Polymer (nano)composites

: key-role of chemistry
Composite :

Heterogeneous association of two or several non-miscible materials, generally of

different chemical nature, forming a multi-phase material characterized by a set of
properties that none of the individual constituent displays separately.
« Natural » composites
Mother-of-pearl « Nacre »
Bone structure
Fibrillar
collagen

« Silk » proteins

Spider thread

Hydroxyapatite
crystals
(500nm x 250nm x 25 nm) Glycin-rich
amorphous
matrix (70%) Crystals of alanine-rich proteins
 Wood structure :

Typical hard wood anatomy

Chemical composition

Constituent Weight fraction(%)

Cellulose 45-50
Hemicellulose 20-35
s
Lignin 22-30
Extractives 0-10
 Wood
structure :

Cellulose
fibers

Lignin matrix
Macrofibril

Microfibri
l
Natural fiber composite
– Crystalline cellulose
– Matrix of hemicellulose,
lignin, and amorphous
Cellulos cellulose
e chains
– High stiffness especially
in fiber direction
 « Synthetic »  composites

- Used for thousands of years like « Pisé » (adobe : blend of mud and straw)

- More recent : concrete (cement and gravel)

- « Modern » composite matérials :

- Polymers filled with particles (end of 19th century)

- Polymers reinforced by continuous fibers (since ~1935)

Definitions :

- Matrix : continuous phase, embedding the dispersed materials. When the

matrix content is much less than the dispersed phase, the matrix can be named
« binder ».
- The dispersed phase is often called « reinforcement » since its main role
aims to enhance the matrix resistance to mechanical constraints.

- These reinforcement materials are usually formed of continuous fibers

(unidirectionial, woven or non-woven mat) or particles (isotropic or anisotropic).
 Various families :

Types of matrices :

- metallic, ceramic, polymeric;

Types de fibers :

- metallic (rares), ceramic, carbon-based, glass, polymeric (Kevlar,

Dyneema…);

Types of « reinforcing » particles :

- silica, alumina, clays (kaolin, mica,…), metals, carbon black, graphite,…

Chapter 2 :

Polymer microcomposites
filled with microparticles
Typical example : polyethylene filled with reinforcing
inorganic particles

Hydrophobic Hydrophilic-surface
polyethylene Particulate fillers

Uniaxial

constraint

Fillers aggregation => Generation of voids => propagation

mechanical brittleness of the rupture
 Uniaxial

constraint

Generation of voids => propagation

of the rupture

(From Prof. G. Marosi)

 Effect of particulate fillers on mechanical properties
Materials Stiffness Brittleness Brittleness
(fast (slow
deformation) deformation)
Young’s Impact Elongation at
modulus strength break
(IZOD test) (tensile test)
(GPa) (J/m) (%)

HDPE* 0.7 80 900.0

HDPE + 40wt% kaolin 3.1 17 1.6

HDPE + 40wt% mica 6.5 20 0.3

HDPE + 40wt% CaSO4 2.8 15 1.3

HDPE + 40wt% CaCO3 2.7 21 3.0

non-homogeneous mineral dispersion
BRITTLENESS
poor mineral-polymer interaction

* High density polyethylene (Mw ~

Tensile testing machine Impact testing machine

ISOD

CHARPY
Solutions ?
1°) Decrease the hydrophilicity of the filler surface
Chemical treatment of the filler surface
(alkoxysilane, alkylamine, Al carboxylates,…)

Improvement of the Poor adhesion

dispersion

Less brittle composite materials

 2°) (Polymer) grafting reaction onto filler surface

 via chemical treatment of filler surface with coupling agents

(vinylic or methacrylic alkoxysilanes, aluminum methacrylates,…)

followed by polymer grafting all along melt blending/processing

Improved dispersion Reinforced adhesion =>

Mechanical rupture within the
matrix !

Rigidity and resistance to break significantly improved

 Filler - Polymer Dispersion / Interaction

• Surface modification of the

filler
Surface agents (monofunctional) : Coupling agents* (difunctional/radical grafting):
-silanes; -vinyl silanes;
-alkylamines; -aluminum methacrylates; ...
-Al carboxylates;
-titanate esters; ...
Better filler dispersion… with at best some improvement of adhesion*

• Filler “pre-encapsulation”
 Surface coating by a crosslinked resin layer (Ceraplast technology)
(as diffuse « ca.12nm » interface of intermediate elastic modulus)
-coupling agent (-unsaturated amines)
-difunctional monomers (dienes, dimethacrylates)
-thermally activated initiators (peroxydes)
Combination of stiffness/toughness - costly

• Polymerization from the filler surface

POLYMERIZATION-FILLED COMPOSITES : PFC’s

Polymerization-Filling Technique
ENIKOLOPIAN N.S., USSR Pat. 763,379 (1976)
HOWARD E.G., US Pat. 4,104,243 and 4,097,447 (1978)
fixation of a Ziegler-Natta type catalyst
onto the filler
olefin polymerization from the filler
surface/pores
Filled-Polyolefin
Filler

Z.-N. Catalyst Olefin

(i.e., ethylene)

PFT on a wide range of fillers :

 acidic surface (kaolin, silica, glass beads,
…)
 basic surface (magnesium hydroxide,...)
 organic fillers (graphite, carbon black,...)
 metallic fillers (nickel, zinc,…)
Polymerization-Filling Technique
Mainly developed for Ziegler-Natta catalysts (transition metal complexes …)

Transition metal (M)

Physical adsorption Chemical grafting

Sublimation, Impregnation Support-OH + MRn

or Deposition

Support-OMRn-1 + RH
Solid (M) phase on the filler
surface

Catalyst types : Ti : TiCl4/AlR3; Ti(BH4)3; Ti(OR)4/AlR2Cl

Zr : Zr(CH2-C6H5)4; Zr(BH4)4
V : VCl4/AlR3 ; (VCl3 + VO(OEt)3)/AlEt2Cl
Cr : CrRCl4; Cr(O2CR)3
Hf : Hf(CH2-C6H5)4; Hf(BH4)4
 Metallocenes : Single Site Catalysts in Olefin Polymerization

 General structure – activation by methylaluminoxane MAO

CH3 CH3
X + Al O M + Al O
M CH3
X
n X n

M = Ti, Zr, Hf MAO for : - methylation

X = Cl, CH3, ... - cationization
- protic scavenger action

 Properties
Ziegler-Natta
-High catalyst activity

mol% comonomer
-Molecular weight control
metallocene
(sensitivity to hydrogen)
-Copolymerization with -olefins
(thermoplastic to elastomer)

molecular masses
PFT via Metallocene Catalysts
Composite
filler

MAO Metallocene Monomer

Deagglomeration Immobilization of Homogeneous

of the filler the active species dispersion of the filler
through
Fixation possible electrostatic
on basic, acidic, interactions
organic, metallic
surfaces
(-)
CH3 (+)
Protection of Al O
Mt
R
active catalyst X n
 PFT via metallocene catalysis : some applications
• Filler precoating : Dispersion of coated glass beads in HDPE
Precoating of glass beads by
either polyethylene (HDPE) or ethylene/1-octene copolymer (LLDPE)
and composites filled with 20 wt% glass beads
Composite E (Gpa) r (%) r (MPa) I.E. (kJ/m2)
HDPE Filler coating
Matrix (wt %)
1a) - 1.7 636 24.7 12.0
1a) HDPE (14.5) 1.3 659 28.5 150.5
10b) - 1.4 4.2 26.4 14.5
10b) LLDPE (7.0) 1.5 6.9 28.9 41.0
a) Melt flow index under 2.16 kg load MI2 = 1g/10min.; b) MI2 = 10g/10min.
• AFM Phase detection coated glass beads/HDPE
composite

bare glass beads/HDPE

composite
 PFC via metallocene-based
Conclusions
catalysts

« Homogeneous » polyolefinic-based composites

Versatility of
 microsized fillers : - acidic (kaolin, silica, ...)
- basic (magnesium hydroxide,...)
- organic (graphite, cellulose,…)
- metallic (nickel, iron,…)
metallocene-based catalysts : Ti,Zr,(Hf),...

Allows for
 « control » over the molecular parameters
- Mn (hydrogen as transfer agent)
- composition (-olefin copolymerization)
 high catalytic efficiency
 performant mechanical properties : stiffness and toughness (even at high
filling)
- filler deagglomeration
- homogeneous filler dispersion (encapsulation)
- enhanced interfacial adhesion