design and optimization of precipitated silica for reinforcing rubber

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Design and Optimization of Precipitated Silica for Reinforcing Rubber Chetan Suryawanshi, Chunyan Chen and Dale W. Schaefer, Department of Materials Science & Engineering University of Cincinnati, Cincinnati, OH 45221-0012, Peyman Pakdel Bridgestone/Firestone Inc 1200 Firestone Parkway Arkon, OH 44317-0001 Lou Gatti J.M Huber Corporation 907 Revolution Street P.O Box 310 Havre De Grace, MD 21078 Jan Ilavsky National Institutes of Standards and Technology Advanced Photon Source Argonne National Labroratory, 9700 South Cass Avenue Argonne, IL 60439 Peter R. Jemian University Of Illinois At Urbana-Champaign Advanced Photon Source Argonne National Labroratory, 9700 South Cass Avenue Argonne, IL 60439

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Design and Optimization of Precipitated Silica for Reinforcing Rubber. Chetan Suryawanshi, Chunyan Chen and Dale W. Schaefer, Department of Materials Science & Engineering University of Cincinnati, Cincinnati, OH 45221-0012, Peyman Pakdel Bridgestone/Firestone Inc 1200 Firestone Parkway - PowerPoint PPT Presentation

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Page 1: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Design and Optimization of Precipitated Silica for Reinforcing Rubber

Chetan Suryawanshi, Chunyan Chen and Dale W. Schaefer,Department of Materials Science & Engineering

University of Cincinnati,Cincinnati, OH 45221-0012,

Peyman PakdelBridgestone/Firestone Inc1200 Firestone ParkwayArkon, OH 44317-0001

Lou GattiJ.M Huber Corporation907 Revolution Street

P.O Box 310Havre De Grace, MD 21078

Jan Ilavsky National Institutes of Standards and Technology

Advanced Photon SourceArgonne National Labroratory, 9700 South Cass Avenue

Argonne, IL 60439

Peter R. JemianUniversity Of Illinois At Urbana-Champaign

Advanced Photon SourceArgonne National Labroratory, 9700 South Cass Avenue

Argonne, IL 60439

Page 2: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Reinforced ElastomersSurface

Treatment Polymer

Additives

1 m

Mastication

Flame or SolutionSynthesis

Forming

Filler

Page 3: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Structural Complexity10

1

0.1

What Controls agglomerate size?When do they form? What controls fragility?

How does Silica/Carbon Reinforce?What is the optimum structure?

What controls aggregate size?What is the optimum size

What is the optimum primary?Are the primaries porous?What controls primary size?

Agglomerates

Primary Particles

Aggregates

Page 4: Design and Optimization of Precipitated Silica for Reinforcing Rubber

10-7 10-6 10-5 0.0001 0.001 0.01 0.1 1 10

Light LS230SAXS BH (UNM)SAXS PH (UNM)Diffraction

Inte

ns

ity

q (Å -1 )

-4.0

-2.0

-3.1

RG = 89

Morphology From Scattering

100,000 nm 200 nm 0.5 nm10 nm

O

OOO

Si

O

Si

O

O

OH O

SiHO

Si

Agglomerate Aggregate PrimaryParticle

NetworkPolymer

Page 5: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Powder Synthesis

Agglomeration

Aging

Aggregation

+

+Nucleation

Growth

Si

OH

O-O O-

Si

O-

OH

O-

Polymerization

Parameters affecting silica polymerization•Temperature•pH•Time•Ionic strength•Shear due to agitation

Page 6: Design and Optimization of Precipitated Silica for Reinforcing Rubber

In Situ Growth

10-2

10-1

100

101

102

103

104

105

106

107

108

109

Inte

nsi

ty

0.0001 0.001 0.01 0.1 1

q (Å-1

)

Stage1

Stage2

Stage3

Stage4

Stage5

Agglomerate regime

aggregate regime

primary particle

UNICAT USAXS

Page 7: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Stabilization TechniquesElectrostatic Stabilization

Steric Stabilization

0.6

0.4

0.2

0.0

Ion

ic s

tren

gth

(m

ol/l)

3002001000

Reaction time (min)

HS119

HS-SA133

HS-SA165HS-SA172

HS-SA183

**

*

*

*

*

Page 8: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Silicic Acid Neutralization

10-1

100

101

102

103

104

105

106

107

108

109

1010

Inte

nsi

ty (

cm)-1

0.0001 0.001 0.01 0.1 1

q (Å)-1

RHS_SA_133_DSM rHS_SA_165_DSM rHS_SA_172_DSM rHS_SA_183_thickness_084_DSM rHS_11_thickness_087_DSM

Unmodified silica

Modified silica 1 HS-SA133

Modified silica 2 HS-SA165

Modified silica 3 HS-SA172

Modified silica 4 HS-SA182

Page 9: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Morphology of Modified Protocols

10-2

10-1

100

101

102

103

104

105

106

107

108

109

1010

Inte

nsi

ty (

cm)-1

0.0001 0.001 0.01 0.1 1

q (Å)-1

'rHS_S1289_011.101' RHS11_baseline 'rHS_SA_183_thick'

Electrostatic

Steric

10-2

10-1

100

101

102

103

104

105

106

Inte

nsi

ty (

cm)-1

0.0001 0.001 0.01 0.1 1

q (Å)-1

Stage 3 Suspensions 'rHS2000-Baseline' 'Copolymer Modified(SE-218-3)' 'Electrostatic modified'

PowderSolution

Page 10: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Agglomerate Evolution

Electrostatic

Steric

Early Slurry

Late Slurry Dry Powder

Page 11: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Comparison of Powder and Rubber Dispersion

10-2

10-1

100

101

102

103

104

105

106

107

108

Int

ensi

ty

0.0001 0.001 0.01 0.1 1

q(Å-1)

-4

-4

HiSil 190 5% in Rubber

HiSil 190 Powder

Page 12: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Mechanical Properties

4

3

2

1

Str

ess

(MP

a)

121086420Strain (mm/mm)

RHS119 rSA_133 rHS_1289 rHS_2000 rRubber

Homemade

Commercial

Unfilled Rubber

Electrostatic

Steric

Page 13: Design and Optimization of Precipitated Silica for Reinforcing Rubber

Filler dispersion in rubber