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ADVANCES IN NANOMER ADDITIVES FOR CLAY/POLYMER NANOCOMPOSITES
byTie Lan, Ying Liang, Gary W. Beall and Karl Kamena
Nanocor Incorporated
Corporate Technical Center
Arlington Heights, Illinois USA
The fundamental bases of clay/polymer nanocomposites are the clay utilized and the
surface modification, which renders that clay compatible with the polymer of interest.
Nanocor's surface modified clays are sold under the trade name, Nanomer. The
selection of appropriate clay involves a number of variables including, among others,
morphology, cation exchange capacity, cationic form, charge density, aspect ratio,
color, and degree of purity. The most critical of these are discussed in some detail as
they relate to surface modification and ultimately the formation of nanocomposites.
There are a number of surface modification options, including onium ion exchange, ion-
dipole treatment and coupling agents. These chemistries are also briefly discussed.
Performance properties for three clay/polymer nanocomposites, epoxy, nylon-6 and
nylon MXD6 are presented.
Additives '99, San Francisco, CA, March 22-24, 1999
INTRODUCTION
Pioneering work conducted at Toyota Central Research Laboratories Inc. on nylon-6
nanocomposites1 has generated several commercial products and stimulated a great
deal of interest in expanding the technology to other resin systems. The majority of
research conducted to date has focused on two broad areas of application. The first is
engineering polymers, where increases in modulus, tensile strength, heat distortion
temperature and retention of impact have made nanocomposites candidates for many
products that have not been traditionally plastic. The second is packaging, where
nanocomposites increase barrier to gases (i.e. oxygen, carbon dioxide, water vapor),
while retaining clarity, and where they expand the hot fill window.
Ube Industries Ltd. offered the first commercial nanocomposite products, a timing belt
cover for Toyota Motors2 and nylon-6 film for packaging3. In October 1998 Bayer AG
announced its intention to offer a line of nylon-6 nanocomposites for food packaging
film4. More recently, Eastman Chemical Company announced it is moving ahead with
the development of thermoplastic nanocomposites for the polyethylene terephthalate
(PET) packaging market5.
A number of factors combine to fuel interest in nanocomposite technology using clay
minerals:
Low loading levels
Transparency
Incorporation flexibility
Safety
Synergies with other additives
Low cost .
Nanocomposites typically contain 2-10% loadings on a weight basis, yet property
improvements can equal and sometimes exceed traditional composites containing 20-
35% mineral or glass. Machine wear is reduced and processability is better.
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Because mineral and glass fillers have densities twice that of polymers, weight sensitive
applications, such as auto parts, offer attractive opportunities.
Nanoclay particles have a dimension below the visible light wavelength. Properly
oriented
The particles are tough. They can withstand solvents, polymerization temperatures and
compounding shear. Consequently, they can be processed without concern about
degradation. The implications are obvious for initial fabrication and for recycle.
Clays are generally innocuous materials and have been used safely in consumer products
for decades. Timelines for regulatory approval are shortened.
A wealth of experience demonstrates they act synergistically with other minerals.
Recent research shows they are also synergistic with glass fiber6, extending flexibility to
create customized systems with unique sets of properties.
Lastly, clays are cost-effective. Research has progressed to the point where clay
nanocomposites can be formulated at cost premiums of 10-30%. Often lower cost
resins can be nanocomposited to perform like higher cost cousins with no premium
whatsoever.
The predominant nanoclay in commercial products, and in on-going research, is
naturally-occurring montmorillonite, the most abundant member of the smectite family of
clays. All smectite clays are impure as mined. They require extensive purification for use
in polymers such as plastic. Smectite clays are hydrophilic and therefore not compatible
with most polymers. They must be surface modified to render them suitable for more
hydrophobic systems. This paper focuses on fundamental mineralogical characteristics
of montmorillonite and how surface modification affects three basic categories of
nanocomposite properties.
BACKGROUND
As stated previously, the two critical factors affecting performance pertain to key
mineralogical characteristics and the types of surface modification used to render
nanoclay compatible with various polymers.
Clay Characteristics
Purity level, cation exchange capacity and aspect ratio are the clay characteristics of
greatest importance.
Purity is critical to achieving maximum increases in mechanical properties for engineering
applications and optimum clarity in packaging. Montmorillonite, as mined contains
between 5 and 35% impurities. These include both crystalline (e.g. quartz, feldspar,
calcite, etc) and amorphous materials (i.e. amorphous silica), which must be
substantially removed prior to surface modification.
In engineering applications impurities act as stress concentrators, resulting in poor
impact resistance. In films and packaging they contribute to haze. It is, therefore,
important to choose deposits that have the lowest amount of impurities or that are
amenable to beneficiation. A study7 comparing elongation-at-break of PVOH
nanocomposites containing clays of different purity levels, demonstrated that
montmorillonite should be at least 97.5% pure in order to ameliorate adverse effects.
Another important factor is cation exchange capacity (CEC). Montmorillonite's CEC
arises mainly from isomorphous substitution of divalent cations (ie. Mg+2, Fe+2) for
trivalent aluminum in the octahedral or innermost layer. Montmorillonites have
considerable substitution, 10-30 times greater than kaolin clay for example, causing a
charge imbalance in the structure that is compensated by exchangeable cations on the
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surface. CEC provides montmorillonite with the surface activity necessary for
acceptance of modifiers.
A final, important factor is the aspect ratio of the clay particle. Montmorillonites are
unique in having a platey structure and a unit thickness of less than one nanometer,
while the other two dimensions are in the micron range. Theoretical aspect ratios range
from 300 to 1500. The average surface area for a montmorillonite in its totally dispersed
(exfoliated) state is in the range of 700 sq. meters/gm. With such lofty aspect ratios and
surface areas, exfoliated montmorillonites should be highly effective as reinforcers and
barrier materials at low addition levels. This is indeed the case.
Surface Modification
Montmorillonite's surface is hydrophilic and requires modification to make it compatible
with most polymer systems. Surface modification can be accomplished through two
primary mechanisms, ion exchange and ion-dipole interaction. The edges of the platelets
can also be treated with traditional silane coupling agents. However, edges account for
less than 1 % of the total surface area. As a result, silane-coupling is normally used as
an adjunct to ion exchange or ion dipole treatment.
Ion exchange modification has been practiced since 19498. The original applications for
these materials were as thixotropes for solvent-based drilling muds, paints and greases.
Ion exchange involves the substitution of onium ions, which contain amine
functionalities, for the exchangeable cations on the platelet surface. Examples of this
type of Nanomer are grades I.24T and I.30TC.
Ion dipole treatment is a relatively new method7. It consists of attaching organic
molecules that contain groups such as alcohols, carbonyls or ethers to the exchangeable
cations on the surface of the clay. These partially-negative charged species interact with
partial positive charges existing on the exchangeable cations. In this process water
molecules are displaced from coordination to the cations and the surface becomes
hydrophobic. Examples of this art are the pyrrolidone-based Nanomers, I.35K and I.46D.
EXPERIMENTAL
Formation of Nanomer powders, epoxy, nylon-6 and nylon MXD6 nanocomposites
Onium ion modified montmorillonites (Nanomers I.24T, I.28E, I.30E, I.30TC and I.28MC)
are manufactured for both epoxy and nylon systems using ion exchange. The process is
a variation of that used traditionally for the manufacture of organophilic clay thixotropes.
The final product form is a flowable powder.
Epoxy nanocomposites are prepared by exfoliating directly in the resin and curing. In this
paper we are reporting results for Dow DER 331 epoxy, cured with two Huntsman
Jeffamine agents, D230 and D400, as well as ECA 100 from Dixie Chemical
Company. Jeffamines are amine-based. ECA 100 is an anhydride. Chemical resistance
data are also reported for Epon 828 cured with Epi-Cure 3164, a mixed-chemistry
curing agent. Both products are available from Shell Chemical Company.
Nylon nanocomposites are prepared using two incorporation routes, one involving
Nanomer addition to nylon monomer such as e-caprolactam with subsequent
polymerization (Toyota technology)* and the other utilizing a twin screw compounder
and high polymer. The results reported for compounding were obtained on
nanocomposites made through a 27mm co-rotating Leistritz D36 compounder.
Nanomers can be added straight or they can be first made into nylon concentrates and
letdown to achieve the desired loading.
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High barrier polymers have also been used to produce nanocomposites. One such
polymer is nylon MXD6, a product of Mitsubishi Gas Chemical Ltd. MGC's grade 6007 is
used to extrude nanocomposite films through the compounding route and the Leistritz
cited above.
Formation of Nanomer concentrates and epoxy nanocomposites
Concentrates such as Nanomer C.40EBA are also designed for epoxy systems and have
been prepared using a number of approaches. Concentrates are useful because they can
be added to neat epoxy with relative ease. In concentrate form a Nanomer is partially
exfoliated, requiring less shear to achieve a uniform mix prior to curing. Nanocor
formulates concentrates with the assistance of neutral (non-ionic) surface modifiers. The
desired clay to epoxy resin (liquid resin) weight ratio varies from 1:75 to 1:1. Modifiers
and epoxy resin co-intercalate into the clay galleries by ion dipole interaction, separating
the clay platelets sufficient to fully exfoliate during letdown. The compositions are
compounded into uniform mixtures and the final product form is also a flowable powder.
* Nanocor is a licensee of Toyota Central Research and Development Laboratories, Inc.
RESULTS AND DISCUSSION
The above-described Nanomers and concentrates can all be utilized to make commercial
nanocomposites. Application possibilities are quite varied, but at present they generally
fall into the categories of those requiring high temperature stability or gas barrier.
Performance characteristics are given for these categories. In addition chemical
resistance data is presented for amine-cured epoxy nanocomposites
All of the data reported in this paper has been generated at Nanocor's Technical Center.
The facility includes laboratory capabilities which mimic full-scale processes at the
company's Mississippi production facility. The Center is also equipped to make
nanocomposite test specimens using both polymerization and compounding routes.
Figures 1 and 2 ( Hard copy ) are Dynamic Mechanical Analysis (DMA) printouts for the
epoxy nanocomposites. Figure 1 covers the amine-cured specimens. An additive loading
of 7% substantially improves modulus, especially in the glass transition (Tg) region.
Improvements below the Tg are in the range of 30-50%, but above the Tg they are
orders of magnitude greater. Perhaps more significant is an upward shift in the Tg of 10-
20C, depending on the Nanomer.
For the higher temperature anhydride-cured nanocomposites at 10% loadings (Figure 2)
modulus improves to a lesser extent, but Tg increases are somewhat greater, 12-23C.
Notice that C.40EBA outperforms I.28E in modulus below the Tg. The situation reverses
above it. This points to the need to match Nanomer surface chemistry to the property-
driven application, rather than simply the polymer itself.
Chemical resistance information is given in Table 1. Nanomer I.30E was exfoliated in
each specimen at 6% loading. Using relative uptake as the comparison basis, the three
nanocomposites show good-to-excellent performance, except in the case of DER 331-
230 exposed to MEK. Resistance to chemical attack is beneficial for many traditional
epoxy applications, most notably coatings.
TABLE 1
RELATIVE UPTAKE (ASTM D543-87) NOTE: Unfilled resin = 1.0
Nanocomposite H
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Toluene MEK
DER! 331-230 0.68 0.72 0.75 0.89 0.85 -
DER" 331-400 0.76 0.68 0.50 0.75 0.34 0.31
EPON 828-3164 0.21 0.15 0.32 0.11 0.85 0.68
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Table 2 ( hard copy ) lists property data for nylon-6 nanocomposites made by both the
polymerization and compounding routes. The one using polymerization contains a
Nanomer in which the surface treatment reacts with the nylon matrix to form a
connected or tethered system. As the data demonstrates, tethering improves mechanical
properties versus an untethered system (I.30TC), but this is not the case for oxygen
transmission. OTR is higher than the untethered system, meaning that for barrier
applications an unthethered system is preferred. It is another example of the need to
match nanoclay surface chemistry to intended application.
An anomaly occurs in impact resistance. Conventional theory would hold that a tethered
system is more stable and consequently impact should improve. This is not the case,
however. Applications needing higher impact require the use of modifiers, even for
tethered systems. Further research is ongoing to determine why this occurs and how to
maintain impact without using modifiers.
Considering the nylon MXD6 nanocomposite, Graph A shows barrier improvement for
oxygen across the entire relative humidity range using just 5% Nanomer. More
significantly, the magnitude of improvement is greatest in the region of highest utility (rh
50-85%). For this nylon MXD6 grade, Nanomer addition shifts the curve down and to
the right. Under carefully controlled laboratory conditions, it is possible to achieve near-
glasslike permeability in the 55-65% rh interval. Lastly, a noticeable improvement in
haze is seen in films exposed to very high relative humidity (90+%). P>
Our experience with nylon MXD6 nanocomposites has led us to re-think the mechanism
of barrier enhancement. Prior theory held that enhancement is due to creation of a
tortuous path to gas diffusion. Platelet orientation work confirms this is a major
contributor, but it does not account for the 100 times permeation reduction that we
observe in MXD under tightly controlled conditions. We have concluded that other, as
yet unconfirmed, factors are at work as well. The issue is under intense study. If
additional mechanisms can be elucidated, applying the knowledge to more commonly
used plastics such as polyolefins, will be of great benefit.
CONCLUSION
One question frequently asked is "how broadly can this technology be applied in the
long run?" It is impossible to give a definitive answer at this state of knowledge. We are
at present developing products for a half dozen additional polymers, and this is by no
means the limit for polymer candidates. Nanocor believes clay nanocomposites can do
much more than enhancing classic engineering properties and barrier. Range-finding
work provides evidence for improvement in electrical performance, uv stabilization, fire
retandancy and control of polymer crystallization. Research in Japan is keying on the use
of partially dispersed systems as three-dimensional "platforms" for additive fixation. As
more industry R&D resources are committed to the technology's potential, further
development in these areas will undoubtedly expand its possibilities.
It is clear that several treatment chemistries can be used to compatibilize
montmorillonite for polymer nanocomposites. The main commercial chemistries are
onium ion and ion dipole treatments. An expanding universe of treatment agents is
amenable to these chemistries.
Montmorillonite-based nanocomposites can be produced commercially, using both
polymerization and compounding routes. The compounding route includes direct
Nanomer incorporation and concentrate letdown options.
Performance properties improve significantly when proper conditions are met with regard
to mineralogy, surface compatibilization and incorporation route.
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Because polymers are complex materials and their real world applications high
performance, care must be taken to match clay purity, morphology and surface
modification to each system's intended purpose. Cost-effective montmorillonite additives
are entering the market now. As more is learned about how and why nanoscale clay
additives interact with polymers, the potential for high-performance, low-cost
nanocomposites will be fully realized.
ACKNOWLEDGEMENTS
Our appreciation for valuable input is given to Dr. Okane Okada and Dr. Arimitsu Usuki
of Toyota Central Research and Development Laboratories, Inc. We also wish to thank
James Ancmon for his work in preparing and testing specimens and Elaine K. McNear
for manuscript preparation.
REFERENCES
Okada, A. and Usuki, A., Materials Science and Engineering, C3. (1995) 109-115
Deguchi, R., Saegusa, S., Ube Industries, Ltd., Nishi, T., Noruma, T., Toyota Motor
Corp., Okada A., Kurauchi, T. Toyota Central R & D Labs, Inc., "Nylon 6-Clay Hybrid-
Synthesis, Properties and Application to Automotive Timing Belt Cover", Proceedings of
the International Congress and Exposition for SAE International, Detroit, MI, February 25
- March 1, 1991.
Fugimoto, T., Ube Industries, Ltd., "Nylon Clay Hybrid for Packaging Applications",
Proceedings of Future Pak 96, Chicago, IL, November 1996.
Scherer, C. "PA for Cast and Blown Film Applications" Proceedings of K98 in Dusseldorf
,Germany, October , 1998
Eastman Chemical Press Release at Nova Pack Americas 99, February 12, 1999,
Wyndham Palace Resort Spa, Orlando, Florida
Goettler, L.A. and Rechtenwald, D.W., Solutia Inc., "Nylon Nanocomposites:
Performance Attributes and Potential Applications", Proceedings of Additives 98,
Orlando, FL, February 1998
Beall, G. W. and Tsipursky, S. J., "Nanocomposites Produced Utilizing a Novel Clay
Surface Modification" Proceedings of Additives 98, Orlando, Florida February 16-18,
1998
Jordan, J.W., "Organophilic Bentonites I", J. Phys. Chem., 59, 294-305 (1949)
Nanomer is a registered trademark of Nanocor, Inc.
Copyright 1999, Nanocor
Nanocor Inc. is a wholly owned subsidiary of AMCOL International Corporation.