Preparation of Polymer/Silica Particle Nanocomposites and Their Applications (/ )

Nov. 5, 2009
KiRyong Ha ( )
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Colorado Colorado

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University of Colorado
Three campuses: Boulder, Colorado Springs and Denver.

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National Parks in Colorado

Mesa Verde National Park

Rocky Mountain National Park

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National Parks in Colorado

Great Sand Dunes National Park

Black Canyon of the Gunnison National Park

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Tourist Attractions
Aspen mountains comprises of 4993 acres, forty lifts and 335 trails along with sharp vertical slopes in the entire Colorado, which makes it more thrilling and stimulating. Aspen Colorado Ski Resort

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Tourist Attractions

Maroon Bells

One Colorado Fall day

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Tourist Attractions

Garden of the gods

United States Air Force Academy

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University of Colorado at Boulder

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Department of Chemical and Biological Engineering Our department has been ranked 19th overall and 10th among public graduate programs by U.S. News & World Report, and ranked 4th in average citations per publication by University Science Indicators.

Dr. Christopher N. Bowman

Associate Dean for Research, Patten Professor of Chemical and Biological Engineering, Clinical Professor of Restorative Dentistry and Co-Director of the NSF I/UCRC for Fundamentals and Applications and Photopolymerizations
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Outlines
1. Introduction - Composites and Nanocomposites - Silica & Silane Coupling Agent 2. Experimental - Silanization of Silica Particles - Characterization (a) FTIR (b) TGA (c) Solid State NMR - Fabrication of Nanocomposites (a) Curing Kinetics using Real Time NIR (b) DMA results 3. Conclusions
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Introduction

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Composite
Definition: Materials containing at least two constituents that can be physically or visibly distinguished. Any two-phase material can be considered a composite.

Composite theory is based the rule-of-mixtures (simple version or modified rule). In almost all cases, the solid dispersed phase is one with the better properties.
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20,000

120,000

Composite

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Effect of Fillers

Functional fillers transfer applied stress from the polymer matrix to the strong and stiff mineral.

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Polymer Nanocomposites

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Polymer Matrices

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Dimensions of Nanoparticles

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Preparation of Nanocomposites

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Why Nanocomposites? Multi-functionality

Small filler size:
High surface to volume ratio Small distance between fillers bulk interfacial material Mechanical Properties Increased ductility with no decrease of strength, Scratching resistance Optical properties Light transmission characteristics particle size dependent
Interaction Zone Particle

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Production of Precipitated Silica

1) Precipitated silica: reaction of an alkaline silicate solution with a mineral acid Na2(SiO2)3.3(aq) + H2SO4(aq) 3.3 SiO2(s) + Na2SO4(aq)

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Production process of fumed silica

2) Fumed silica Flame pyrolysis of silicon tetrachloride

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Fumed Silica

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TEM of SiIica (OX-50 & AS380)

Formation of aggregates due to high temperature manufacturing process.

TEM of Aerosil OX-50

TEM of Aerosil 380

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Evonik technical bulletin No. 11

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Fumed Silica for Insulating Materials

Reliable and most cost-effective way to reduce both energy use and CO2 emissions.

Thermal Conductivity vs Total Pressure & Pore Size

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Hydrophobic Treatment of Fumed Silica

Silica is hydrophilic in due to silanol (Si-OH) groups on the surface. These silanol groups may be chemically reacted with various reagents to render the silica hydrophobic
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Properties of Hydrophobic Fumed Silica

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Production of Monodisperse Nanoparticles

3) Stber-Process Hydrolysis Si(OC2H5)4+ 4H2O Si(OH)4+4C2H5OH Condensation Si(OH)4 SiO2+ 2H2O both in a NH3 alcohol solution
-monodisperse, spherical silica nanoparticles that range in size from 52000 nm.

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Particle-Matrix Compatibility

Regardless of filler size and shape, intimate contact between the matrix and mineral particles is essential, since air gaps represent points of permeability and zero strength.
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SiIane Coupling Agent

General Formula:

R: Amino, vinyl, epoxy, chloro, mercapto, methacryloxy, acryloxy, etc.) X: Hydrolyzable group typically alkoxy, acyloxy, halogen or amine.
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Gelest Catalog 3000-A, Silicon compounds: Silanes & Silicones, p. 166, Gelest Inc.

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SiIane Coupling Agent

Silane coupling agents have the ability to form a durable bond between organic and inorganic materials. Enhance interfacial adhesion via chemical bonding.

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Gelest Catalog 3000-A, Silicon compounds: Silanes & Silicones, p. 166, Gelest Inc.

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Silane Coupling agent Treatment

Modification with organosilane depends on the ability to form a bond with silanol groups, -Si-OH, and/or aluminol groups (-Al-OH) on the filler surface.
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Typical Silane Coupling Agents

Generally the reactivity differences between methoxy and ethoxy silanes are not a problem. At typical hydrolysis pH (acidic ~5, basic ~ 9), both versions hydrolyze in under 15 minutes at 2% silane concentrations.

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Applying a Silane Coupling Agent

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Silane Effectiveness on Inorganics

Hydroxyl-containing substrates vary widely in concentration and type of hydroxyl groups present.

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Silane Coupling agent Treatment

SEM photomicrographs of fractured silica-filled epoxy composite a) silica without silane treatment, b) silica with silane treatment.
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CO2 Reduction

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Established Nanotechnologies

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Green Tires

Lower rolling resistance Fuel economy lower carbon dioxide emissions lower global warming impact
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Green Tires

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Green Tires
How can the Silane coupling agent meet the needs?

Si-69; Bis-[-3-(triethoxysilyl)propyl]-tetrasulfide
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Green Tires
Silica Silane: How it Works

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Green Tires
Silica Silane: How it Works

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Green Tires How it works

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Silanes to Meet the Need

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New Silanes for Silica Tire 1

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Green Tires

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Experimental

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Properties of SiIica (OX-50 & Aerosil 380)

1) Noncrystalline form of silicon dioxide (SiO2) Fumed silica - OX-50: Low specific surface and only slight tendency to agglomerate. ( 2.2 Si-OH/nm2) - Aerosil 380: Highest specific surface area (2.5 Si-OH/nm2) - Hydrophilic grades. 2) BET Surface Area [m2/g]: 50 (+-) 15, 380 (+-) 30 3) Average primary particle size: 40 nm, 7 nm 4) Tapped density: 130 g/L, 50g/L 5 Density: 2.2g/cm3 6) Hardness: 5.36.5 (Mohs Scale) Fillers for transparent scratch-resistant coating 7) Refractive index: 1.46 Very close to the most organic monomers 8) Tensile strength: 48.3 MPa 9) Bulk modulus: ~37 Gpa 10) Youngs modulus: 71.7 GPa Fillers for reinforcing
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Experimental
Three parameters which will be dealt here: 1)Filler surface modification 2) Filler concentration 3) Particle size and the particle dispersion state.

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E. Chabert, M. Bornert, E. Bourgeat-Lami J.-Y. Cavaille, R. Dendievel, C. Gauthier, J. L. Putaux, and A. Zaoui, Materials Science and Engineering A 381, 302-330 (2004)

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Experimental
Materials:
1) Silica OX-50 & Aerosil 380 2) -methacryloxypropyltrichlorosilane (MPTS) 3) [(Biscycloheptenyl)ethyl]tricholorosilane (BCTC) 4) TMPTMP (Trimethylolpropane tris(3-mercaptopropionate) -3 functional S-H -n20 = 1.518, d=1.21 g/ml -b.p. = 220 at 0.3mm Hg, m.w. = 398.56 5) TMPDE (Trimethylolpropane diallyl ether) -2 functional allyl ether groups -nD =1.458, d= 0.955 g/ml -b.p. = 135/13mmHg, m.w. = 214.30
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Experimental
6) GDMP (Glycol Dimercaptopropionate) Chemical Formula: (HSCH2CH2COOCH2)2 CAS #: 22504-50-3 - 2 functional S-H b.p.: 175-195C, m.w.: 238.32 n25 = 1.5-1.51, d = 1.219
7) DMPA (2,2-dimethoxy-2-phenyl-acetophenone) C6H5COC(OCH3)2C6H5, photoinitiator, m.p. = 67~70)

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Silane treatment procedure (Dean-Stark trap)

To make monolayer of silane coupling agent on the silica, water must be removed from the reaction system. 1) Silica particles were dried by heating under vacuum 2) Dean-Stark trap was used to remove water in the toluene solvent. 3) Dried silica particles were added to the reaction flask with dried toluene. 4) Silane solution and triethylamine (catalyst) were added and stirred under nitrogen for 18 hrs. 5) The particles were washed with several kinds of solvents and dried in the vacuum oven.

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Surface Groups of SiO2 Particles

or isolated

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Evonik technical bulletin No. 11

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Drying of OX-50 (FTIR Spectrum of of Pressed Disks)

Pressed OX-50 without any treatment
Before heating

After 1hr heating at 150

By drying process, increase of the intensity at 3747cm-1, which is caused by isolated Si-OH was observed (150 for 1hr).

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MPTS OX-50 FTIR Spectrum

C=O stretching

C=C-H stretching peak of methacrylate

Disappearance of isolated SiOH

Aliphatic C-H

C=C

Pressed MPTS OX-50 Pressed Disk

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FTIR Results (C=O Peak Change)

H-bonded C=O C=C

Free C=O

(c)

(b)

(a)

(a): Pure MPTS liquid, (b): Anhydrous toluene was used to prepare (multilayer), (c) Reflux method was used to prepare.
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Q. Liu et al., JOURNAL OF BIOMEDICAL MATERIALS RESEARCH 57(3), 384-393 (2001).

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Degradation Pattern by TGA

TGA can be used to determine silane content (MPTS on OX-50 & AS380)

M.W. of degrading part: 7 C + 2 O + 11 H = 7 x 12 + 2 x 16 + 11 x 1 = 127 (Assuming all Si-OH groups reacted; T3 formation) Bond energy of the Si-O-Si bond (444 kJ/mol) Bond energy of the Si-C bond (306 kJ/mol) Bond energy of the C-C bond (345 kJ/mol).
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Maher Abboud, Michelle Turner, Etienne Duguet and Michel Fontanilleb, J. Mater. Chem., 1997, 7(8), 15271532.

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TGA Results
TGA thermogram of MPTS OX-50 & Aerosil 380

TGA results: m (100 800) 1.65 wt % loss for OX-50 and 11.8 wt % loss for Aerosil 380 Surface area: 7.6 times, wt loss = 7.2 times
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TGA Results
TGA thermogram of BCTC silane coupling agent

TGA results: m (100 800) Reflux method: (1.587% & 1.577% = avg. 1.58% ) weight loss Two step degradation characteristics
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Solid State NMR Results (13C & 29Si)

Cross-polarization combined with magic angle spinning (CP/MAS) were used to get NMR spectra. 4 mm ZrO2 rotor Calibration: TMS
29Si

= DSX Bruker 400Mhz Delay time: 3 sec Contact time: 2 msec Spinning rate: 6kHz
13C

= Bruker Avance II+ Spinning rate: 9KHz Delay time: 3 sec Contact time: 2.5 msec
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Solid State 29Si NMR

From 29Si CP/MAS NMR, it is possible to differentiate the different types of silicon atoms present in the silica particles: Q4, Q3, and Q2, that is, in the bulk, on the surface bonded to one OH and to two OH, respectively. T1, T2, and T3 correspond to the silicon atoms contained in the silane molecule which have formed one (or two, or three, respectively) Si-O-Si bond with the silica particle, or one Si-O-Si binding between two silanes.

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29Si

NMR Spectrum of Pristine OX-50 & AS380

Pristine OX-50
29

Si NMR Spectrum of AS380

1000 800 600

1200 1000 800

-100.1(Q3) -91.3(Q2)

Signal

Signal
-100 PPM -150 -200

400 200 0 -200 -400 0

-99.76(Q3)

600 400 200 0 -200

-50

-50

-100

-150

-200

PPM

29Si

NMR can detect three types of silicon atoms at about -90, -100, and 110 ppm, designated Q2, Q3, and Q4 according to the number of OSi groups bound, as shown below, where R is H or alkyl. Q2 = (RO)2Si(OSi)2, Q3 = ROSi(OSi)3, Q4 = Si(OSi)4

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R. Joseph, S. Zhang, and W. T. Ford, Macromolecules, 29, 1305-1312 (1996).

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29Si

NMR Spectrum of MPTS OX-50 & MPTS AS380

29

Silane Treated OX-50 (Reflux method)

Si NMR Spectrum of MPTS AS380
3000 2500 2000
Signal

-101.2(Q3) -57.0(T2) -67.2(T3)

-108.5(Q4)

800

600

-56.5(T2) -48.5(T1)

1500 1000 500 0 -500 0 -50

-99.9(Q3)

Signal

400

200

-100 PPM

-150

-200

-200 0 -50 -100 -150 -200

PPM

Silanol signals of pristine OX-50 (Q2 & Q3) decrease upon silanization compared to Q4 signal for MPTS treated OX-50 sample. MPTS AS380 has lower T3 and higher T1 contents compared to MPTS OX50.

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13C

NMR Spectrum of MPTS OX-50(3 days vacuum dried sample)

MPTS modified OX-50
1200 1000 800

C=C
*

Intensity

600 400 200 0 -200 200

150

100

50

PPM

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. R. Joseph, S. Zhang, and W. T. Ford, Macromolecules, 29, 1305-1312 (1996).

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13C

NMR Spectrum of MPTS AS380

(after 3 days more

vacuum dried sample)

One more peak at 58.4 ppm observed:

1)Rotation about the CO C bond may be highly restricted due to hydrogen bonding of C=O groups of methacryl with Si-OH groups on the silica surface, therefore peak splittings due to conformational differences may be observed. 2)Residual ethanol
8000

MPTS modified Aerosil 380

**

6000

Intensity

4000
58.4

2000

-2000 200

150

100

50

Ethanol: 18.4 and 58.3 ppm

* : 22.0 & 16.5 ppm

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PPM

R. Joseph, S. Zhang, and W. T. Ford, Macromolecules, 29, 1305-1312 (1996).

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29Si

NMR Spectrum of BCTC OX-50

29Si Solid State NMR (bicycloheptenylethyltrichlorosilane treated OX-50)

1400 1200 1000

T2

Q3 T3

Q4

Four peaks at -107.9, -103.2, 66.5, -58.0 ppm

Intensity

800 600 400 200 0 0 -50

-100

-150

-200

PPM

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13C

NMR Spectrum of BCTC OX-50

BCTC modified OX-50
1800 1600 1400 1200

(after 3 days

vacuum dried)

Peaks at 136.2, 131.6, 58.1, 48.8, 44.7, 41.9, 32.0, 29.0(shoulder), 27.2, 16.9, and 10.0 ppm 11 peaks But BCTC has 9 carbons in the molecule. Therefore, 2 more peaks may be caused by endoand exo- form of BCTC. Peaks at 136.2 and 131.6 ppm are by olefinic C=C.

C=C

Intensity

1000 800 600 400 200 0 -200 200

150

100

50

PPM

Ethanol: 18.4 and 58.3 ppm

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Dispersion test in H2O

2 ml water only in the vial. OX-50 silica dispersed well in the water. Some MPTS OX-50 dispersed, but most of them in the bottom of the vial. Most BCTC OX-50 stayed in the bottom of the vial. Hydrophilicilty OX-50 > MPTS OX-0 > BCTC OX-50

a) MPTS OX-50 in water b) BCTC OX-50 in water c) OX-50 in water

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RTIR measurement by NIR

5.0 mW/cm2 intensity 320~500 nm wavelength [{10 mol % TMPTMP+ 90 mol % GDMP} + TMPDE] +0.2 wt % DMPAC=CH combination photoinitiator

Decrease of this peak area was used.

After UV

band

Before UV

S-H band

1st overtone of TMPDE C=C-H band

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J. B. Ang, D. JT. Hill, P. J. Pomery, and H. Toh, Polym. Int., 52, 1689-1693 (2003).

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Real Time FTIR

Monitoring reactions in real-time. Peak area change with UV irradiation was generated in real time, that is, the data from both UV curing and FTIR monitoring are collected simultaneously to follow the time dependent decrease of the C=C bond.

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Peak area change with UV irradiation time

6 5 4

Peak Area

UV irradiation started here

3 2 1 0 -1 0 1 2 3 4 5

Time (min)

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Fabrication of Nanocomposite

Mixing
Silica particle

Mixing + UV

Composite

Ene Monomer

Thiol monomer + DMPA solution

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DMA Measurement Conditions

1. 1 1/2 days storage in the dark at ambient conditions for UV irradiated samples 2. Strain % = 0.8 %, frequency: 3Hz 3. Room temperature -80 equilibrate for 2 mins heating 3/ min rate to 180 4. Measurement of three specimens to get average value

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DMA Curves for (TMPDE+GDMP) system

Black curve: Pristine

10000
DMA10%ox-a DMA10%mpts-a DMApri-b DMA10%bctc-a

2.5

1000

100

10

lllllll lll llll l ll lllllll l ll l ll l l l llll ll l l ll l ll l l l l l ll l llll l ll lll l ll ll lll ll l l l ll l l l lll l l l ll l l l l l ll l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l ll l l l l l l ll l ll l l l l ll l l ll l lll l ll ll l ll l l ll ll l l ll l l l l ll lll l ll ll l l ll l l l ll l l ll l lllll l lll l l ll ll l ll lll l ll l l ll l l ll ll l l ll l ll l l ll l l l l lll l l ll l l l ll l ll l ll l lll l lll l lll ll l l l lll l l ll l l ll ll lll l lll l l l ll l l ll ll l ll l l l l llll lllll l ll ll ll lll llllll l llllll lllll lllll l l l l ll lll llllllllll l llllllllll l ll l l ll l ll ll llllllllllllll llllllllll lll l ll lllllllllll ll llllllllllllllllll l ll ll lll llllllllllllllllllll lll ll l llllllllll llllllllll llllllllll lllllllllllll ll l l l l l l l ll llll l l ll l l ll l ll ll lll llllllllllllllllll ll l

2.0

1. Modulus in the glassy (-70) and rubbery region (100) increased by addition of fillers whether the fillers were modified or not. Good reinforcing effects. 2. The intensity of the tan peak in all the filler added polymers was reduced compared to pristine (TMPDE+GDMP) system through reduction of the polymer concentration. 3. Tg was very little affected by the incorporation of fillers.

Storage Modulus (MPa)

1.5

Shoulder?

1.0

0.5

0.0

0.1 -80

-0.5 -30 20 70 120 170

Universal V4.3A TA Instruments

Temperature (C)

Tan Delta

4. Shoulder peak can not be

removed after heating, cooling and reheating cycle.

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R. B. Bogoslovov, C. M. Roland, A. R. Ellis, A. M. Randall, and C. G. Robertson, Macromolecules, 2008, 41, 1289-1296.

Effects on Tg
(-25.4 ~ -27.5 : small effect on Tg means weak interactions between resin molecules and filler surface)

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Glassy Region Storage Modulus

Storage Modulus at -70C
3.0 2.8
OX-50 MPTS OX-50 BCTC OX-50 AS380 MPTS AS380

Storage Modulus (GPa)

2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 0

Generally increase with filler contents.

10

15

20

Filler Contents (wt %)

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Rubbery Region Storage Modulus

- Strong surface area effect. (AS380 and MPTS AS380 vs. OX-50 and AS 380). - Resin system with OX-50 showed lowest storage modulus at 20 wt% filler concentration, which may be caused by the poor dispersion stability of OX-50, causing agglomeration.

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Particle Size Effect on Transparency

AS380 (primary particle size: 7 nm) incorporated nanocomposites are more transparent than those of OX-50 (primary particle size: 40nm) incorporated nanocomposites.

(a) 15% OX-50

(b) 15% AS 380

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FE-SEM Results for TMPTMP+TATATO

To investigate the dispersion state of the silica nano-partilces in the cured resin, cured composites were fractured in liquid nitrogen, and then the morphology of the fractured surface were observed with FE-SEM.
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Results for (TMPDE+GDMP) System

1. The moduli of the TMPDE+GDMP system with silica particles increased. 2. Nanocomposite with smaller particle sizes such as AS380 & MPTS AS380 as fillers showed higher modulus than those of OX-50 & MPTS OX-50 incorporated nanocomposites.

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Thank you for your kind attention.

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