

silica particles

Samples A, B, C

Sample D

2)

a )

Acetone supercritical conditions

4)

b
supercritical fluid

)

Figure IV.2 Illustration of the synthesis scheme for aerogel porous silica spheres by 'in situ' process either with sol (1b path): sample D or with independent solutions (1a path): samples A, B, and C.

In all the experiments the v volume ratio, v

TMOS , was fixed at 0.05. This TMOS acetone

highly diluted sol was used to avoid the gelification of the sol before the supercritical conditions were reached. The hydrolysis parameter, h, is defined, as in previous chapters, as the molar ratio h
H 2O . The h value was varied from 2 to 8 in order to observe the TMOS

effect of water concentration in the morphology of the aerogel microparticles. The obtained samples were: A (h=2), B (h=4) and C (h=8).

Chapter V Silica aerogel microparticles

184

Table IV.1 Mean particle size obtained by varying the hydrolysis parameter, h. Sample A B C h 2 4 8 Mean Particle Size Distribution width 1.2 m 1.7 m 2.2 m 0.2 m 0.7 m 0.6 m

In a second set of the experiments the same ratio were reproduced but the solvent and water were placed in the reactor independently in two vessels, one with the hydrolysis solution (water + acetone) and in the other the precursor solution (TMOS + acetone), avoiding the premature gelification because the temperature effect. See process in Figure IV.2. A bimodal distribution in particle sizes was found as seen in Table IV.2.
Table IV.2 Mean particle size obtained by independent solutions and v volume ratio 0.05

a )
1.2

Sample D

h 4

Particle Size 630nm 1.2 m

AEROGEL MICROPARTICLE CHARACTERIZATION

Particles were collected and characterized by a Leica 360 Scanning Electronic Microscope (SEM), a JEM 100CX Transmission Electron Microscope (TEM), a Nanoscope III Digital Instruments Atomic Force Microscope (AFM), N2 adsorption-desorption (Micromeritics ASAP 2000 instrument), and He-pycnometry. In all the ‘in situ’ experiments, a white dry powder was uniformly distributed all over the walls and base of the reactor with a deposition thickness from 10 to 100 m depending on the initial parameters. No liquid was found, indicating a complete reaction of the initial reactives of the sol.

Chapter V Silica aerogel microparticles

185

=400nm =1.8 m Initial conditions

=2.2 m

=75nm

Figure IV.3 Several microparticles were collected depending on the initial conditions

An approximate value of the apparent density of the powder was obtained by measuring the mass of a known volume of powder. The apparent powder density was between 0.06g/cm 3 and 0.08g/cm3 depending on the initial parameters. The surface area of the particles was characterized by nitrogen absorption (Brunauer, Emmet and Teller method). The technique allows us to obtain the surface area of a material using the adsorption and desorption of an inert gas, usually nitrogen. Gas adsorption measurements reveal the microspheres to have surface areas from 400 to 600 m2/g, similar values to those found on their monolithic counterparts. By pycnometry technique, it was checked that the skeleton density has the same value to that of the silica (2.2 g/cm3) [18]. The particle surface microstructure was characterized by several microscopy techniques (SEM, TEM and AFM) and it is shown in the following sections. 1.2.1 Scanning Electron Microscopy

An example of a SEM micrograph from A experiment (h=2) is shown in Figure IV.4. The formation of two kinds of morphologies: interlinked fibers and isometric spherical particles are evidenced when a zoom is performed in this image (see Figure IV.5).

Chapter V Silica aerogel microparticles

186

100 m

Figure IV.4 Porous deposition of silica aerogel microparticles for A sample with 100 m of thickness.

As already mentioned, the type of morphology depends on the rate of depressurization a high venting rate implied the presence of interlinked fibbers.

7.5 m

750 nm

Figure IV.5 a. Referring to sample A: Scanning electron micrograph of aerogel spherical shape silica particles narrowly distributed in size, particle diameter between 0.50 and 2 m. b. Fiber-like structure with a diameter of 75 nm and a length of some microns.

Chapter V Silica aerogel microparticles

187

The mean particle diameter and the particle size distribution could be modified by changing the values of the h parameter. See from Figure IV.6) to 8). Table IV.1 shows the variation for the high temperature experiments of the mean particle diameter , and the width of the

distribution 2 , when the TMOS dilution in acetone was fixed at 0.05 and the hydrolysis parameter, h, was changed.

15

=1.2 m m 2 =0.2 m m
Gaussian f it (0.3-2.6 0.1) Mean SD Ar ea --------------------------------------------1,18293 0,24649 8,4838

10

5

0

0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6

Particle diameter ( m)
Figure IV.6 SEM micrograph and particle size distribution for sample A: v = 0.05, h=2.

2

30

=1.7 m m = 0.7 m
Gaussian f it Mean SD ----------------------1,676 0,359

20

10

0

0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6

Particle diameter ( m)
Figure IV.7 SEM micrograph of the spherical particles and its particle size distribution for sample B: v = 0.05, h=4.

Chapter V Silica aerogel microparticles

188

=2.2 m 2 = 0.6 m
40
Gaussian f it Mean S D -----------------------------2,176 0,309

30

20

10

0

0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8

Particle diameter ( m)
Figure IV.8 SEM micrograph and particle size distribution for Sample C. Where v = 0.05 and h=8.

The size of the collected particles was very sensitive to the water/alkoxide concentration ratio: the higher the ratio, the smaller the particles, maintaining the width of dispersion constant. The size distribution and mean size value were measured by Coulter in order to compare the results by those obtained by SEM. Figure IV.9a-b compares the Coulter technique and image analysis size distribution for A sample =0.05, h=2.
Mean particle diameter = 1.2 ± 0.4 m
6
8

Number particles (%)

Number particles (%)

5 4 3 2 1 0

Coulter Particle Distribution

6

SEM Particle Distribution

4

2

0,0

0,5 1,0 1,5 2,0 Particle diameter (um)

2,5

0,0

0,5 1,0 1,5 2,0 Particle diameter (um)

2,5

3,0

Figure IV.9 a) Coulter size distribution for A sample = 0.05, h=2.

Figure IV.9 b) SEM size distribution for A sample = 0.05, h=2.

Both techniques show a similar particle size distribution.

Chapter V Silica aerogel microparticles

189

Independent solutions In the case of independent solutions, sample D, a differentiated morphology was observed. This experiment allows us to observe the effect of water in the interlinkage of the microstructure. Two different structures were observed, one placed inside the water recipient, it is structured as a spider's web. This feature was formed by interlinkage of nanometric spheres giving place to a fibrilar structure (Figure IV.10).

Figure IV.10 Spider’s web with a fiber diameter of 60 nm collected from the recipient where initially the water was dissolved in acetone.

The second structure was found overall the reactor as a 'snow' powder formed by micrometric spheres, distributed as a bimodal function.

10

Gauss(2)

8

Peak Cent er Widt h Height ----------------------------------------------------------1 0,632 0,352 6,34 2 1,244 0,182 3,72 -------------------------------------------------------

=1.2 m =0.6 m 2 1=0.2 m 2 2=0.1 m
1 2

Nombr e par t ícules

6

4

2

0

0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6

Particle diameter
Figure IV.11 Bimodal particle size distribution for D sample.

Diàmet r e par t ícula (um)

( m)

Chapter V Silica aerogel microparticles

190

1.2.2

Transmission Electron Microscopy

The preparation method that was employed was by grounding a small amount of silica aerogel into a fine powder in a mortar. The powder was ultrasonically suspended in inert liquid (methyl alcohol) and the finest particles are selected after decantation. A droplet of the suspension is then put on the usual electron microscope copper grid. TEM analysis was useful as to visualize with more detail the contact region between the microparticles as can be seen in Figure IV.12, although the resolution was not good enough as to visualize the fine nanostructure of the microspheres.

250 nm

Figure IV.12 Sample A, TEM microphotograph shows the contact area between particles.

The degree of necking between particles was mainly related to the remaining time of the dispersed sol at supercritical conditions. Further studies should be undertaken in order to better determine this phenomena. 1.2.3 Atomic Force Microscopy

To visualize the roughness and microstructure of the particle’s surface an Atomic Force Microscope (AFM) in non-contact mode was used. The AFM probes the surface of a sample with a sharp tip, a couple of microns long and less than 100Å in diameter. The tip is located at the end of a cantilever that is 100 to 200µm long. Forces between the tip and the sample surface cause the cantilever to deflect. A detector measures the cantilever deflection as the tip is scanned over the sample, or the sample is scanned under the tip. The measured cantilever deflections allow a computer to generate a map of surface topography. AFM can be used to

Chapter V Silica aerogel microparticles

191

study insulators. Non-contact AFM is one of several vibrating cantilever techniques in which an AFM cantilever is vibrated near the surface of a sample. The spacing between the tip and the sample for non-contact AFM is on the order of tens to hundreds of angstroms. In noncontact mode, the system vibrates with amplitude of a few tens of angstroms for a stiff cantilever near its resonant frequency (typically from 100 to 400 kHz). Changes in the resonant frequency or vibration amplitude as the tip comes near the sample surface are detected. There exists a relationship between the resonant frequency of the cantilever and variations in sample topography. Thus, changes in the resonant frequency of a cantilever reflect changes in the tip-to-sample spacing so allows to image sample topography. In order to visualize the microstructure of the A particle’s surface an AFM was used. Before the observation the particles were dispersed. A small quantity of powder (0.5 mg) was dispersed in distilled water (50 ml) using ultrasounds (5 min). AFM was used in a high amplitude resonant mode (‘tapping’ mode). The scale rate was around 1Hz. Squared images were acquired by using a digitalization rate of 256 points per line. The set of AFM images (Figures IV.13, 14, and 15) show the process of the high-resolution images taken at the superior part of the curvature of the sphere. Figure IV.13 (14 m x 14 m) shows two localized microspheres.

Figure IV.13 AFM micrograph (14 m x 14 m) for A silica aerogel powder

These images are represented in dual mode. The left microphotography shows a height image (z range from 0 m to 3 m). At the right part is a phase image; therefore it is possible to obtain some differences in the material (in this case only from substrate to microparticle).

Chapter V Silica aerogel microparticles

192

When the feature is sharper than the tip, the shape of the tip will dominate the image, in these images this effect is reflected in the ‘shadow’ on the spheres.

Figure IV.14 Sample A, Surface of a microsphere by AFM. Lateral dimensions: 1 m x 1 m. The colored scale corresponds to vertical amplitude of 15 nm.

The images were taken at the upper part of the microsphere (2-3 m of diameter). Figure IV.14 (1 m x 1 m). Because many samples have features with steep sides, tip imaging is a common occurrence in images, in this case because the surface convexity the roughness is not clearly observed. A plane fitting was applied (Nanoscope III; Digital Instruments) on the data type images. The plane fit calculates a single polynomial of a selectable order for our selected image and subtracts it from the image. A second order has been used to correct the distortion. The image’s distortion was removed almost entirely reflecting ‘a flat surface’ A flatten portion of one particle were taken at the superior part of the curvature of one sphere as shown in Figure IV.15.

Chapter V Silica aerogel microparticles

193

Figure IV.15 Sample A, Surface of a microsphere by AFM. Lateral dimensions: (500nm x 500nm). The colored scale corresponds to vertical amplitude of 15 nm.

Figure IV.16 shows the roughness of the surface microspheres at high resolution (500nm x 500nm). The scale mark in z is of 0-15 nm. From those micrographs was possible to make the image treatment for the surface analysis and roughness study. Figure IV.16 shows the surface analysis study:

Figure IV.16 Micrographs of the microspheres surface by AFM: Roughness analysis.

It was observed that the surface of the microspheres had a micro-roughness only detectable using this technique. The z range controls the vertical range of the image, corresponding to the full extent of the color table and the scanning length of the 500 nm. It was also possible to observe the existence of interlinked particles of few nanometers of diameter (5-30 nm) and

Chapter V Silica aerogel microparticles

194

the presence of pores of few nanometers (5-50 nm) of diameter. This structure is very similar to that of an aerogel [19-20]. Using the AFM technique, with the ’contact mode’, a trial to calculate the density of the particle and determining if the spheres can be assimilated to an aerogel or xerogel was attempted. By the roughness analysis of the surface the Rms parameter can be obtained, it is defined by:
Rms z2 z i zi is la height in each point and z is the mean height value. In our sample
2

the value was of 1 nm. This value is considered micro-roughness, that was the reason that it was not observed neither by SEM nor TEM. Figure IV.17 shows the surface of the sphere in three dimensions that will help us for interpreting the obtained images.

Figure IV.17

Three-dimensional AFM micrograph.

Figure IV.18 shows the results of a cross-section analysis of one of the microspheres.

Chapter V Silica aerogel microparticles

195

Horitzontal distance: 20 nm Horitzontal distance: 50 nm

Figure IV.18 Sample A. Cross-section analysis of the surface of one microsphere by AFM. Lateral dimensions (500nmx500nm). The colored scale corresponds to vertical amplitude of 15nm.

2.

SOL-GEL ROUTE TO DIRECT FORMATION OF SILICA AEROGEL MICROPARTICLES USING SUPERCRITICAL CARBON DIOXIDE

Alternatively, a low-temperature synthesis was performed by using supercritical carbon dioxide as solvent and formic acid as condensation agent. In previous works, sol -gel reactions were directly performed in supercritical carbon dioxide as a reactive medium by using formic acid as condensation agent to obtain aerogel monoliths [21]. We named this approach as low temperature synthesis to differentiate it from the first method where it was needed to reach the critical temperature of the solvent >200ºC (ethanol) while the critical temperature of CO 2 is 32ºC. Four types of low temperature experiments were performed and are described in the four sections:

Chapter V Silica aerogel microparticles

196

Section 2.1: ‘In situ’ low-temperature microparticles. The metal-organic precursor and the hydrolysis solution (HCOOH) were placed inside the reactor in different ways either as a sol or as independent solutions. Section 2.2: Injection of precursor and hydrolysis solution at supercritical conditions. This approach consisted in injecting the precursor (TEOS/TMOS) and condensation solutions (formic acid) in supercritical CO 2, under several critical conditions. The injection of liquids was achieved through a very fine nozzle using a syringe pump. Section 2.3: Injection of precursor and hydrolysis solution in liquid CO 2: An alternative route to this one was to inject the reactive in liquid CO 2 and dissolving the remaining water and alcohol from the sol reaction in a continuous flow of liquid CO 2, then reach the CO 2 supercritical parameters and vent the autoclave. Section 2.4: Injection of prepolymerized precursor in supercritical CO 2. The prepolymerized reactive was inject in supercritical CO 2, then the temperature was reduced until liquid CO 2 and the remaining water and alcohol from the sol reaction were dissolved in a continuous flow of liquid CO 2, then reach the CO 2 supercritical parameters and vent the autoclave.
2.1 ‘IN SITU’ LOW-TEMPERATURE MICROPARTICLES: TEOS, HCOOH, AND SUPERCRITICAL CO 2 AS A SOLVENT

A process for making monolithic silica gels at low temperature is by reaction of tetralkoxy orthosilicates (TEOS), with a strong carboxylic acid (p.e HCOOH) [22]. In this process, the water does not need to be present as a reactant because the hydrolysis reaction is caused by the carboxylic acid. In that case, supercritical CO 2 can be used as solvent for the sol-gel reactions. The supercritical extraction of the silica gel is performed under supercritical CO 2 conditions (temperature and pressure of 31 C and 71 Bar, respectively). Figure IV.19 shows a sketch of an ‘in situ’ low-temperature process. The metal-organic precursor and the hydrolysis solution (HCOOH) were placed inside the reactor in different ways either as a sol or as independent solutions. Then, the temperature and pressure were raised over CO 2 supercritical conditions waiting a certain period of time. In this case, supercritical CO 2 was expected to dissolve the precursor and formic acid (formic acid is miscible in supercritical CO 2 and water is immiscible) leading to the formation of a fine and uniformly aerogel powder dispersed overall the reactor. Figure IV.19 shows a scheme of one of the ‘in situ’ low temperature microparticles processing.

Chapter V Silica aerogel microparticles

197

TMOS + EtOH

SCCO2
HCOOH

Figure IV.19 Sketch of an 'in situ’ low-temperature microparticle production process.

Several experiments were developed in order to optimize the quality of the silica aerogel microparticles. It is important to point out that these experiments were changed mainly by varying the following four parameters:
TABLE IV.3 Experimental parameters to microparticles by 'in-situ' low-temperature process obtain

a )

Parameter HCOOH/precursor ratio P and T of the reactor during the dissolving step P and T of the reactor during the drying step Time at supercritical conditions

Range From 1 up to 24 P from 90 to T from 40 to 200 bar 200 bar 55 C 55 C P from 90 to T from 40 to From 1 to 24 hours

Figure IV.20 shows an experiment where HCOOH/TMOS was fixed at four. This solution when is synthesized outside of the reactor gels in 4 hours.

Chapter V Silica aerogel microparticles

198

Figure IV.20 SEM micrograph of microparticles obtained by ‘in situ’ low-temperature process in two vessels, one containing EtOH+TEOS the second one with water+NH3+NH4F.

Again, as in the ‘in situ’ at high temperature process, two kinds of morphologies were collected, spherical particles and microfibers. In this case, the shape of the microparticles was not as defined as in the high temperature method. Moreover, the diameter of the fibers was much larger (a diameter of 750 nm and a length of 5 microns).
2.2 PRECURSOR DIRECTLY INJECTED IN CO2 SUPERCRITICAL

CONDITIONS AT LOW TEMPERATURE

Our approach for preparing aerogel powders at low temperature by direct injection of the precursor at CO 2 supercritical conditions mainly concerned the dissolution of the injected precursor and formic acid in supercritical CO 2 (the sol or the individual solutions), followed by the sol-gel process and drying under supercritical conditions. The injection of liquids was achieved through a very fine nozzle using a syringe pump. The reactor conditions were in the temperature range of 313-368 K and pressure range of 100-150 Bar. The contact time between precursor and hydrolysis solution at supercritical CO 2 conditions was varied from 1 to 24 hours and the duration of the pressure release in all the experiments was of 30 min.

Chapter V Silica aerogel microparticles

199

2.2.1

Injection of hydrolysis and precursor solutions independently

This section describes the results of the process for the processing of silica aerogel particles by the independent injection of the sol components in the reactor using supercritical CO 2 as solvent. To avoid clogging of the nozzles the TEOS was diluted in ethanol. Next figure shows the steps followed for one of the experimental procedures:
Injection of HCOOH and TEOS/TM OS in supercritical CO 2

HCOOH

SC-CO2

Step i) +ii)

TEOS

SC-CO2

Step iii)

Particles of SiO2

Step iv)+v)

Figure IV.21 Schematic design of the injection process. Step i) Drive the reactor at CO 2 supercritical conditions in order to obtain supercritical fluid before the injection of the sol. Step ii) Inject HCOOH in the reactor using a nozzle. It acts as hydrolysis reactive in the sol-gel reactions. Step iii) Injection of TEOS/TMOS. Step iv) Remaining certain time at supercritical conditions until gel microparticles were formed. Step v) Slow depressurization in order to avoid the damage of the aerogel microstructure

Several experiments were performed under different injected ratios of HCOOH/precursor. Figure IV.22 shows the SEM characterization for one of the processing particles process with HCOOH/TEOS=12.

Chapter V Silica aerogel microparticles

200

Figure IV.22 SEM micrograph obtained from the powder at low temperature process. Injection of TEOS and HCOOH with molar ratio=12. The injected TEOS was diluted in EtOH with vTEOS/vethano =1. Remaining 3 hour at 150Bar and 85 C.

The powder was formed by microspheres aggregates of spheres with diameters between 100nm and 1 micron. In this case, the particle size distribution was not as narrow as those obtained at high temperature. The resulting particles are less spherical in shape due to neck forming between two of more particles. In order to obtain better-defined shape microspheres by reducing the necking between particles, the HCOOH/precursor molar ratio was reduced from 12 to 6 and the remaining time at supercritical conditions was reduced from 3 hours to one hour. Next SEM micrograph shows a closer up of the particle powder collected under these last conditions.

Chapter V Silica aerogel microparticles

201

Figure IV.23 SEM micrograph obtained from the aerogel powder following a low temperature process. Injection of TMOS and HCOOH with 1/6 molar ratio and v TMOS/vacetone=1. Remaining 1 hour at 150Bar and 55 C

The microparticle had a better-defined spherical shape (smaller necking) but still a very wide size distribution, the particle size range from 100nm to 1 m. To better understand the process that occurs inside the reactor a cartoon is shown in Figure IV.24.
HCOOH CO2

EtOH

TEOS

Figure IV.24 Scheme of what happens inside the reactor while the formation of silica aerogel microparticles by injection at supercritical conditions.

Chapter V Silica aerogel microparticles

202

When the autoclave was full of CO 2 in supercritical conditions (marked in blue) the HCOOH (marked in yellow) was injected (volume of the autoclave is 2 liters). The amount of t he injected HCOOH was of the order of 10 ml; depending on the number of CO 2 molecules outnumber the HCOOH molecules by few order of magnitude. Then, each HCOOH molecule was surrounded by CO 2. Gel microparticles scattered all over the reaction. At supercritical conditions the gel porous was filled with supercritical CO 2, therefore no capillary forces collapsed the pores when the fluid was vented. In the reactor, there also were the molecules resulting from the reaction, water and alcohol in very small quantities marked in orange. 2.2.2 Injection of sol

Aerogel powder was obtained by a new approach injecting the sol at carbon dioxide supercritical conditions. It is important to remark that the sol was constituted by HCOOH since it is miscible in supercritical CO 2. Next figure shows a scheme of the aerogel powder processing by injection of a sol at supercritical conditions.

SC-CO2

P=150Bar T= 80C

Sol 50ml TEOS : EtOH : HCOOH 60ml : 60ml: 12ml
3 h at SC- CO2 conditions Depressurization 30min

SiO2 particl es

Figure IV.25 Scheme of ‘in situ’ injection of the sol in supercritical carbon dioxide

Next SEM images show interlinked microspheres with neck diameters between 100 and 500nm and particle diameters between 1 and 3 m.

Chapter V Silica aerogel microparticles

203

Figure IV.26 SEM image of the silica aerogel powder collected
with in jection of a sol with HCOOH/TEOS=5, and v TEOS/vEtOH =1. Remaining three hours at supercritical conditions 150Bar and 80 C.

The particles obtained by the injection of the sol did not show large differences with those obtained by the injection of the precursors separately. The later one presents the advantage that avoids the obstruction of the nozzle.
2.3 ‘IN SITU’ INJECTION IN LIQUID CO2

An alternative method to the ones injecting at CO 2 supercritical conditions (described in previous sections), was to inject the reactants in liquid CO 2 and dissolve the remained water and alcohols formed during the reactions by continuous flow of liquid CO 2. Then, reach the CO 2 critical parameters and after a given time, vent the autoclave. The experiment were performed following these steps: i) ii) iii) iv) v) vi) Preparation of the sol with variable HCOOH/TEOS ratios Reactor full with liquid CO 2, that acts as solvent media. Inject HCOOH in the reactor using one nozzle. Injection of TMOS by using a second nozzle. Increase of P, T until supercritical CO 2 conditions. Slow depressurization.

Chapter V Silica aerogel microparticles

204

Step ii) and iv) can be substituted by one injection step spraying directly the sol. Next figure shows the steps followed by an 'in situ’ injection in liquid CO 2 experiment. Step ii)
liquid CO2

Step v)
SC-CO2

Step iii)+iv)
Sol TEOS + HC OOH

Step vi)

Aerogel SiO2 microparticles

Figure IV.27 Scheme of the route pursued for the processing of
silica aerogel microparticles using liquid CO2 as solvent. Step ii) Reactor full with liquid CO2 . Step iii)+iv) Injection of the sol. Step v) autoclave under supercritical condit ions. Step vi) Vent the autoclave and the silica aerogel microparticles are collected.

Depending on the experimental concentration ratios of TEOS/HCOOH/SCCO 2, diverse particle agglomerations were obtained. Figure IV.28 show the SEM micrographs of aerogel microparticles collected when the injection of TEOS and HCOOH onto liquid carbon dioxide.

Chapter V Silica aerogel microparticles

205

Figure IV.28 Scanning electron micrograph of aerogel silica particles obtained drying at supercritical carbon dioxide at 45 C, 100 bar when injecting the reactive at liquid carbon dioxide: HCOOH/TEOS=6, and TEOS dissolved in ethanol at vTEOS /vEtOH =1.

In this picture, the neck forming between particles is evidenced compared to the method by injection at supercritical CO 2. A closer up of a broken neck allowed to observe the porous structure inside the microspheres. The shape of the particles was much better defined and the size distribution was very narrow. The particle size distribution is also narrow and, in general, by this method the mean particle size is smaller (<1 m) than in the previous explained one where the particles were between one and two microns.
2.4

INJECTION

OF

PREPOLYMERIZED

PRECURSOR

IN

SUPERCRITICAL CO 2 Finally, in order to obtain particles with larger surface area, prepolymerized reactive was injected in supercritical CO 2 After the injection of the sol, the temperature was reduced to 15 C maintaining the pressure at 100 Bar meaning that liquid CO 2 filled the reactor. The liquid CO 2 dissolved the remaining water and alcohol from the sol reaction. An exchange of liquid CO 2 was done in a continuous flow, until all the water and alcohol was substituted. Then the CO 2 supercritical parameters were reached and after a while the autoclave was vented.

Chapter V Silica aerogel microparticles

206

Step i)

Step iii)

Step ii)

Step iv)

Step v)

Figure IV.29 Scheme of silica aerogel microparticles at low temperature by the injection of prepolymerized precursor and by addition of liquid CO 2 exchange. Step i) Drive the reactor at CO 2 supercritical conditions in order to obtain supercritical fluid before the injection of the sol. Step ii) Injection of H5. Step iii) Filling the reactor with liquid CO 2. Step iv) Remaining certain time at supercritical conditions until gel microparticles were dried. Step v) Slow depressurization in order to avoid the damage of the aerogel microstructure.

Figure IV.30 shows some of the particles obtained following the above described process.

Chapter V Silica aerogel microparticles

207

Figure IV.30 Alkoxide precursor injected at supercritical CO 2. One hour at 45 C, 100Bar. 1 hour of CO 2 liquid exchange.

A more porous surface was observed by SEM compared to the previous injection methods. That may be caused by the CO 2 liquid - ethanol exchange process that facilitated to reduce the shrinkage of the solid skeleton in the gel microparticles. The size of the collected particles ranged from 200nm to 600nm. BET method was used to determine the surface area of those particles, SBET= 520 m2/g. It is a large value compare to that of pure silica (S BET =35 m2/g) but not very large compare to H5 aerogels (1000 m2/g).

Figure IV.31 Two-steps precursor injected at supercritical CO 2 One hour at 45C, 100Bar. 1hour CO 2 liquid exchange.

Chapter V Silica aerogel microparticles

208

4.

CONCLUSIONS

Reactions inside an autoclave open a whole range of possibilities for one step synthesis of microparticles. The sol was solubilized in supercritical acetone to obtain powders of small particles with narrow size distribution. Indeed, these microspheres syntheses were based on hydrolysis and condensation in the supercritical fluid. The size of the collected particles was very sensitive to the water/alkoxide concentration ratio: the higher the ratio, the smaller the particles. Moreover, small changes on the depressurization rates results on very differentiated morphologies, a slow and controlled venting of the autoclave leads to the formation of monodispersed particles, spherical in shape, and narrowly distributed in the range of 0.5 to 2 m, otherwise fiber-like structures are present. In the case of using supercritical carbon dioxide as a solvent, the resulting particles are less spherical in shape due to necking formation between two or more particles. The particle size distribution is also narrow and, in general, the mean particle size is smaller (<1 micron) than in the previously described method. Classical ways for obtaining aerogel particles involve high-temperature and high-pressure reactions. However there are other ways to obtain aerogel particles based on the use of supercritical CO 2 medium and a condensation agent sufficiently soluble in CO 2 (formic acid has been proved to be a suitable one). In this case, the working temperature is lower. Aerogel particle formation in the supercritical phase under the conditions employed is dependent on the solubility of the reactive. The most porous microparticles were obtained when using twosteps synthesis by injection of the precursors in CO 2 supercritical conditions and adding a solvent exchange step ethanol- liquid CO 2.

5.

REFERENCES
fabrication and applications (Material Research 3. 4. Society Proceedings, Pittsburg, 1995), p. 372 M. Nogami, J. Mater. Sci. 17, 2845 (1982). H. T. Blair, R.B. Mattews, Annual Meeting Abstracts. Am. Ceram. Soc. , 355 (1991)

1. W. Stöber, A. Fink, and E. Bohn, J. Colloid Interface Science 26, 62 (1968). 2. D. L. Wilcox, M. Berg, T. Bernat, D. Kellerman, J.K. Cochran, in Hollow and Solids Spheres Science and and Microspheres:

Technology Associated with their

Chapter V Silica aerogel microparticles
5. C. J. Brinker, and G. Scherer, in SolGel Science (Academic Press, New York, 1990). 6. A. Van Blaader, and A. P. M. Kentgens, J. Non-Cryst. Solids 149, 161 (1992). 7. J. G. Liu, D. L. Wilcox, J. Mater. Res. 10, 84 (1995). 8. K. J.Pekarek, J. S. Jacob, E. Mathiowitz, Nature 367, 258 (1994). 9. Unger, K., et al., US Patent No. 4,775,520 (1988) 10. Unger, K., Kaiser, C. German Patent DE 195 30 031 A1 11. MacNair, J.E., Patel, K.D., Jorgens, J.W. Anal. Chem., 71, 700 (1999) 12. MacNair, J.E., Lewis, K.C., Jorgens, J.W. Anal. Chem., 69, 983 (1997) 13. M. Barj, J.F. Bocquet, K. Chhor, and C. Pommier, J. Mater. Sci. 27, 2187 (1992). 14. K. Chhor, J.F. Bocquet, and C. Pommier, Mater. Chem. Phys. 32, 249 (1992).

209
15. X. Y . Zeng, Y. Arai, and T. Furuya, Trends Chem. Eng. 3, 205 (1996). 16. D. W. Matson, R. D. Smith, J. Am. Ceram. Soc. 72, 871 (1989). 17. P.G. Debenedetti, fluids, in 3·rd on International supercritical symposium

(Proceedings,

Strasburg, 1994), p. 213 18. N. Tohge, G.S. Moore, and J.D. Mackenzie, J. Non-Cryst. Solids 63, 95 (1984). 19. R. w. Stark, T. Drobek, M. Weth, J. Fricke, and W.M. Heckel, Ultramicroscopy 75, 161 (1998). 20. C. Marlière, F. Despetis, P. Etienne, T. Woignier, P. Dieudonné, and J. Phalippou, J. Non-Cryst. Solids 285, 148 (2001). 21. ‘Process for making inorganic gels’ Patent US5558849, issued 1996-0924 Sharp Kenneth G 22. D. A. Loy, E. M. Russick, S. A. Yamanaka, Chem. and 4, B.M. 749 Baugher, (1997). Mater

Ch a pt er VI

SILICA AEROGEL FILMS

SECTION OUTLINE
1. APPLICATIONS OF AEROGEL FILMS ...................................................................................... 212 1.1 1.2 1.3 1.4 1.5 2. ELECTRONIC.............................................................................................................................. 212 OPTICAL...................................................................................................................................... 213 THERMAL.................................................................................................................................... 214 A COUSTIC.................................................................................................................................... 214 ENVIRONMENT AND OTHERS................................................................................................. 214

SOL-GEL COATING METHODS .................................................................................................. 215 2.1 2.2 2.3 2.4 2.5 DIP COATING ............................................................................................................................. 215 SPIN COATING............................................................................................................................ 216 SPRAY COATING......................................................................................................................... 217 SURFACE TENSION COATING ................................................................................................. 217 SUBCRITICAL DRYING BY SURFACE DERIVATION................................................................. 217

3.

REFERENCE EXPERIMENTAL RESULTS ............................................................................. 217 3.1 DIP COATING ............................................................................................................................. 217 a) Low-Temperature dip coating .................................................................. 218 b) High-Temperature drying ........................................................................ 219 3.2 SPIN COATING............................................................................................................................ 221 a) Spin coating with High-Temperature drying .............................................. 222

4.

PROPOSED NEW METHODS: ‘IN SITU’ PREPARATION AT HIGH PRESSURE AND

INJECTION AT SUPERCRITICAL CONDITIONS ............................................................................. 224 4.1 ‘IN SITU ’ PREPARATION AT HIGH PRESSURE......................................................................... 224 4.1.1 4.1.2 4.2 227 5. 6. CONCLUSIONS .................................................................................................................................. 230 REFERENCES ..................................................................................................................................... 231 ‘In situ’ high temperature .......................................................................................... 225 ‘In Situ’ low temperature coating method ............................................................. 225

SPRAY COATING BY DIRECT INJECTION IN SUPERCRITICAL CO2 AT LOW TEMPERATURE

Chapter VI Silica aerogel films

212

Sol-gel processing has proved to be an important method for producing amorphous porous silica films. A variety of processing techniques has been developed to minimize shrinkage and prevent cracking of the films. One of the most successful methods is to avoid altogether the capillary forces by drying the gel at temperature and pressure above the critical point of the solvent. The resulting aerogel film retains most of the original volume of the wet gel and is potentially useful as a wide range of applications due to its low density, high surface area and low thermal conductivity. This chapter is organized in four sections. Section 1 summarizes some of the aerogel film applications. The most used techniques for obtaining films in the sol-gel processes and its most used characteristics are summarized in section 2. In addition, dip coating and spin coating were used as a pattern methods to be compared with the results from the „in-situ‟ method developed in our laboratory. Section 3 shows some of the silica aerogels films obtained by spin and dip coating methods. Section 4 shows the proposed „one-pot‟ methods to process silica aerogel films and the achieved experimental results. The acquired „Laboratory Scale Plant‟ provided the possibility to better rationalize the number of free parameters in the experiments and make simpler the realization of those „one-pot‟ tests.

1. section.

APPLICATIONS OF AEROGEL FILMS

The most used applications for aerogel film either in thick or thin type are described in this
1.1 ELECTRONIC

 Thick organic aerogel films ( 0.5mm) are formed by capillary fill, and then pyrolyzed to carbon aerogel films for use in aerocapacitors.  Thin aerogel films ( 2 m) are formed on silicon wafers to provide a low dielectric constant in integrated circuits. SiO 2 aerogel films are a promising material because it has a low dielectric constant due to its inherent high porosity that is controllable in the fabrication process. The dielectric constant for aerogels is around 2.0 and its value depends on the porosity. The basic technological trend in ultra large-scale integration of electronic circuits is the realization of higher speed devices with closer packing density, which results in a multilevel interconnection structure. Improving a chip's insulation is one way

Chapter VI Silica aerogel films

213

to avoid the problem. Good insulators let chip designers place interconnects close together without slowing down the electrical signals. Air, the perfect insulator, has a dielectric constant of 1.0 but it is not possible to hold chips together with air. Silicon dioxide, the material now used on most chips, rates at about four. Therefore, aerogel‟s dielectric constant may be as low as 2.5. The aerogel chip insulator could more than double computing speeds 1, 16 .

Figure VI. 1 Aerogel film as a chip insulator. 1.2 OPTICAL

 Thick aerogel films ( 0.2mm) are used as cover slips on solar cells and on optical fibers. A method for fabricating a lightweight solar cell 2 is provided by preparing a low density silica aerogel substrate at densities between 0.01-0.1 g/cm3, then a dielectric planarization layer of SiO 2 is applied to the substrate surface and one or more photovoltaic thin film layers are deposited on the planarization. These solar cells, with their low-density aerogel substrates, are much lighter than prior solar cells. This is advantageous in satellite applications since the solar array weight is substantial. Such lightweight solar cells of the invention also find further advantage on the ground, e.g. for solar-powered vehicles in which weight is a primary concern. Silica aerogel films are also used in optical fiber 3 . The problem to be solved is to enable transmission of more light at a larger light receiving angle by fixing a silica aerogel via a resin to the surface of a film-like base material. Thin aerogel films ( 30 m) are coated on the outside of glass laser pump tubes, on solar energy collectors 4 , and on thin film detectors as low mass optical coating. The aerogel acts as a refractive index match between the pump tube glass and air, to minimize reflection of internally generated light. Some thermal detector have an optical coating comprising an aerogel film with greater porosity than 80% 5 . An optional optical impedance matching layer may be deposited over the porous film.

Chapter VI Silica aerogel films

214

1.3

THERMAL

 Thick sheets ( 1mm) of silica aerogels are coated with thin film layers of metal, and then laminated together to form a super-insulating thermal heat shield block 6 . The aerogel layer may also contain infra-red (IR) opacifier and/or fibers. It is sandwiched between two films.  Thin aerogel films ( 25 m) have been formed on glass substrates for use in „cool‟ infrared (IR) detectors. The aerogel film serves as a thermal barrier to shield the IR detector elements from the heat radiated by the substrate materials 7 .
1.4 ACOUSTIC

 Thick aerogel films ( 0.5mm) are formed on the surface of ceramic transducers to serve as acoustic impedance matching layers 8-12 . Thin films of silica aerogel on silicon have acoustic waveguide properties. The large mismatch between the acoustic properties of the silica aerogel film and substrate in creates pronounced dispersion in the velocities and leads to unusual acoustic behavior: over a relatively large range of wavelengths, the group velocities of certain modes are less than 50 m/s-nearly ten times slower than the intrinsic velocities of the nanoporous silica and more than one hundred times slower than those of silicon. Acoustic impedance matching between a transducer and the irradiated medium can be achieved using quarterwave or impedance gradient layers 13-14 . SiO 2 aerogels are suitable materials for both purposes. To investigate matched transducers for air applications, sound intensity measurements were performed with and without aerogel quarterwave layer for different types of piezoceramic transducers. Ways to employ aerogel layers for the acoustic matching of piezoceramics are discussed.
1.5 ENVIRONMENT AND OTHERS

 Thick aerogel films ( 0.5mm) are formed on the surface a metal mesh matrix for getters in decontamination. A porous lightweight getter that collects particulate and molecular contaminates. Such composite getters are useful in decontamination in semiconductor manufacturing processes and storage and in decontaminating optical systems including a space-based telescope. In other embodiments, the getter can be mounted in air conducts to

Chapter VI Silica aerogel films

215

serve as a filter therefore, can be mounted in a photocopier for capturing of toner fog, it can be mounted in areas of semiconductor manufacturing for collecting contaminates 15 .

2.

SOL-GEL COATING METHODS

Some important applications require the aerogels to be as films. To do that, certain experimental details should be taken in account. Since there is a large surface area in contact with the atmosphere, the solvent evaporation rate should be slowed down. Thus, the coating is usually done in a saturated solvent vapor chamber. A second step is required to supercritcally dry the coating. Another important requirement is the substrate surface preparation previous to coating because gels do not stick well to unprepared surfaces and any kind of grease must be eliminated. Bonding to the surface is enhanced by etching the substrate surface with a mild alkaline solution and then raising it with an alcohol immediately prior to film deposition. Next subsections summarize the most used techniques for obtaining silica aerogel films in the sol-gel processes (2.1 to 2.5) together with two new methods developed in our group. These „one-pot‟ techniques present the great advantage to perform the whole process inside the autoclave. In addition, dip and spin coating were used as pattern methods to compare the results with those of the „one-pot‟ methods.
2.1 DIP COATING

Substrates are dipped into a precursor solution and slowly withdrawn from it. They are then placed edgewise and vertical in a holder that is located within the solvent vapor sat urated chamber. The disadvantage of this method is the low homogeneity of the obtained films, since the solvent is evaporating and gravidity draining the film acquires a wedge-like shape. The main characteristics of dip coating films are: i) thickness lower than few microns depending on the viscosity of the precursor and withdrawal rate. ii) Gelation time of the film took only a few minutes because the rapid evaporation of the solvent. iii) The coated substrates can be either Pyrex glass or silicon wafers. iv) The coated films are immersed in the corresponding solvent until ready for supercritical drying. Some of the resulting films are shown in section 3.

Chapter VI Silica aerogel films

216

FigureVI. 2 shows the main steps of the dip-coating process.

Figure VI. 2 Stages of the dip coating process: (a-e) batch; (f)
continuous. (17)

2.2

SPIN COATING

The most used procedure to form gel films is by dropping the precursor solution onto a spinning substrate while its spin rate increases. Spinner is then turned off and stopped with a brake (causing minimal loss of solvent during gelation). The main problem is the low homogeneity of the films and the need to work in a solvent saturated chamber, also it is necessary to find the balance between the two main forces, centrifugal and viscous (friction). The main characteristics of spin coating films are: i) thickness lower than two microns. ii) The gel is formed within a few minutes. iii) The substrates used are silicon wafers up to 1 cm of diameter. iv) The substrate coated with the gel film is immersed in solvent to age until the supercritical drying.

Figure VI. 3 Stages of the spin-coating process 17 .

Chapter VI Silica aerogel films

217

Different type of catalyst and several TEOS/EtOH ratios were attempted with the purpose of processing spin-coating films with a wide variety of porosity. Some of the results are shown in section 3.
2.3 SPRAY COATING

Usually this technique is used to coat thicker single layer. films as thick as 80

m In this

method, the solution precursor is directly sprayed onto the substrate (supported in a vertical position within the chamber). Excess solution drains by gravity leaving a thick film that gels within a few minutes. The surface of the gel is smooth and continuous. In the same manner that in the previously mentioned methods, the coated substrate is immersed in solvent after gelation until ready for supercritical drying.
2.4 SURFACE TENSION COATING

In this coating method, surface tension is used to draw the liquid onto the solid surfaces. A feature is made by forming a space between the substrate to be coated and another flat surface (treated to prevent bonding to the gel so that should be removable after drying process). Liquid precursor fills the available volume by capillarity when the element is dipped into the solution. The spacers are used to separate the substrates by the desired film thickness. Common film thicknesses are from 2 to 50 m.
2.5 SUBCRITICAL DRYING BY SURFACE DERIVATION

In this technique, aerogels are prepared by dip-coating at ambient pressure 18-19 without needing of supercritical drying. To achieve that, surface groups (organosilyl-terminated surfaces) are added to the gel, making drying shrinkage reversible: as the solvent is withdrawn, the gel springs back to a porous state. Final pore volume of the ambient pressure aerogel is a result of competing effects: the capillary stress induced collapse, and condensation /polymerization reactions which tend to stiffen the matrix resisting the collapse. The surface organic groups reduce capillary stresses due to contact angle modification and offer resistance to pore collapse. 3. REFERENCE EXPERIMENTAL RESULTS
3.1 DIP COATING

This technique has been used as a guide to compare with the „one-pot‟ experiments. Film thicknesses were of few microns depending on the initial molar ratios of the precursor sol.

Chapter VI Silica aerogel films

218

The gel film can be supercritically dried at CO 2 conditions (Section 3.1.a) or under the supercritical conditions of the gel solvent (Section 3.1.b). a) Low-Temperature dip coating A low temperature test comparing dip coating and „in situ method‟ (see section 4) has been performed under the same supercritical drying experiment. The sol-gel synthesis is the same for the two type of coating process: equivalent molar ratio, TEOS/EtOH/H2O=1/12.6/34.7 and equivalent catalyst concentration (citric acid 0.03M). Acid catalyst has been used because in acid conditions the contact surfaces of necks in the gel increases and may facilitate the film formation.

In situ +Dip coating SCCO 2
2mlTEOS+20mlEtOH 2mlTEOS+20ml EtOH 1ml H O+ 2 catalitzador ac cítric

Dip coated substrate

Figure VI. 4 Scheme of co mparat ive experiment, the d ip coated
samples were dried under the same experimental conditions that the ‘low temperature’ coated samples.

In the case of dip-coating, the sol is prepared outside of the reactor and the substrates are dipped in the sol before gelling. They are immediately placed in a saturated atmosphere avoiding the evaporation of the solvent. For the in situ process, the two independent solutions were placed inside the autoclave. When the substrates were ready for the supercritical extraction P and T were increased until supercritical CO 2 conditions 150bar (Pc=73bar) and 80 C (Tc=31 C). The autoclave remains 5 hours under these conditions. In this step is when the sol-gel process occurs; in addition, some longer time was required to age the film. Figure VI.5 shows the inhomogeneous but comparable films that were obtained by the dip-coating and on the „in situ‟ method.

Chapter VI Silica aerogel films

219

Figure VI. 5 SEM of the inhomogeneous films, dip coating at the left
and ‘in situ’ experiment at the right.

It should be remarked that the surfaces of the substrates were untreated so the homogeneity of the films could be improved making a surface treatment on the substrates. Comparing both experimental results, the morphology of the films seems to be very similar indicating that in the „in situ‟ method the sol-gel process has been preceded in a similar way than for the classical method. b) High-Temperature drying In order to optimize the synthesis parameters of the aerogels films several dip-coating tests have been attempted. The sol-gel dip coatings following a high temperature route were dried under supercritical ethanol conditions at 100bar (Pc=63bar) and 255 C (Tc=235 C). The film morphology is modified by varying the aging time of the gel films that remains under saturated atmosphere conditions. Figure VI.6 shows some of the experiments when using a sol-gel process with a very short gelation time (few minutes). The reactive ratios are TMOS/MetOH/H2O/NH4OH=1/12/4/6,5.10-4. Several types of morphologies were produced by changing the aging times under saturated solvent (1 or 2 minutes).

Chapter VI Silica aerogel films

220

Figure VI.6 shows four SEM images obtained in two different aging times (one and two minutes) and in different saturated conditions, left side for non-saturated and right side for methanol saturated atmosphere.

a)

b)

c)

d)

Figure VI. 6

Dip coating silica aerogels with reactives ratios of

TMOS/MetOH/H2 O/NH4 OH=1/12/4/6,5.10-4 . Figure VI.a) 1 min of aging at room conditions. Figure VI.b) 1 min of aging under methanol saturated atmosphere Figure VI.c) 2 min aging under room conditions Figure VI.d) 2 min aging under methanol saturated atmosphere.

It can be observed that in the two experiments without saturated atmosphere (a and c) small particles have been formed on the film surface. The presence of particles increases when increasing the aging time. On the other side, in presence of saturated atmosphere no particles are found (b and d). The films are more homogeneous and without cracks. Figures VI.7 and 8 show a detail of the porous microstructure of the aerogel coating under different aging time, one and two minutes, respectively.

Chapter VI Silica aerogel films

221

Figure VI. 7 Dip-coated substrate 1 min o f aging time in methanol Figure VI. 8 Dip-coated substrate 2 min o f aging time in methanol

When the aging time is increased, the structure becomes more colloidal and less polymeric. The film morphology seems to be more porous when decreasing aging time.
3.2 SPIN COATING

This technique has also been used in order to optimize the sol-gel procedure for film formation and to use the obtained films as evaluation of the quality of the „in situ‟ experiments. A wide study has been performed using different catalysts and different ratio of TEOS/ethanol. The film thickness obtained by this process is usually lower than 2 m. The

Chapter VI Silica aerogel films

222

drying procedure has been performed at solvent supercritical conditions (section 3.2.a) and with CO 2 liquid exchange (section 3.2.b). a) Spin coating with High-Temperature drying In order to optimize the synthesis parameters of the aerogels films several spin-coating experiments have been tested. The sol-gel spin coatings following a high temperature route were dried under supercritical ethanol conditions at 100bar (Pc=63bar) and 255 C (Tc=235 C). The reactive ratios in the
-4

methanol

gel

spin

coating

are

TMOS/MetOH/H2O/NH4OH=1/12/4/6,5.10 . The film morphology and coating thickness is modified by varying the aging time of the coated substrates that remains under saturated atmosphere conditions. Figure VI.9 shows four SEM images for one of the experiments when using a sol-gel process with a very short gelation time (few minutes). The reactive ratios are TMOS/MetOH/H2O/NH4OH=1/12/4/6,5.10 -4.

Chapter VI Silica aerogel films

223

a)

b)

c)
Figure VI. 9

d)
a) An homogeneous film is observed with particles deposited over the coating. Figure VI.b) shows a closer up of those particles. In Figure VI.c) shows a cross -section of the film. It is possible to observe that the thickness of the spin coating is of the order of 2 m. The film shows some cracks as observed in Figure VI.d ).

Since the films are so thin, the gelification speed is accelerated because evaporation rate is high. Then special attention must be taken to avoid the premature drying of the films at ambient conditions. In view of the fact that in this experiment it was not possible to work under a completed saturated atmosphere the coating presented some cracks (Figure VI.9b). The microstructure of the spin-coating films was similar to that obtained by „one-pot‟ method.

Chapter VI Silica aerogel films

224

4.

PROPOSED NEW METHODS: ‘IN SITU’ PREPARATION AT HIGH PRESSURE AND INJECTION AT SUPERCRITICAL CONDITIONS

A new technique based on supercritical fluid technology for the production and processing of aerogel film has been developed in our group. Two alternative methods are shown. „In situ‟ preparation will be described in section 4.1 and „spray in supercritical CO 2 method‟ in section 4.2.
4.1 ‘IN SITU’ PREPARATION AT HIGH PRESSURE

A substrate was placed in the autoclave directly over the recipient containing a diluted sol, which was previously prepared out of the reactor. As a second option, the subst rate was placed over two independent vessels containing the sol-gel solutions: the precursor solution (precursor dissolved by the solvent) and the water solution (water and in some cases a catalyst). The method consisted of four main steps:
i)

The substrates -previously treated to enhance adherence-, the precursor, the solvent, and some water were introduced in the autoclave before sol gellifies. See Figure VI.10.

ii)

The reactor was driven above solvent supercritical values. At supercritical conditions, the sol components (the metal-organic precursor, the solvent and water) were dragged by the supercritical fluid and the components were distributed over the entire reactor.

iii) iv)

The sol gellifies and then, temperature is increased above the supercritical value. Finally, the solvent is extracted under supercritical conditions of the solvent.
substrate sol in process of gelification solvent supercritical conditions

sol

Figure VI. 10 ‘In situ’ preparation at h igh pressure: The substrate is
placed over the recipient containing the sol that is dragged by the supercritical flu id and deposited on the substrate surface.

Chapter VI Silica aerogel films

225

Some examples will be more extensively explained, in section 4.1.1 when using ethanol in supercritical conditions and section 4.1.2 for supercritical CO 2. 4.1.1 ‘In situ’ high temperature

Some experiments were performed placing two vessels inside the autoclave one with the dissolved precursor in ethanol solution and the other one with hydrolyzing solution, and then the autoclave was driven until supercritical ethanol conditions following the above described method. In all the attempted high temperature tests a white powder was found spread over the inside walls of the autoclave vessel (see Chapter V: Silica aerogel particles). For that reason, further studies were needed in order to improve the „in situ‟ method. To get a better route two changes were proposed. The first change was to vary the sol-gel conditions by varying the TEOS/EtOH/H2O ratios with the intention to increase the contact of the neck surfaces between particles leading to film morphology. The second change is to cool the substrate whiles remaining at supercritical conditions (during step iii) allowing the condensation of droplets on the surface. 4.1.2 ‘In Situ’ low temperature coating method

Aerogels films were obtained at low temperature (without needing to use water) by using CO 2 as solvent in the synthesis of the gels (see more details of the synthesis on section 2.1.b). As an example, Figure VI.11 illustrates one scheme of these experiments.

Chapter VI Silica aerogel films

226

A

B

Silica aerogel

C

Figure VI. 11

‘In situ’ Low-T experiment. (A) The precursor and the

hydrolysis solution were placed inside the autoclave as independent solutions placing two vessels. The first vessel contains the precursor solution (TEOS dissolved in ethanol) and the second vessel contains the hydrolysis solution (HCOOH dissolved in ethanol). (B) Then, the two solutions were dragged at low temperature by supercritical CO 2 . (C) After a while, the sol gellify and supercritical CO2 extraction was processed.

The autoclave was leaded to supercritical CO 2 (200Bar, 80 C) during 24 hours. The experiment failed, since it was observed that the amount of the liquid in both vessels diminished but no coating was obtained. Instead, few particles were found on the substrate surface (described in Chapter V: Silica aerogel particles). In order to optimize the film formation a series of „in situ‟ low temperature experiments were tried changing the following parameters: -Ratio of HCOOH/precursor. -Pressure and temperature of the supercritical fluid. -Time of permanence in supercritical conditions.

Chapter VI Silica aerogel films

227

One of the experiments performed trying to improve the results, was decreasing the TEOS concentration in ethanol (EtOH/TEOS =12) and the substrates were treated by an alkaline solution (NaOH) and dipped in a solution with water and acid catalyst (1M HF). The idea is to avoid the formation of particles by using the immiscibility of water in CO 2. In this case, a thick porous film was obtained on the substrate.
4.2 SPRAY COATING BY DIRECT INJECTION IN SUPERCRITICAL CO2 AT LOW TEMPERATURE

A new initiative was seek to obtain silica aerogel films in a „one-pot‟ process. The idea was to spray the sol-gel reactives directly in the autoclave at supercritical conditions. This method was based on the injection (by using a nozzle) of the precursor (TEOS or TMOS dissolved in EtOH) at supercritical CO 2 conditions. After that, the injected precursor reacts with the HCOOH that covers the substrate, in these reactions the supercritical CO 2 acts as the solvent of the sol. Subsequently, after the gelification of the sol, the supercritical extraction of the solvent from the gel film was performed on supercritical CO 2 conditions (temperature and pressure of 31 C and 71 bar, respectively). As a final result, a silica aerogel film was achieved at low-temperature without the presence of water. Figure VI.12 shows the scheme of the experiments for the injection of TEOS (at supercritical CO 2) over a substrate covered with HCOOH. The scheme exemplifies two different routes marked as 1) and 2) corresponding to two different ratios of the injected solutions.

Chapter VI Silica aerogel films

228

Figure VI. 12 Injection of TEOS dissolved in EtOH (at supercritical
CO2 conditions) over a HCOOH covered substrate. For process 1), the mo lar rat io was HCOOH/TEOS=6 and the volume ratio was v EtOH /v TEOS=10. For p rocess 2), the molar rat io was HCOOH/TEOS=12 and the volume ratio was v EtOH /v TEOS=1.

For process 1), the molar ratio was HCOOH/TEOS=6 and the volume ratio was v EtOH/v TEOS=10. A porous but cracked film was obtained, and no microparticles were found on the substrate and inside the autoclave. Next Figure shows the SEM image of the film under the above-described conditions.

Figure VI. 13 SEM image of a film obtained by spraying (in
supercritical CO2 ) TEOS+EtOH on the HCOOH wet substrate.

Chapter VI Silica aerogel films

229

It was observed that this film was porous and reasonably homogeneous. Figure VI.14 shows a closer up of the film morphology, its microstructure was very similar to that of a bulk aerogel.

Figure VI. 14 Micrograph of a detail of the film microstructure.

For the process number 2), see Figure VI.8, the substrate was initially covered just by HCOOH (not dissolved in ethanol) and the ratios were increased to HCOOH/TEOS =12, and v EtOH/vTEOS =1 in order to accelerate the gelification process. A porous and nonhomogeneous 100 m thick film was obtained. Some microparticles were on the substrate but no powder was found inside the autoclave. In order to better understanding the process that occurs inside the reactor a scheme is shown in Figure VI.15.

CO 2

EtOH HCOOH On the substrate TEOS

Figure VI. 15 Cartoon picture of what may happen inside the
autoclave when TEOS (marked in violet) dissolved in EtOH (marked in green) is injected on the reactor wh ile the substrates are dipped in a HCOOH solution (marked in yellow).

Chapter VI Silica aerogel films

230

This cartoon gives an idea about what may happen inside the autoclave: When the autoclave is full of CO 2 molecules in supercritical conditions (marked in blue), the TEOS (marked in violet) dissolved in EtOH (marked in green) is injected on the reactor while the substrates are dipped in a HCOOH solution (marked in yellow). Then, supercritical CO 2 (marked in blue) acts as the reactive media of the sol and contributes that the sol-gel process occurs on the surface of the substrate. 5. 1) CONCLUSIONS The main objective of this chapter has been to synthesize aerogels as homogeneous films and with good adherence to the substrate. The coated substrates were Pyrex glass slides and silicon wafers. 2) Four methods were tried: dip and spin coating were used to evaluate the results of the two „one-pot‟ proposed methods. Spin coating processed films were more homogeneous and thinner than dip coated films. By varying the aging time and the viscosity of the coating gel, we were able to obtain a variety of film porosities. The processed films by spin coating were useful to evaluate the quality of the „in situ‟ and spray coating experiments. 3) The „In situ‟ methods (at low or high temperature) give a wide variety of morphologies. When the aging time was not long enough microparticles were obtained. The presence of catalyst on the hydrolysis solution accelerates the sol-gel process and then allows a better control of the homogeneity of the films. Another important factor is the ratio between the sol-gel reactive a too large concentration of hydrolysis solution results in particulate powder. 4) Spraying the sol-gel components directly in supercritical conditions seems to be the most appropriate and simple method to obtain aerogel films by „one-pot‟ processing. The substrate was covered by HCOOH and the precursor was sprayed through a nozzle, the CO 2 at supercritical conditions acts as the reactive medium. When the aging time was too short, the sol-gel process was not finished and then microparticles were found spread over the reactor. Under the optimized conditions, homogeneous and porous films were manufactured. An important factor to control the porosity and morphology of the coatings was the precursor/HCOOH molar ratio. 5) Further essays may be performed in order to find a technique to measure the porosity of the films in order to ensure the presence of silica aerogel structure. One possible technique is by elipsometry, which may allow measuring the density of the films.

Chapter VI Silica aerogel films

231

6) 7)

Further characterization of the films should be carried out (density, thickness, adherence to different substrates, etc.). Accurate theories of in situ and spray directly in supercritical conditions would permit better control of these processes and would allow the design of specific coating protocols for specific applications. 6. REFERENCES
7. “Coated film insulation, used for thermal Low-Dielectric Constant Thin-Film Composite Material." M.S. thesis, Department of Mechanical, Aerospace, and Nuclear Engineering University of Virginia, August 1998 2. “Lightweight US5221364, Hotaling Steven P 3. “Silica aerogel film and its production, optical fiber“ Tsubaki Kenji; Yokoyama Masaru; Yokogawa Hiroshi; Sonoda Kenji, JP10300995, issued 1998-11-13 4. “Developed sol-gel spray coatings for solar energy collectors”. Brinker C Jeffrey; 24. 5. “Low mass optical coating for thin film detectors”, Cho Chih-Chen; Beratan Howard R US Patent US5929441, issued 1999-07-27. 6. “Coated film with aerogel layer with low thermal conductivity and good mechanical DE19606114, stability” issued Patent 1997-08-21 Fraval Hanafi R, U.S Patent:WO0010044, issued 2000-02solar cell” Patent issued1993-06-22, electronic applications,

1. M. Bunzendahl, "Development of a

noise absorption or membranes” Patent DE19537821, issued 1997-0417 Frank Dierk, Schwertfeger Fritz, Zimmermann Andreas 8. “Acoustic waveguide properties of a thin film of nanoporous silica on silicon”. Rogers, John A.; Case, Carlye, Appl. Phys. Lett., 75(6), 865867, 1999 9. “Acoustic properties and potential applications of silica aerogels”. Gibiat, V.; Lefeuvre, O.; Woignier, T.; Pelous, J.; Phalippou, J. Non-Cryst. Solids, 186, 244-55 1995 10. “Applications for silica-based aerogel products on an industrial scale” M. Scmidt, F. Schwertfeger. Mat. Res. Soc. Symp. Proc. Vol 521 1998 11. “Evaluation of the acoustic properties of silica aerogels” Conroy, John F. T.; Hosticka, Bouvard; Davis, Scott C.; Norris, Pamela M. 82 Porous, Cellular and Microcellular Materials, 25-33 1998 12. “Localization of acoustic vibrations in aerogels” Vacher, R.; Courtens, E.

Frank Dierk; Schwertfeger Fritz; Zimmermann Andreas.

Chapter VI Silica aerogel films

232

Ultrason. Symp. Proc., (2), 1237-9 (English) 1989. 13. “Modified silica aerogels as acoustic impedance ultrasonic matching devices” layers Gerlach, in R.;

Kraus, O.; Fricke, J.; Eccardt, P. C.; Kroemer, N.; Magori, V. J. NonCryst. Solids, 145(1-3), 227-32 1992. 14. “Flexible aerogel composite for mechanical stability and process of fabrication” Patent WO 9938610, issued 1999-08-05 Coronado, Paul R; Poco, John F. 15. „Aerogel US5470612 A. 16. “Rapid aging technique for aerogel thin films” US5753305, issued 199805-19, Jeng Shin-Puu; Smith Douglas M; Ackerman William C 17. .D.E Bornside et al. J. Appl. Phys. 66 (1989) 5185. 18. "Preparation Xerogels by Modification", of High Brinker, Porosity Surface C.J., Chemical mesh , getter„, issued Patent 1995-11-28

Hotaling Steven P, Dykeman Deidra

Desphande, R.,Smith, D.M., U.S. Patent No. 5,565,142, issued October 15, 1996.

19. "Ambient
Preparing

Pressure Aerogel

Process Thin

for

Films",

Brinker, C.J., Prakash, S. U.S. Patent No.5,948,482, issued September 7, 1999

CONCLUSIONS

This section provides an overview of the conclusions of each of the chapters presented in this thesis. The preparation of silica aerogels deals with the combination of the silica solid matrix (formed by interlinked silica nanoparticles) and nanometer-sized pores (filled with air). Such combination results in the unique optical, thermal, acoustic, and mechanical properties of aerogels. In this work it has been shown that there is a direct connection between the chemistry of the sol-gel process and the structure of the gels and consequently, on the microstructure of the aerogels. The choice of the precursors and the chemical reaction parameters determines the physical properties of the final silica aerogels. It has been shown that it is possible to control porosity and transparency by adjusting the so-called sol-gel parameters, which include the type and concentration of alkoxide precursor, acid or base catalyst, and water content. Tetramethoxysilane as metal alkoxide precursor (TMOS): To obtain transparent aerogels the best synthesis is obtained by using methanol as solvent with the presence of base catalyst at low concentrations. This synthesis has been labeled as M-series. Varying the TMOS concentration in acetone gels proves to be an easy way for controlling density and porosity of the resulting aerogels. The study of the influence of the TMOS/acetone concentration of the sol on the density of the aerogels was performed by using the so-called A-series. M ethanol gels are very transparent while acetone aerogels have a white shading and their opacity decreases with increasing TMOS content. For all the samples of A-series, monolithic structures without cracks were obtained. The A1 aerogels were especially fragile. Cracked gels were produced when ethanol was used as a solvent. It was found that the gel time, t g , widely expands from few minutes to several days, depending on the type of solvent and catalyst combinations, with shortest t g being for methanol solvent and sodium hydroxide catalyst. This effect is a result of the shortest chain length and branching of the methanol compared to the other solvents.

Conclusions

234

Tetraethoxysilane as metal alkoxide precursor (TEOS): Aside from TMOS, other esters of orthosilicic acid like TEOS were used to obtain silica aerogels. TEOS is not only less toxic when compared to TMOS but it is cheaper too. Hence, TEOS is a more suitable precursor for the commercial production of silica aerogels. The best quality TEOS aerogels, in terms of monolithicity and transparency, without much shrinkage were obtained by using weak base or acid catalyst, TEOS molar concentration in alcohol: between 5 and 7, and excess of stoichiometric amount of water with values between 5 and 8. Strong acidic catalyst gave transparent but cracked aerogels, whereas weak acids yielded monolithic and transparent aerogels. The conditions considered optimal concentration of reactive were for TEOS/EtOH/H 2O =1/5/7, 1/7/5, 1/7/6, and 1/7/8. The reaction was more easily controlled with the presence of low concentration of acid citric catalyst (0.01<c<0.03). On the contrary, taking the m precursor concentration (m= TEOS/EtOH) lower than 5 (m< 5) and higher than 9 (m> 9) values resulted in opaque, high density as well as cracked aerogels. The effect of ethanol content over the TEOS gels allowed aerogel density to decrease. In addition, it can be concluded, that an increase in solvent content reduces the probability of mutual collisions of hydrolyzed alkoxides molecules (Si OH), resulting in a decrease in the rate of polymerization reaction. One can state that to produced a good quality aerogels, the most favorable condition of the preparation were when the ‘two-step method’ was followed, a first step in acidic conditions and a second one in basic conditions. The two-steps aerogel density increases as the concentration of catalyst increases, due to the fact that at too large catalyst concentrations, the colloidal particles and pores are smaller and therefore the gels tend to shrink and become denser. In all two-steps obtained aerogels to enhance the aging process, the gels were soaked in an alcohol/water/catalyst mixture of equal proportions to the original sol. The gels were maintained in this solution up to 24 hours. After that, water was removed by soaking the gels in an ethanol solution. In conclusion, although a slightly more laboriously synthesis, the twostep process appears to be the best synthesis method to obtain low-density (from 0.03 to 0.1g/cm3 ), non-cracked, and very transparent aerogels with a high surface area (8001000m2 /g). For all the metal alkoxide precursors, it was observed a decrease of gel time by either increasing the amount of water or decreasing the concentration of the precursor. It should be pointed out that for the same synthesis and drying conditions, gels washed in ethanol

Conclusions

235

exhibited a lower bulk density and the incidence of cracking or fracture of aerogels was significantly lower. This difference in bulk density is attributed to the presence of water during drying process that caused a larger shrinkage giving a denser bulk structure.

Physical characterization of silica aerogels has been widely investigated. The aerogels were characterized by BET, IR, UV-VIS spectroscopy, light scattering, SEM, and TEM techniques. Aerogels from diverse sets presented clear differences in shrinkage, transparency and porosity. Initial parameters, such as solvent, catalyst and water content, have a pronounced influence in the pore structure and optical transparency of the final aerogel. Different microstructures, from macroporosity to mesoporosity, have been obtained by varying the initial sol parameters. The surface area and porosity of the resulting aerogels has been discussed using the BET technique, M and A-series showed similar surface areas (from 400 to 600 m 2/g). The translucence of the aerogel samples indicates the presence of macropores, although they are not accounted by BET. In order to evaluate the effect of the macropores on the transparency, light transmission experiments have been performed. The optical transmission of the aerogels was measured at a wavelength of 900 nm in order to compare quantitatively the degree of transparency of the samples at the visible range. The lowest transmission was obtained for more diluted sol conditions (A1), the percentage of transmission was of 23% for a sample with a thickness of 1 cm and the highest transmission for denser aerogel (A4), the percentage of transmission increased up to 40%. Aerogel transparency increases with the TMOS concentration due to lower macropores content. The percentage of light absorbance depending on the intensity of the Rayleigh scattering has been related to the diameter size of the scatter centers, <
pore >Rayleigh ,

larger porous leads to lower transmission.

It is important to point out that pore size distribution has been described by a proposed model using BET, optical transparency and density measurements. From that model, it has been concluded that: The opacity in A1 is explained by the large value of
V, where V= Vpore -VBET, which

corresponds approximately to the macropores not measured by BET (~ 90% for A1). UVVIS measurements allowed to confirm this hypothesis giving a A1 pore diameter,
<
pore >Rayleigh,

of 150 nm. A2 and A3 have a pore size distribution with an important number

of micropores and/or macropores, but the mean pore diameter obtained is within the

Conclusions

236

mesopore range. A4 presented a mesopores distribution, which is totally accounted by the BET technique, and agrees with the mean pore value obtained by optical measurements. M have a pore size distribution that is mostly accounted by BET (~80%). Its mean value is similar for both techniques, BET and optical measurements. The nephelometer measured the angular and polarization dependence of light scattered at visible regions. It has been proved that intensity measurements at fixed angle provide information about the size of scattering centers. Angular measurements at different wavelength have demonstrated the necessity of performing scattering measurements to obtain information outside of the Rayleigh regime. The presence of the correlation function (r) in the scattered intensity equations has permitted to use light scattering measurements to determine density-density correlation in the aerogels medium, and to extract information about the inhomogeneities of the aerogel microstructure. It was assumed that the correlation function consists of a short-range exponential part, 1(r), and a long-range gaussian part, 2(r). The model proposed was able to fit the experimental data by the variation of the a1, a2 and w parameters. The model was fitted with four different wavelengths. Further studies should be undertaken in order to improve the fitting of the data with the aim of extracting structural information from the scattered intensity and to normalize the intensity for each laser beam. New correlation functions are proposed to fit the experimental data.

Since bulk material properties are a function of aerogel microstructure, then efforts to direct imaging aerogels at molecular level have been taken by using SEM and TEM. The morphological features, such as particle shapes and particle arrangements, of the series of acetone silica aerogel A-series, and the base catalyzed aerogel with methanol as solvent (M) has been examined by Scanning and Electron microscopy (SEM and TEM). An estimation of the particle size has also been evaluated. SEM images show that the aerogels have a granular appearance composed by spherical particles. A1 sample is built by smaller interconnected particles than the denser A4 sample. A4 showed the smallest pores, although particles were larger than those of A1. M aerogel shows an interconnected structure with smaller particle size. TEM technique has provided molecular information about the aerogels and to distinguish the different parts of the structure of the aerogel. Individual chains and

Conclusions

237

crosslinking junctions have been visualized. TEM microscopy was used to examine the surface replicas in stereo with a tilt series at 20k-80k magnifications. The stereoscopic images have made possible a three-dimensional visualization of the aerogel structure.

The microindentation technique has proved to be a non-destructive, suitable dynamical method to assess the parameters that characterize the mechanical behavior of extremely porous materials such as aerogels, despite their brittleness and softness. Silica aerogels of different mechanical responses have been obtained by varying the initial parameters in the TMOS sol-gel polymerization process, such as alkoxide concentration, solvent, drying process, as well as the carbon addition. Young’s modulus, hardness and the elastic parameter, that measures the percentage of elasticity versus plasticity, have been evaluated for these aerogel samples. It has been shown that the evolution of the parameters describing the mechanical behavior as a function of the bulk density follows power-scaling laws. A relation of the type, E with ~2.9 was found for the A-series. The evaluated exponents are 2.0 and -3.2 for hardness, and elastic parameter, respectively. As a function of aerogel density, two different regimes of mechanical behavior are observed. The lowest density aerogels are elastic but the denser aerogels are elasto-plastic materials. The large dependency of Young’s modulus on the density as well as the change from elastic to plastic behavior has its origin on the aerogel microstructure. Further structural and modelisation efforts are needed for a deeper understanding of these dependencies. The effects of the solvent, being methanol or acetone, on the silica aerogels have also been studied. It was found that for samples with similar density values, the ones obtained using acetone have higher hardness and Young’s modulus values than those obtained from methanol, but with less elastic recovery. Moreover, the effect of the drying process has been studied. It has been shown that the process with CO 2 -acetone exchange causes a slight improvement in hardness and a relevant increase in the elastic modulus, mostly due to larger shrinking effects. An improvement of the material’s elasticity is needed for some applications. Carbonreinforced aerogels present a more elastic response to indentation compared to silica aerogels. The addition of small amounts of powdered carbon as filler in silica aerogels increases the elasticity of the composite and keeps the hardness similar to silica matrix values.

Conclusions

238

It has been found that including small amounts of activated carbon inside the fragile silica network dramatically increases its elastic indentation recovery. This is reflected in the shape of the indentation curves as well as in the increase of the elastic parameter value. Young’s modulus values obtained for carbon-reinforced aerogels show a similar variation to the carbon mass fraction as that predicted by a commonly used model for composite materials. The measured hardness values corresponding to the total elastoplastic deformation do not show such a prominent dependency on the carbon mass fraction as the elastic parameter and Young’s modulus do and values of hardness are similar to those measured for the pure silica aerogel.

A simple and versatile method to obtain silica aerogel particles based on the hydrolysis and subsequent condensation of silicon alkoxides (TMOS/TEOS) in several supercritical f luids has been proposed. The sol-gel route at supercritical conditions reduces the number of steps of the traditional microparticle sol-gel processing. To obtain aerogel silica powders at low temperature the synthesis has been performed using supercritical carbon dioxide as solvent. Following the ‘in situ’ high-temperature method, spherical and fiber silica particles have been produced by ‘one-pot’ method using the sol-gel process with supercritical acetone as a solvent. The spherical particles showed a very narrow size distribution. The particle size is controlled by varying the relative amounts of alkoxysilane, water and acetone. Other important parameters in order to control the particle size are the relative time, t/tgelification, and the way of introducing the reactants in the autoclave. Silica aerogel microparticles have also been produced at low-temperature by ‘one-pot’ process by injecting the reactive under CO 2 supercritical conditions. In this case, less spherical in shape particles were obtained because the existence of necking between particles. The most porous aerogel microparticles have been produced when using two-steps synthesis and introducing a liquid CO2 exchange. Major focus was given on the understanding of the particle formation mechanisms and on the conditions to tailor the particle morphology, size and porosity. The morphology of the particles has been characterized by electron microscopy (SEM and TEM) and Atomic Force Microscopy (AFM). The microstructure observed on the silica aerogel surface was similar to that one of bulk silica aerogels. Coulter technique has also been used to account for the particle size distribution. In addition, BET surface area, pore volume and mean pore diameter of the aerogel microparticles have been obtained from nitrogen sorption isotherms.

Conclusions

239

Aerogel films have a wide range of applications. The main objective of film chapter has been to synthesize aerogels as homogeneous films. Two ‘one-pot’ methods have been described. A recently set up ‘laboratory scale plant’ has provided us with the possibility to better rationalize the number of free parameters in the experiments and simplify the realization of such. We have also performed some dip coating and spin coating experiments to compare the results of those with our methods. When dealing with dip and spin coating methods to produce aerogel films, the solvent evaporation rate should be slowed down since there is a large contact area of the forming gel with the atmosphere. Thus, the coating is usually done in a saturated solvent vapor chamber. A second step is required to supercritically dry the coating. Further characterization of the films should be done (density, thickness, adherence to different substrates, etc.).

ANN EX I

SUPERCRITICAL FLUIDS

A supercritical fluid is defined as a fluid above its critical temperature (T C) and its critical pressure (PC). The critical point represents the highest temperature and pressure at which the substance can exist as a vapor and liquid in equilibrium. A ‘physical’ way to explain what is happening in a supercritical fluid is that when two molecules approach each other in a fluid, at a temperature where their relative speed is likely to be low, their mutually attractive forces will bring a temporary association between them. If there is a sufficient density of molecules, there is the possibility of condensation to a liquid. On the other hand, if the temperature and the probable relative speeds are high, the attractive force will be too weak to have more than a slight effect on the molecular velocities, and condensation cannot occur however high the molecular density. It is therefore reasonable to expect, on the basis of molecular behavior, that for every substance there is a temperature below, which condensation to a liquid (and evaporation to a gas) is possible, but above which these processes cannot occur. That there is a critical temperature above, which a single substance can only exist as a fluid and not as either a liquid or gas. The phenomenon can be easily explained using the phase diagram for pure carbon dioxide (Figure AI.1).

Annex I. Supercritical fluids

244

Figure AI. 1

Phase diagram of a single substan ce, carbon dioxide.

The phase-diagram is schematic, and the pressure axis is non-linear. It shows the areas where carbon dioxide exists as a single gas, liquid, solid phase or as a supercritical fluid. The curves represent the temperatures and pressures where two phases coexist in equilibrium (at the triple point, the three phases coexist). Moving along the gas-liquid curve, increasing both temperature and pressure, then the liquid becomes less dense due to thermal expansion and the gas becomes denser as the pressure rises. Eventually, the densities of the two phases converge and become identical, the distinction between gas and liquid disappears, and the end of the coexistence curve is defined as the critical point. The substance is now described as a fluid. The critical point has pressure and temperature coordinates on the phase diagram, which are referred to as the critical temperature, Tc, and the critical pressure, p c, and which have particular values for particular substances, some examples are shown in the table below.

Annex I. Supercritical fluids

245
Substances useful as supercritical fluids, with critical

Table AI. 1 parameters

Solvent H20 NH3 CO2 CH3CH2OH CH3OH CH3CN Hexane

Critical pressure Pc (atm) 216 110 70 62 77 47 32

Critical temperature Tc (°C) 374 132 31 243 240 275 235

It was 170 years ago that Baron Charles Cagniard de la Tour showed experimentally the disappearance of the distinction between the liquid and gas phases. In the experiment, it was observed through a view cell how the meniscus between a liquid and a gas disappeared at the critical temperature.

Figure AI. 2 Disappearan ce of the meniscus at th e critical point. The meniscus separating a liquid (bottom) from its vapor (top) disappears at the critical point. The liquid state does not exist above the critical temperature, regardless of the pressure that might be applied to the substance.

Annex I. Supercritical fluids

246

Supercritical fluids exhibit important characteristics such as compressibility, homogeneity, and a continuous change from gas-like to liquid-like properties. These properties are characteristic of conditions inside supercritical fluid region. The more fundamental interest in supercritical fluids arises because they can have properties intermediate between those of typical gases and liquids. Compared with liquids, they have lower densities and viscosities and greater diffusivities. The conditions may be optimum for a particular process or experiment. Furthermore, properties are controllable by both pressure and temperature and this characteristic compared with a liquid, leads to that more than one property can be optimized. The main disadvantages are their cost and inconvenience of the higher pressures needed. Consequently, supercritical fluids are exploited only in particular areas. The critical point for carbon dioxide occurs at a pressure of 73.8 bar and a temperature of 31.1°C. These parameters make equipment design relatively simple. Carbon dioxide is available as a convenient supercritical fluid substance. Carbon dioxide has so far been the most widely used, because of its convenient critical temperature, low price, chemical stability, non-flammability, stability in radioactive applications and non-toxicity. Large amounts of CO 2 released accidentally could constitute a working hazard, but hazard detectors are available. It is an environmentally friendly substitute for other organic solvents. Its polar character as a solvent is intermediate between a truly non-polar solvent and weak polar solvents.

BIBLIOGRAPHY

This annex is adapted from the introduction to Fundamentals of Supercritical Fluids by T. Clifford, published by the Oxford University Press in 1998.

ANN EX I I

TECHNICAL DESCRIPTION OF THE JOIN ICMAB-CM HIGH PRESSURE-HIGH TEMPERATURE LABORATORY *

The laboratory is composed by two main equipments (a laboratory scale plant and pilot plant). The high pressure-high temperature lab was created by ICMAB and Carburos Metalicos in 1995 to investigate develop and promote new supercritical fluid applications. The lab was designed to allow the maximum possible types of experiments, proposed by research groups or industries. The high pressure-high temperature facility is able to work up to 400 ºC and 500 bars with CO 2, as a supercritical fluid. However, others supercritical fluid can be used, if necessary. The flexibility is one of the more important aspects of the ICMAB pilot plant. Temperature, pressure and flow rate can be easily tuned to work at different conditions. This flexibility allows planning different operations and to control pressurization, depressurization and heating rates with great accuracy. The collected pressures have an uncertainty of 0.7%. CO 2 was chosen as main supercritical fluid due to the advantages that offer (Table AI.1). Although its safety, some preventive measures must be taken when CO 2 is used. It may produce immediately hazardous and asphyxiating atmospheres. Fast liquid CO 2 depressurization produce solid CO 2 and it can block pipes. CO 2 can be recycled as much as needed and product solubility can be tuned by controlling pressure and temperature

Table A.I. 1

Advantages of carbon dioxide as supercritical fluid

Advantages Non-toxic Non-flammable Cheap Readily available Highly selective Low viscosity High diffusivity

*This

section was taken from Supercritical Training Course. J. Torres and R. Solanas

Annex II. Technical description of the join ICMAB-CM High pressure-high temperature Laboratory

248

1.

DESCRIPTION OF THE HIGH PRESSURE-HIGH TEMPERATURE PLANT

The experimental apparatus used for drying is shown in Figure A.I.1.

Figure A.I.1 Pilot plant and its three unites: 1) CO 2 supplier and liquefier (blue square), 2) reactors – pressure, temperature and flow rate control (violet square), 3) and conditioning before releasing (green square).

Table AI.2 gathers the technical description of the pilot plant.
Table A.I. 2 Pilot plant technical data

Maximum pressure: Maximum temperature: Number of reactors: Reactors volume: Heating Power: CO2 maximum flow rate: Cosolvent maximum flow rate: Computer controlled plant

500 bar 400 ºC 3 1-2 liter 14.5 kW (5 heaters) 40 Kg/h 1,8 l/h

The chamber pressures given have an uncertainty of ±0.7percentage. Additional features: Work with liquid and solid samples Recycling CO 2 Feed cosolvent

Annex II. Technical description of the join ICMAB-CM High pressure-high temperature Laboratory

249

Spray liquids inside reactors Data recording for temperature, pressure and CO 2 flow rate Different working conditions at each reactor Adsorption tower before venting Alternative gases (nitrogen,) can be fed SCF sampling 2-litre agitated reactor with quartz viewer Different types of filters are available As it is shown in figure 1 the plant is divided in three unites: 1) CO 2 cylinders and its liquefier, 2) 3 reactors of 2 liters– pressure, temperature and flow rate control, and 3) the control releasing facilities (a safety vessel of 51 liters). The first and third units are located outdoors and the second inside the lab. Unit 1: CO2 supplying and liquefier Composed by: Two CO 2 cylinders set each one with four cylinders 85 liters liquefier with its temperature and level control Two chillers Glycol cooling closed loops (with a pump included) to maintain the CO 2 in liquid phase Five pressure transmitters Six relief valves Three thermocouples, to control temperature of the cylinders Seven on/off valves, to control feeding of the CO 2 Several manual valves, to control the feeding in case of electronic failure

Annex II. Technical description of the join ICMAB-CM High pressure-high temperature Laboratory

250

Figure A.I.2 Outdoors view: high-pressure pump, CO2 liquefier, chillers, and cylinders.

Unit 2: Reactors with its corresponding pressure, temperature and flow rate control Composed by: High pressure pump (to feed the CO 2) outdoor Five control valves for pressure and flow rate control Seven on/off valves to control CO 2 feeding Three reactors (pressure maximum: 500 bar temperature maximum: 400 ºC): two 2-liter capacity reactor and one 1-liter capacity extractors. Five heaters (one for CO 2 preheating, one for each reactor and piping) Two mass flow meters Sampling loop Two heat exchangers for CO 2 Four pressure transmitters Four-safety pack composed by one relief valve and one pressure switch.

Annex II. Technical description of the join ICMAB-CM High pressure-high temperature Laboratory

251

Fourteen k thermocouples to control the temperature in different parts of the plant and turn off the heating in case of safety Several manual valves in case of automatic valves failure

Figure A.I.3 High pressure - high temperature vessel

Unit 3: System of releasing

Figure A.I.4 High pressure - high temperature pilot plant

Composed by: Safety vessel (51 liters), designed to collect toxic or dangerous supercritical solutions, avoiding releasing them to the atmosphere, during overpressures and emergency shutdowns.

Annex II. Technical description of the join ICMAB-CM High pressure-high temperature Laboratory

252

Adsorption tower filled with activated carbon Two pressure transmitter Two-safety pack composed by one relief valve and one pressure switch One control valve One on/off valve Several manual valves Safety system (safeguards) The most dangerous hazard is a rupture of the reactor, vessels or pipes under pressure, due to an overpressure or high temperature. A safety 10 mm polycarbonate screen protects the plant. Overpressure safeguard: At each reactor, safeguards are redundant in four levels: i) Software does not allow pressure set point higher than the maximum pressure. ii) Presence of a pressure transmitter control– if measured pressure is higher than safety set point, the plant stops. iii) Pressure switch, and iv) level is controlled by relief, then, the overpressure is released. High temperature safeguard: At each reactor, safeguards are redundant in two levels: i) Software does not allow temperature set point higher than the maximum temperature of the plant. ii) Thermocouple – if measured temperature is higher than safety set point, heater is turned off. CO 2 high concentration safeguard: In the laboratory, there are two O 2 sensors and a fan to renew air. Personal protection safeguards: high temperature gloves, safety glasses, small masks for organic solvent and powder. Wrong operation safeguard: special software was designed to avoid wrong operation. Switches and position detectors avoid wrong operation, too. Safety vessel. Water hammer appears after suddenly opening or closing an On/off valve, when the pressure difference between valve inlet and outlet is high. It could be dangerous and it must be avoided or diminished. 1.1.1 Description of the laboratory scale plant

Lab scale plant has an agitated 300 ml vessel, able to work up to 414 bars at 20 ºC or 227 bars at 454 ºC. Samples can be liquids and/or solids and co-solvents can be fed.

Annex II. Technical description of the join ICMAB-CM High pressure-high temperature Laboratory

253

Esquema Planta Petita Laboratori Supercritic

B A

Esquema Planta Petita Laboratori Supercritic

esquema planta petita.dwg

Figure A.I.5 Description of the laboratory scale plant and its two unites: 1) CO2 supplier and liquefier (A square), 2) reactor– pressure, temperature and flow rate control (B square),

Annex II. Technical description of the join ICMAB-CM High pressure-high temperature Laboratory

254

9 5 1 6

2
Figure A.I.6 Picture of lab scale plant. It is composed by: (1) reactor (red line), (2) chiller (g reen line), (4) pressure valves (black lines), (5) nitrogen and carbon dioxide gas connection (white line), (6) CO 2 liquid pump (yellow line), and (9) pressure, temperature, and flow rate control system.

A ‘zoom’ up of the reactor allows distinguishing the pressure valves and the realizing system and the connections for the cooling/heating system.

Annex II. Technical description of the join ICMAB-CM High pressure-high temperature Laboratory

255

Magnetic Analogical manometer stirring drive CO2 Gas pipe Control panel

Valve control

Rupture disk Thermocouple Pre-heater Pressure valves
Figure A.I.7 Detail of the s mall of lab scale p lant

Annex III

INTRODUCTION TO ADSORPTION ANALYSIS AND TO THE BET MODEL

1.

INTRODUCTION TO ADSORPTION ANALYSIS

When a gas or vapour is brought into contact with a solid, the solid takes up part of it. The molecules that disappear from the gas either enter the inside of the solid, or remain on the outside attached to the surface. The former phenomenon is termed absorption (or dissolution) and the latter adsorption. When the phenomena occur simultaneously, the process is termed sorption. The phenomenon of adsorption was discovered over two centuries ago. The solid that takes up the gas is called the adsorbent, and the gas or vapour taken up on the surface is called the adsorbate. It is not always easy to tell whether the gas is inside the solid or merely at the surface because most practical absorbents are very porous bodies with large internal surfaces. It is not possible to determine the surface areas of such materials by optical or electron microscopy because of the size and complexity of the pores and channels of the material. The gas adsorption itself, however, can be used to determine the accessible surface area of most absorbents. In this section the adsorption of N 2 at cryogenic temperatures on silica aerogels and silica microparticles was investigated
1.1 THEORY OF ADSORPTION

Molecules and atoms can attach themselves onto surfaces in two ways. In physisorption (physical adsorption), there is a weak van der Waals attraction of the adsorbate to the surface. The attraction to the surface is weak but long ranged and the energy released upon accommodation to the surface is of the same order of magnitude as an enthalpy of condensation. During the process of physisorption, the chemical identity of the adsorbate remains intact, i.e. no breakage of the covalent structure of the adsorbate takes place. In chemisorption (chemical adsorption), the adsorbate sticks to the solid by the formation of a chemical bond with the surface. This interaction is much stronger than physisorption, and, in general, chemisorption has more stringent requirements for the compatibility of adsorbate and surface site than physisorption. The physisorption classification for the pore size is given by:Macropores: when pore diameter ( 0) is Micropores: when
0

50nm (0.05 m), Mesopores: when 2nm

0

50nm,

2nm.

Annex III.Introduction to adsorption analysis and to the BET model

258

This definition is not exact because the filling of the pore depends on the shape of them and is influenced by the adsorbate properties and for the adsorbent/adsorbate interactions. The total accessible volume present in the micropores is considered as adsorption space, this process is called micropores filling; different at the superficial coverage occurred on the open macropores mesopores walls. The mesopores physisorption occurs in two steps: monolayer adsorption and capillary adsorption. In the monolayer adsorption, all adsorbate molecules are in contact with the adsorbent surface. In the multilayer adsorption not all the molecules adsorbate are in direct contact with the adsorbent surface because the adsorption space is covered for multilayer molecules. In the capillary adsorption the residual space of the pore that is empty after the multilayer adsorption is filled by a condensed, separate of gaseous phase by meniscus. The capillary condensation is frequently followed by hysteresis. This process does not exist in the micropores filling. In physisorption, the monolayer capacity, n mono, is defined as the adsorbate quantity needed to cover all the absorbent surface with a complete molecule monolayer and Vm as the volume of the maximum gas absorbed usually taken to be a monolayer. The energy of adsorption depends on the extent to which the available surface is covered with adsorbate molecules. This is because the adsorbate can interact with each other when they lie upon the surface (in general they would be expected to repel each other). The fractional coverage of a surface is defined by the quantity :
Number of occupied adsorption sites Total number of possible sites

(1)

At any temperature, the adsorbate and the surface come to a dynamic equilibrium, that is, the chemical potentials of the free adsorbate and the surface bound adsorbate are equal. The chemical potential of the free adsorbate depends on the pressure of the gas, and the chemical potential of the bound adsorbate depends on the coverage, . Thus, the coverage at a given temperature is a function of the applied adsorbate pressure. The variation of specific surface area adsorbent (As) is calculated by: with P at a given T is called an adsorption isotherm. Adsorption hysteresis is obtained when adsorption and desorption curves are different. The

As

N A nmono

m
is the molecular area occupied per absorbate N 2: 16.2Ų, m is

Where: N A is Avogadro's number, the mass of the sample
1.2

THE LANGMUIR MODEL

Langmuir suggested the earliest model of gas adsorption. The model is limited to monolayer adsorption. If one assumes that all adsorption sites are equivalent then the adsorption and desorption rate is independent of the population of neighbouring sites. Then one can derive a simple formula for an adsorption isotherm.

Annex III.Introduction to adsorption analysis and to the BET model

259

Consider the equilibrium: A+S A.S (2) Where: A is the free adsorbate, S is the free surface, A.S is the substrate bound to the surface. The rate of adsorption will be proportional to the pressure of the gas and the number of vacant sites for adsorption. If the total number of sites on the surface is N, then the rate of change of the surface coverage due to adsorption is:

d dt

ka P N (1

)

(3)

The rate of change of the coverage due to the adsorbate leaving the surface (desorption) is proportional to the number of adsorbed species:

d dt

kd P N

(4)

In these equations, ka and kd are the rate constants for adsorption and desorption respectively and p is the pressure of the adsorbate gas. At equilibrium, the coverage is independent of time and thus the adsorption and desorption rates are equal. The solution to this condition gives us a relation for :

kP V 1 k P Vm
where :k = ka / kd, .V= volume of gas absorbed at pressure P

(5)

Note that because k is equilibrium constant, the value of k at various temperatures determined from the Langmuir isotherm allows for the evaluation of the enthalpy of adsorption, Van't Hoff equation: ads, through the

d ln k dT

H ads RT 2

(6)

As the strength of the interaction between the adsorbent and the adsorbate increases the value of p increases and the surface coverage increases faster as the pressure is increased. To use the Langmuir model adsorption data are plotted in the form:

P V

1 kVm

P Vm

(7)

Vm is calculated plotting P/V against P and find Vm from 1/slope of the line. In practice, it has been found that the Langmuir model is rarely a useful model to fit gas adsorption data and hence calculate the surface area. The Langmuir model is only applicable when adsorption at low coverage. The Langmuir isotherm is found to be useful only at very small coverage (submonolayer) but is generally applied to all cases involving chemisorption.

Annex III.Introduction to adsorption analysis and to the BET model

260

2.

THE BET MODEL

Brunauer, Emmett and Teller developed several models of gas adsorption on solids, which have become the effective standard for surface area measurements. The models were generalisations of Langmuir theory monolayer adsorption to multilayer adsorption. The BET isotherm is useful in cases where multilayer adsorption must be considered. Nitrogen is the most commonly used BET adsorption gas because of its inertness to chemical interaction with most materials and the ready availability of liquid nitrogen to control the temperature of the adsorption process. The standard 2 parameter BET isotherm gives the amount of gas adsorbed as a function of the relative pressure of the adsorbing gas:

n n mono
where

V Vm

c ( P / P0 ) (1 P / P0 ) 1 ( c 1)( P / P0 )

cx (1 x ) 1 ( c 1)x

(8)

V = Volume of gas adsorbed at pressure P, V m = Volume of gas covering the surface with a monomolecular layer, n/nmono is the ratio of the moles adsorbed to the moles adsorbed in a single monolayer.Po = Saturation pressure of the gas (vapour pressure), i.e. the pressure of the gas in equilibrium with bulk liquid at the temperature of the measurement., x = P/Po = Relative pressure. c = a constant for the gas/solid combination. The isotherm can be converted to a linear form for ease of extracting the values of V m and c. The constant c represents the relative strengths of adsorption to the surface and condensation of the pure adsorbate. Simple theory predicts an approximate value of this constant as:
H ads / RT H vap / RT

c

e e

(9)

The constant c is related to the difference between the heat of adsorption of the first layer (H 1) and the heat of liquefaction (HL), Where H1-HL= H, is also known as the net heat of adsorption. R = gas constant (8.31447 J K-1 mol-1) T = temperature (K) The BET model is used to measure the surface areas of several porous materials. The BET isotherm is found to describe adequately the physisorption at intermediate coverage ( = 0.8 - 2.0) but fails to represent observations at low or high coverage. The BET isotherm is reasonably valid around =1.0, however, and this is useful in characterising the area of the absorbent. If one can determine experimentally the number of moles of adsorbate required to give , =1.0 (i.e. a monolayer), one can determine the specific surface area of the absorbent.

A

surface area of absorbent m 2 mass of absorbent g

(11)

Practically, one measures the number of moles adsorbed as a function of equilibrium pressure, i.e. one does not directly measure . Algebraic rearrangement of the BET isotherm to produce a linear

Annex III.Introduction to adsorption analysis and to the BET model

261

equation is usually applied to experimental data. For surface area measurements the BET equation is used in the form:
x n( 1 x ) 1 n mono c ( c 1) x n mono c

Over the range where the BET isotherm is valid (in the range P/Po = 0.05-0.30), a plot of x/n(1-x) vs x will be linear. The slope and intercept of this line will allow the determination of nmono (or Vm) and c.
Vm
c

1 Slope Y
Y

int ercept

from the best fit straight line.

Slope 1 int ercept

from the best fit straight line.

Finally, the BET surface area is then calculated from:
A m2 / g N A nmono / m

(13)

Where: is the molecular area occupied per absorbate N 2: 15.8 (16.2)Ų N A is Avogadro's number m is the mass of the sample Vm is in cm³ at STP/g. The adsorption process is generally taken as completely reversible, but, under some conditions the isotherm may exhibit different shapes upon desorption as compared to absorption. This is called hysteresis. Sometimes hysteresis data can be used to determine the structure and size of pores in the absorbent. We will therefore need to generate an isotherm for both absorption and desorption.
2.1 EXPERIMENTAL PROCEDURE

We will perform the adsorption measurements in a commercial vacuum manifold called the ASAP 2000, manufactured by Micromeritics Instrument Corporation. The ASAP 2ooo system consists of one analyser and a multi-function control module. The analyser it is designed for completely automatic operation. Two separate internal vacuum systems are included-one for sample analysis and one for sample preparation. It contains one sample analysis port and two sample preparation ports. The sample P0 (saturation pressure) tube is located next to the sample analysis port. Since the analysis results are expressed in units of surface area per gram of sample, the true weight of the sample must be known, is necessary to determine the weight of the sample before degassed: Must solid materials absorb moisture and other contaminants when exposed to the atmosphere. The sample must be clean when analysis is performed. The sample is heated and placed under vacuum to remove moisture and other contaminants. This process is referred to as degassing the sample. The approach to equilibrium is perceptibly slow, especially at high coverage. It would in principle take an infinite time for equilibrium to be exactly established. The nature of the isotherm and the required precision of the measurement suggest that equilibrium pressures need be known only to a few percent. Recordding of the equilibrium pressure generates the data needed to determine the number of moles adsorbed on the solid as a function of (equilibrium) pressure and to generate the adsorption isotherm.

Annex III.Introduction to adsorption analysis and to the BET model

262

The desorption measurement is performed to see if there is any hysteresis or non-equilibrium effects in the adsorption/desorption cycle. This is basically performed in reverse of the procedure above. The value of the constant c in the BET equation affects the shape of the isotherm mainly at low relative pressures (P/Po) as is shown below.
2.2 BJH PORE VOLUME AND AREA DISTRIBUTION CALCULATION

For adsorption data, the relative pressure and volume adsorbed data points pairs collected during an analysis must be arranged in reverse order from which the points were collected during analysis. All calculations are performed based on a desorption model, regardless of whether adsorption or desorption data is being used. The data used in these calculations must be in order of strictly decreasing numerical value. The data set is composed of relative pressure (Pr), volume adsorbed (Va) pairs from (Pr1, Va1) to (PrN, VaN) where (PrN=0, VaN=0) is assumed as a final point. Generally, the desorption branch of an isotherm is used to relate the amount of adsorbate lost in a desorption step to the average size of pores emptied in the step. A pore loses its condensed liquid adsorbate, known as the core of the pore, at a particular relative pressure related to the core radius by the Kelvin equation (16). After the core has evaporated, a layer of adsorbate remains on the wall of the pore. The thickness of this layer is calculated for a particular relative pressure from the thickness equation. This layer becomes thinner with the successive decreases in pressure, so that the measured quantity of gas desorbed in a step is composed of a quantity equivalent to the liquid cores evaporated in that step plus the quantity desorbed from the pore walls of pores whose cores have been evaporated in that and previous steps. Barret, Joyner, and Halenda developed the method (known as BJH method). A pore filled with condensed N 2 liquid has three zones: The core: evaporates all at once when the critical pressure for the radius is reached; the relationship between the core radius and the critical pressure is defined by the Kelvin equation.(16) The adsorbed layer: composed of adsorbed gas that is stripped off a bit at a time with each pressure step; the relationship between the thickness of the layer and the relative pressure is defined by the thickness equation. The walls of the cylindrical pore itself: the diameter of the empty pore is required to determine the pore volume and the pore area. End area is neglected. The total pore volume, Vp, is often derived from the amount of vapour adsorbed at a relative pressure close to unity by assuming that the pores are then filled with condensed adsorptive in the normal liquid state. The pore size distribution is the distribution of pore volume respect to pore size. The computation of the pore size distribution involves a number of assumptions (pore shape, mechanism of pore filling, validity of Kelvin equation, etc.). Application of the Kelvin equation Mesopore size calculation are usually made with the aid of the Kelvin equation in the form

Annex III.Introduction to adsorption analysis and to the BET model

263

1 r1

1 r2

RT p In o 1g 1 v p
is the surface tension of the liquid

Which relates the principal radii, r 1 and r 2, of curvature of the liquid meniscus in the pore to the relative pressure, p/po, at which condensation occurs; here condensate and v1 is its molar volume. It is generally assumed that this equation can be applied locally to each element of liquid surface.In using this approach to obtain the pore radius or pore width, it is necessary to assume: (i) a model for the pore shape and (ii) that the curvature of the meniscus is directly related to the pore width. The use of the physisorption method for the determination of mesopore size distribution is subject to a number of uncertainties arising from the assumptions made and the complexities of most real pore structures. It should be recognised that derived pore size distribution curves may often give a misleading picture of the pore structure. On the other hand, there are certain features of physisorption isotherms (and hence of the derived pore distribution curves) which are highly characteristic of particular types of pore structures. Physisorption is one of the few non-destructive methods available for investigating mesoporosity, and it is to be hoped that future work will lead to refinements in the application of the method - especially through the study of model pore system and the application of modern computer techniques.
3. REFERENCES

S. Brunauer, "Physical Adsorption" (Princeton University Press, Prin ceton, N. J., 1945) S. Brunauer, P. H. Emmett and E. Teller, J. Amer. Chem. Soc., 60, 309-319 (1938) I.Langmuir, J. Am. Chem Soc., 38, 2219,(1916); 40, 1368, (1918) Langmuir, J. Amer. Chem. Soc., 40, 1361 (1918); Langmuir, J. Amer. Chem. Soc., 54, 2798 (1932); Langmuir, Nobel Lecture, 1932]. P. Atkins, "Physical Chemistry" 5th ed (Freeman, New York, 1994) G. A. Somorjai, "Principles of Surface Chemistry (Prentice-Hall, Englewood Cliffs, N. J. 1972) Drake ,J.M.; Nitrogen Adsorption on Porous Silica: Model-Dependent Analysis; Journal of Physical Chemistry; v.98, 1994, p. 380-2

Sign up to vote on this title
UsefulNot useful