The Effect of Inorganic

FullereneFullerene-like Nanoparticles &

Nanotubes on Polymer properties
NanoMaterials, Ltd.
Presented by Dr. Alla Zak
February 7th , 2011

NanoMatetrials (NML) was

established in 2002 as a result of
Successful Transfer from Science to
Industry.

Weizmann Institute of Science

Laboratory of Prof. Reshef Tenne
1992 discovery

NML Offices and R&D Labs

Nes Ziona, HiHi-Tech Park

Synthesis of Inorganic nanoparticles from layered transition metal

dichalcogenides (WS2 and MoS2) :
Inorganic Fullerene-like nanoparticles (IF) and Nanotubes (INT)

Platelet

MoS2 Fullerene-like
Nanoparticle

WS2 nanotube

TEM images of IFIF-WS2

NanoMaterials
Pilot plant

80kg
80kg reactor

NanoLubNanoLub- trade name of IF based Materials .

Products based on NanoLub:

Engine and gear oil concentrate

Sonol engine oil with NanoLub

*

Bicycle chain lubricants

Formulated grease
Grease concentrate (paste)

Solid lubricant for ball bearings

Lab Reactor for WS2 Nanotube synthesis

New product WS2-INT succeeded in scale up.

New applications - strengthening of composite materials

and reduction of their friction and wear.
Lab Reactor

Growth mechanism of WS2

Nanotubes

Inorganic WS2 Nanotubes

SEM images

TEM
SEM

Inorganic FullereneFullerene-like Nanoparticles

properties

Nanosize 5050-350 nm, semispherical shape

IF withstand 25 GPa Shockwave pressure [1
[1]
IFIF-WS2 nanoparticles withstand 12.5 GPa
uniaxial compression stress.[
stress [2]
Popular stiffness for individual IF 350350-360
Nm-1 [2]
pellet generates impact shock
IF exhibited exfoliation under ~1
~1 Gpa uniaxial
pressures from a few GPa up to a few
pressure probably caused by shear force at the
tens of Gpa . [1]
contact point during tribological test [3
[3*]
Low friction solid lubricant[3
lubricant[3]

[1] The dynamic pressure resistant performance

of IF cages was investigated via shock recovery
experiments... The shock-absorbing ability of the IF
enables them to survive pressures up to 25 GPa
accompanied with concurrent temperatures of up
to 1000 C without any significant structural
degradation or phase change.
1.
2.
3.

Y. Q. Zhu, et. al. ,Nottingham University, UK,

Advanced Materials, vol. 17, (2005), 1500-1503
O. Tevet, et al., Nanotechnology 21 (2010) 365705 (6pp)
Joly-Pottuz L, et al., N 2006, J. Appl. Phys. 99 023524

AFM cantilever probe in HRSEM [2]

Inorganic WS2 Nanotubes properties

Size: 8080-120nm
120nm in diameter , 1010-20 m
in length
Shock wave resistance for pressed INT
powder 21
21GPa,
21GPa, collapse under
35GPa[
35GPa[4
GPa[4]
Young modulus from tensile and bending
tests for individual INT: 152152-170 GPa
[5,6]
Tensile strength and strain are * 4-16GPa
16GPa
[4]
WS
nanotubes
are
capable
of
and 5-214%
14% [5
[5]
withstanding shear stress caused by shock
waves of up to 21 Gpa. Under similar shock
conditions, WS2 tubes are more stable than
carbon nanotubes (CNT), the latter being
transformed into a diamond phase.

[4] Shock-Wave Resistance of WS2 Nanotubes, Y.

Q. Zhu, H. W. Kroto, J. Am. Chem. Soc., 2003, 125
(5), 1329-1333
[5] I.Kaplan-Ashiri, et al., PNAS, January 17, 2006
vol. 103 no. 3 523528
[6] I.Kaplan-Ashiri, et al., (2004) J. Mater. Res. 19,
454-459.

Nanocomposites with IF and INT

Target::
Target
To enchance mechanical properties of the polymer matrix by inclusion of
Inorganic NanoParticles (INP) in polymer matrices.
Basis:
The combination of the polymer flexibility with special properties of
inorganic nanoparticles should achieve the target. The properties are:
1. High Modulus, 2. High Impact Resistance, 3. Low Friction, 4. Nanosize a)
allow small amounts of filler

filler
gain in weight, b) decrease of local stress
*
concentrations in polymer, etc.
Different matrixes were studied:
*Polyacetal [7]
*Epoxy (different types) [7
[7,8]
*Isotactic polypropylene (iPP
(iPP)
iPP) [9
[9]
*Polyphenylene sulfide (PPS) [10
[10]
10]
*Polyetheretherketone (PEEK) [11
[11]
11]
*Polymethiyl methacrylate (PMMA, perspex)
perspex)
*Silicone adhesives

The Composites start from Dispersion.

IF and INT could be Homogenously Dispersed in
different polymer matrixes
SMA
F1000
(Sartomer)
Sartomer)

Al
substrate

Dr. F. Solomon-Tsvetkov, Daren laboratories, 2005, 2007

coating
IFIF-WS2
particles

Polyphenylenesulfide (PPS) nanocomposite with

IFIF-WS2
It was suggested that IF accelerate the crystallization
rate of PPS, and this due to
the nucleation effect of the IFIF-WS2 favours the formation of small imperfect
crystals, which can provide excellent rigidity to the crystalline PPS.

Increase in storage modulus of 4040-75%

75%

M. Naffakh, C. Marco, M. Gmez, J. Gmez-Herrero, I. Jimnez, J. Phys. Chem. B 113,

10104 (2010)

Polyetheretherketone (PEEK) nanocomposite with

IFIF-WS2
Polymer coatings have been produced using aerosolaerosol-assisted deposition
process
1-20%
20% of IFIF-WS2 increase Hardness and Modulus by up to 6767- 60%
60% ;
1% IFIF-WS2 increase the T of decomposition by 2020-30
30C (not shown)

X. Hou, C.X. Shan, K.-L. Choy, Univ. Nottingham, Surf. & Coat. Tech. 202 (2008)
2287-2291.

Friction for PEEK / IFIF-WS2

nanocomposites
2.5% IFIF-WS2 reduce COF by up to 70%
70%

2.5% IF

X. Hou, C.X. Shan, K.-L. Choy, Surface & Coatings Technology 202, 2287 (2008)

Modulus, tensile strength, thermal stability, thermal conductivity (not

shown), crystallization temperature (not shown) of PEEK exhibited
remarkable improvement with the addition of IFIF-WS2.
Storage modulus increased by up to 31%
31% and Tg by up to 17 C

Novel MeltMelt-Processable Polyether ether ketone (PEEK)/Inorganic FullereneFullerene-like WS2

WS2
Nanoparticles for Critical Applications M. Naffakh et al. , J. Phys. Chem. B 2010,
2010, 114,
114, 11444
1144411453

Thermogravimetric analysis (TGA) for

PEEK / IFIF-WS2 nanocomposite
The incorporation of the IFIF-WS2 nanoparticles induces a remarkable
thermal stabilization of the polymer matrix and Nanoparticles as well,
with an increase of the initial and final degradation temperature (Ti) by
5555-60 C in air and N2 atmospheres (20
(20
20C/min)

"

Novel MeltMelt-Processable Poly(ether ether ketone)(PEEK)/Inorganic FullereneFullerene-like WS2

WS2
Nanoparticles for Critical Applications M. Naffakh et al. , J. Phys. Chem. B 2010,
2010, 114,
114, 11444
1144411453

Epoxy Nanocomposite with IF-WS2

IFIF-WS2 enhances:
shear strength,
shear modulus,
modulus,
& peel strength of
epoxy;

Evidences for chemical

interaction between the
nanoparticles and the
epoxy by FTIR (ATR
mode):

R-O-S

100% increase

M. Shneider, H. Dodiuk, S. Kenig and R. Tenne, J. Adhesion Sci. Technol., 24, 10831095 (2010)

Dispersion of INT
First type synthesis

INT after High mixing

New synthesis - less agglomerated INT

Increases dispersion from 10%
10% to 80%
80%

Optic Microscope analysesanalysesbad resolution and depth of focus but

good tool for day to day lab investigations
INT in Silastic J (very viscose adhesive):
a) Initial hand mix 50:
b) Final mix with 0.1% of
50:50;
50;
NT

5m
5m

INT in Silastic J SEM images

The effect of WS2 nanotubes on the

properties of Epoxy based nanocomposites
Tg increased by 6.5C
49%
49% improvement
in Fracture Toughness

0.5%

E. Zohar S. Baruch, M. Shneider, H.

Dodiuk,
S. Kenig, R. Tenne and H. D. Wagner,
INTINT-WS2 concentration [%wt]

J. Adhesion Science and Technology 0

(2010)
115, in press

EpoxyEpoxy-INT
nanocomposite

85%
85% improvement in Peel Strength

39%
39% improvement
in Shear Strength

E. Zohar et al., J. Adh. Sci. and Tech. 0 (2010), 115,

in press

Tribological properties of Epoxy - IF/INTIF/INT-WS2

nanocomposite
Pin on disk, 0.35 m/sec, 20 N, 0.25 MPa,
MPa, Dry friction
53%
53% and 88%
88% reducing of wear for 1wt% IF and 0.5wt% INT
Reproducible results
2
1.8
1.8
1.6
1.4

Wear,
m/min

1.2
1
0.84
0.8
0.6
0.4
0.22
0.2
0
Neat Epoxy

IF-WS2 1%

INT-WS2 0.5%

Prof. L.Rapoport, Tribological lab., HIT, June 2010

2004 The first work on nanocomposite with IFIF-WS2 in Epoxy and

Polyacetal (Delrin)
Inorganic Nanoparticles filled polymer composites show
low friction and high wear resistance

Friction Force, N

= 0.6

=0
=0.3

Time, min
1 - Delirin; 2 - Delrin & 1.7 wt% IF-WS2
Pin on disk tester, dry conditions. Delrin is a commonly used material
for tribological applications; 2 times, wear ~5 times; transfer film
mechanism;
L.Rapoport,et all, Adv. Eng. Mat., 2004,
2004,6, No 1-2

Pin on disk tester, adding of paraffin oil every 5min.

Epoxy resin has poor tribological characteristics;
IF reduce brittleness of epoxy (SEM); 3times, wear ~10
~10
times; transfer film
= 0.06

Friction force, N

Epoxy

Epoxy & IF

=0.02

=0.007

Time, min
1 - Epoxy; 2 - Epoxy & 10wt% IF-WS2
mechanism;
L.Rapoport,et all, Adv. Eng. Mat.2004
Mat.2004,
2004,6, No 1-2

Zussman Group, Technion (2010

Summary
1. INTINT- and IFIF- WS2 are very promising materials
for enchancing mechanical and thermal
properties of the different polymer matrixes.

2. Inorganic Nanoparticles could be successfully

dispersed in organic solvents and in polymer.
3. The production of IF is in industrial scale today
and INT will be shortly.

Thanks for NanoMaterials team

and to all over the world
researchers

Thank you for your attention !

7. Polymer Nanocomposites with Fullerene-Like Solid Lubricant, L. Rapoport, O.

Nepomnyashchy, R. Popovitz-Biro, Yu Volovik, B. Ittah, and R. Tenne, Adv. Eng. Mater., 6,
44-48 (2004);
8. a) Toughening of Epoxy Adhesives by Nanoparticles, A. Buchman, H. Dodiuk-Kenig, A.
Dotan, R. Tenne and S.Kenig, J. Adhesion Sci. Tech. 23,
23 753768 (2009); b) The Effect of
Tungsten Sulfide Fullerene-Like Nanoparticles on the Toughness of Epoxy Resins, M.
Shneider, H. Dodiuk, S. Kenig and R Tenne, J. Adhesion Sci. Technol., 24, 10831095
(2010); c) The Effect of WS2 Nanotubes on the Properties of Epoxy Based
Nanocomposites, E. Zohar, S. Baruch, M. Shneider, H. Dodiuk, S. Kenig, R. Tenne, H.D.
Wagner, J. Adh. Sci. Tech., in press.;
9. Influence of Inorganic Fullerene-Like WS2 Nanoparticles on the Thermal Behavior of

Isotactic Polypropylene (iPP),

(iPP Naffakh et all, J. Polym. Sc.: Part B, 2007, 2309-2321;
10. a) Unique Isothermal Crystallization Behavior of Novel Polyphenylene
Sulfide(PPS)/Inorganic
Sulfide(PPS
Fullerene-like WS2 Nanocomposites, M.Naffakh, C. Marco, M. A. Gomez, I. Jimenez, J.
Phys. Chem. B, Vol. 112, No. 47, 2008; b) J. Phys. Chem. B 2009, 113, 71077115 ; c) Use
of Inorganic Fullerene-like WS2 to Produce Novel High-Performance Polyphenylene
Sulfide Nanocomposites: Role of the Nanoparticle Concentration , 2010 , submitted.

11. a) Microstructures and tribological properties of PEEK-based nanocomposite

coatings incorporating inorganic fullerene-like nanoparticles , X.Hou, C.X. Shan, K.-L.
Choy, Surface & Coatings Technology 202 (2008) 22872291; b) Novel Melt-Processable
Poly(ether ether ketone)(PEEK)/Inorganic
Fullerene-like WS2 Nanoparticles for Critical
ketone)(PEEK)/
Applications M. Naffakh, A. M. Dez-Pascual, C. Marco, M. A. Gomez, and I. Jimenez, J.

Phys. Chem. B 2010, 114, 1144411453