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先进材料与工程前沿
高分子纳米复合材料
于中振
北京化工大学 材料科学与工程学院 有机无机复合材料国家重点实验室
2014
Rapid Development of Materials
New York, 1938
Fujian, 宋元
Paris, 1889
Florida, 1981
Application of Polymeric materials
PA 6 NH2 + CH2 CH O DGEBA CH O CH2 + NH2 PA 6
PA 6
NH
CH2
CHOH
DGEBA
CHOH
CH2
NH
PA 6
Composition Nylon 6 Nylon 6 / Epoxy (0.3 phr) Nylon 6 / Epoxy (0.6 phr)
Mw
31, 000 36, 000 41, 000
Polymer 2005, 46, 5986
Binary Nanocomposite (B1)
Nylon 66/Organoclay (80/5)
Composites Science and Technology 2006, 66, 3097
Binary Blend (B2)
Nylon 66/SEBS-g-MA (80/15) 90 nm
Improved Dispersion Quality
SEM photographs of freeze-fractured surface
(a) 0.6 m (b) 0.2 m
Nylon 6 / POEg (80 / 20)
Nylon 6 / POEg / Epoxy (80/20/0.3)
Mn
20, 000 24, 000 26, 000
Dual Roles of the Epoxy in Nylon 6 / POEg
Increased melt viscosity of nylon 6 matrix by chain extension reaction
in situ formed nylon 6-co-epoxy-co-POEg copolymers by coupling reactions at nylon 6/POEg interface
PE + CB
PS
Gubbels F, et al. Macromolecules 1994, 27, 1972
Selective Localization of CB
PE 5%
PE/PS
3% PS 8% Interface 0.4%
Gubbels F, et al. Macromolecules 1994, 27, 1972
PP / CB + CNT
Filled with an Insulating Filler
PP + CNT + CaCO3
CaCO3 0% 20% 30%
Yu J, et al. Polymer 2008, 49, 3826
Using Two Conducting Fillers
CNT
CB
Kim JK, et al. ACS Appl. Mater. Interfaces 2009, 1, 1090
Using Two Conducting Fillers
Epoxy / CB / CNT
Kim JK, et al. ACS Appl. Mater. Interfaces 2009, 1, 1090
Embrittlement
blended with an immiscible polymer
Wu S. Polymer 1985, 26, 1855
Nylon 66/Rubber Blends:
1400
c = 0.3 μm
EPDM-g-MA Content in Nylon 66
1200
25 Notched Izod impact strength (J/m)
1000
15
800
10
600
Air Bus 2005
1 橡胶增韧聚合物 及增韧机理
Toughening of Nylon 66 with SEBS-g-MA
Polymer 1992, 32, 284
To Reduce Stiffness Loss
Approaches
To reduce rubber content by increasing viscosity of matrix To reduce rubber content by decreasing viscosity of rubber
Approach to Decrease Loading of Filler
Blended with an immiscible polymer
PP / CB + PS
Filled with an insulating filler PP / CNT + CaCO3
Use two conducting fillers
Smaller d
c
= d [ ( / 6 )1/3 – 1]
η d ~ 1 η m
minimum d
Wu S. Polymer 1987, 27, 335
η d > 1 η m
To increase m To decrease d
Compatibilization: Nylon 6 / POEg
Nylon 66 + SEBS-g-MA + Organoclay (Nylon 66 + SEBS-g-MA) + Organoclay
N1
N2
(Nylon 66 + Organoclay) + SEBS-g-MA Nylon 66 + (SEBS-g-MA + Organoclay)
N3
N4
Quantification of Clay in Nylon 66 Matrix and SEBS-g-MA Particles
Contribution of Epoxy Monomer
1200
Nylon 6/POEg
1000
Nylon 6/POEg/Epoxy (0.3 phr)
Notched Izod impact strength (J/m)
800
600
400
200
0 0 5 10 15 20 25 30 POEg content (wt %)
Reduced Toughness
Nylon 6 / ABS
CNT
CB
Meincke O, et al. Polymer 2004, 45, 739
Approach to Decrease Filler Loading
Blended with an immiscible polymer
PP / CB + PS
(Nylon 66 + SEBS-g-MA) + Organoclay
d ~ 202 nm
Nylon 66 + (Organoclay + SEBS-g-MA)
N2
N 3
N 4
N4
d ~ 137 nm
d ~ 281 nm d ~ 281 nm
Location and Exfoliation of Clay
400
c = 0.3 m
200
0 0.01 0.1 1 10
Matrix ligament thickness (µm)
Wu S. Polymer 1985, 26, 1855
HDPE/Rubber Blends
c = 0.6 m
c = 0.6 m
Argon AS. Polymer 1999, 40, 2331
Acta Materialia 2007, 55, 635
Sub-Surface Deformation
Notch
Fracture Surface
Subsurface Deformed Zone
N3: (Nylon 66+Clay)+SEBS-g-MA
Composites Science and Technology 2006, 66, 3097
Dispersion of SEBS-g-MA
Nylon 66 + Organoclay + SEBS-g-MA (Nylon 66 + Organoclay) + SEBS-g-MA
N1
N3
d ~ 120 nm
Reduce loading of conductive filler
1. Toughening of Nanocomposites
Nylon 66
Toughener: SEBS-g-MA
SEBS
ቤተ መጻሕፍቲ ባይዱ
O
O
O
Organoclay: Cloisite® 30B
CH3 N
+
CH2CH2OH
CH2CH2OH
Polymer 2005, 46, 5986
Effect of Blending Sequence
B0: Nylon 66 Binary Nanocomposites B1: Nylon 66/Organoclay (80/5) B2: Nylon 66/SEBS-g-MA (80/15) Ternary Nanocomposites N1: (Nylon 66 + SEBS-g-MA + Organoclay) (80/15/5) N2: (Nylon 66 + SEBS-g-MA) + Organoclay (80/15/5) N3: (Nylon 66 + Organoclay) + SEBS-g-MA (80/5/15) N4: Nylon 66 + (SEBS-g-MA + Organoclay) (80/15/5)
T < 100 nm Graphene
Increased Conductivity
Carbon Black Nanotube Nylon 6
Meincke O, et al. Polymer 2004, 45, 739
Reduced Ductility
Nylon 6 /ABS
CB
CNT
Meincke O, et al. Polymer 2004, 45, 739
Filled with an insulating filler PP / CB + CaCO3 Use two conducting fillers
PP / CB + CNT
Blended with an Immiscible Polymer
PE/PS (45/55) Cocontinuous Blend with 1% Carbon Black CB at PE/PS Interface
Reaction between anhydride and amine groups
CH C O O CH2 C O POEg + NH2 PA 6
CH CH2 POEg
O C NH C OH O
PA 6
- H2O
CH
C
O N PA 6
CH2 C O POEg
Chain Extension Reaction of Epoxy
Yu ZZ. J Appl Polym Sci 1998, 69, 1711
Improved Stiffness
2.5
Nylon 6/POEg Nylon 6/POEg/Epoxy (0.3 phr)
2
Flexural modulus (GPa)
1.5
1
0.5 0 5 10 15 POEg content (wt %) 20 25 30
To add glass fiber/inorganic particle in plastic/rubber blends
Toughening of plastics with rigid inorganic particles
Matrix Ligament Thickness ( )
L
d
= d [ ( / 6 )1/3 – 1]
2
高分子纳米复合材料 导电和增韧
Why Nanocomposites ?
Diameter Number Area
1 μm 1 A
100 nm 1,000 10 A
10 nm 1,000,000 100 A
Conductive Fillers
D < 100 nm Carbon Black
L < 100 nm Fiber/Tube
PP / CB + PS Filled with an insulating filler
PP / CB + CaCO3
Use two conducting fillers
PP / CB + CNT
Purposes
make a polymer conductive and super-tough
高分子纳米复合材料
于中振
北京化工大学 材料科学与工程学院 有机无机复合材料国家重点实验室
2014
Rapid Development of Materials
New York, 1938
Fujian, 宋元
Paris, 1889
Florida, 1981
Application of Polymeric materials
PA 6 NH2 + CH2 CH O DGEBA CH O CH2 + NH2 PA 6
PA 6
NH
CH2
CHOH
DGEBA
CHOH
CH2
NH
PA 6
Composition Nylon 6 Nylon 6 / Epoxy (0.3 phr) Nylon 6 / Epoxy (0.6 phr)
Mw
31, 000 36, 000 41, 000
Polymer 2005, 46, 5986
Binary Nanocomposite (B1)
Nylon 66/Organoclay (80/5)
Composites Science and Technology 2006, 66, 3097
Binary Blend (B2)
Nylon 66/SEBS-g-MA (80/15) 90 nm
Improved Dispersion Quality
SEM photographs of freeze-fractured surface
(a) 0.6 m (b) 0.2 m
Nylon 6 / POEg (80 / 20)
Nylon 6 / POEg / Epoxy (80/20/0.3)
Mn
20, 000 24, 000 26, 000
Dual Roles of the Epoxy in Nylon 6 / POEg
Increased melt viscosity of nylon 6 matrix by chain extension reaction
in situ formed nylon 6-co-epoxy-co-POEg copolymers by coupling reactions at nylon 6/POEg interface
PE + CB
PS
Gubbels F, et al. Macromolecules 1994, 27, 1972
Selective Localization of CB
PE 5%
PE/PS
3% PS 8% Interface 0.4%
Gubbels F, et al. Macromolecules 1994, 27, 1972
PP / CB + CNT
Filled with an Insulating Filler
PP + CNT + CaCO3
CaCO3 0% 20% 30%
Yu J, et al. Polymer 2008, 49, 3826
Using Two Conducting Fillers
CNT
CB
Kim JK, et al. ACS Appl. Mater. Interfaces 2009, 1, 1090
Using Two Conducting Fillers
Epoxy / CB / CNT
Kim JK, et al. ACS Appl. Mater. Interfaces 2009, 1, 1090
Embrittlement
blended with an immiscible polymer
Wu S. Polymer 1985, 26, 1855
Nylon 66/Rubber Blends:
1400
c = 0.3 μm
EPDM-g-MA Content in Nylon 66
1200
25 Notched Izod impact strength (J/m)
1000
15
800
10
600
Air Bus 2005
1 橡胶增韧聚合物 及增韧机理
Toughening of Nylon 66 with SEBS-g-MA
Polymer 1992, 32, 284
To Reduce Stiffness Loss
Approaches
To reduce rubber content by increasing viscosity of matrix To reduce rubber content by decreasing viscosity of rubber
Approach to Decrease Loading of Filler
Blended with an immiscible polymer
PP / CB + PS
Filled with an insulating filler PP / CNT + CaCO3
Use two conducting fillers
Smaller d
c
= d [ ( / 6 )1/3 – 1]
η d ~ 1 η m
minimum d
Wu S. Polymer 1987, 27, 335
η d > 1 η m
To increase m To decrease d
Compatibilization: Nylon 6 / POEg
Nylon 66 + SEBS-g-MA + Organoclay (Nylon 66 + SEBS-g-MA) + Organoclay
N1
N2
(Nylon 66 + Organoclay) + SEBS-g-MA Nylon 66 + (SEBS-g-MA + Organoclay)
N3
N4
Quantification of Clay in Nylon 66 Matrix and SEBS-g-MA Particles
Contribution of Epoxy Monomer
1200
Nylon 6/POEg
1000
Nylon 6/POEg/Epoxy (0.3 phr)
Notched Izod impact strength (J/m)
800
600
400
200
0 0 5 10 15 20 25 30 POEg content (wt %)
Reduced Toughness
Nylon 6 / ABS
CNT
CB
Meincke O, et al. Polymer 2004, 45, 739
Approach to Decrease Filler Loading
Blended with an immiscible polymer
PP / CB + PS
(Nylon 66 + SEBS-g-MA) + Organoclay
d ~ 202 nm
Nylon 66 + (Organoclay + SEBS-g-MA)
N2
N 3
N 4
N4
d ~ 137 nm
d ~ 281 nm d ~ 281 nm
Location and Exfoliation of Clay
400
c = 0.3 m
200
0 0.01 0.1 1 10
Matrix ligament thickness (µm)
Wu S. Polymer 1985, 26, 1855
HDPE/Rubber Blends
c = 0.6 m
c = 0.6 m
Argon AS. Polymer 1999, 40, 2331
Acta Materialia 2007, 55, 635
Sub-Surface Deformation
Notch
Fracture Surface
Subsurface Deformed Zone
N3: (Nylon 66+Clay)+SEBS-g-MA
Composites Science and Technology 2006, 66, 3097
Dispersion of SEBS-g-MA
Nylon 66 + Organoclay + SEBS-g-MA (Nylon 66 + Organoclay) + SEBS-g-MA
N1
N3
d ~ 120 nm
Reduce loading of conductive filler
1. Toughening of Nanocomposites
Nylon 66
Toughener: SEBS-g-MA
SEBS
ቤተ መጻሕፍቲ ባይዱ
O
O
O
Organoclay: Cloisite® 30B
CH3 N
+
CH2CH2OH
CH2CH2OH
Polymer 2005, 46, 5986
Effect of Blending Sequence
B0: Nylon 66 Binary Nanocomposites B1: Nylon 66/Organoclay (80/5) B2: Nylon 66/SEBS-g-MA (80/15) Ternary Nanocomposites N1: (Nylon 66 + SEBS-g-MA + Organoclay) (80/15/5) N2: (Nylon 66 + SEBS-g-MA) + Organoclay (80/15/5) N3: (Nylon 66 + Organoclay) + SEBS-g-MA (80/5/15) N4: Nylon 66 + (SEBS-g-MA + Organoclay) (80/15/5)
T < 100 nm Graphene
Increased Conductivity
Carbon Black Nanotube Nylon 6
Meincke O, et al. Polymer 2004, 45, 739
Reduced Ductility
Nylon 6 /ABS
CB
CNT
Meincke O, et al. Polymer 2004, 45, 739
Filled with an insulating filler PP / CB + CaCO3 Use two conducting fillers
PP / CB + CNT
Blended with an Immiscible Polymer
PE/PS (45/55) Cocontinuous Blend with 1% Carbon Black CB at PE/PS Interface
Reaction between anhydride and amine groups
CH C O O CH2 C O POEg + NH2 PA 6
CH CH2 POEg
O C NH C OH O
PA 6
- H2O
CH
C
O N PA 6
CH2 C O POEg
Chain Extension Reaction of Epoxy
Yu ZZ. J Appl Polym Sci 1998, 69, 1711
Improved Stiffness
2.5
Nylon 6/POEg Nylon 6/POEg/Epoxy (0.3 phr)
2
Flexural modulus (GPa)
1.5
1
0.5 0 5 10 15 POEg content (wt %) 20 25 30
To add glass fiber/inorganic particle in plastic/rubber blends
Toughening of plastics with rigid inorganic particles
Matrix Ligament Thickness ( )
L
d
= d [ ( / 6 )1/3 – 1]
2
高分子纳米复合材料 导电和增韧
Why Nanocomposites ?
Diameter Number Area
1 μm 1 A
100 nm 1,000 10 A
10 nm 1,000,000 100 A
Conductive Fillers
D < 100 nm Carbon Black
L < 100 nm Fiber/Tube
PP / CB + PS Filled with an insulating filler
PP / CB + CaCO3
Use two conducting fillers
PP / CB + CNT
Purposes
make a polymer conductive and super-tough