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Membr. Sci. 1993, 80, 189. d) I. F. J. Vankelecom, E. Merckx,
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A. J. Hill, Science 2002, 296, 519.
[12] J. P. Boom, I. G. M. Punt, H. Zwijnenberg, R. de Boer, D. Barge-
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[13] D. Q. Vu, W. J. Koros, S. J. Miller, J. Membr. Sci. 2003, 211, 311.
Toughness of Spider Silk at High
and Low Temperatures**
By Yong Yang, Xin Chen, Zhengzhong Shao,*
Ping Zhou, David Porter, David P. Knight,
Fritz Vollrath
The outstanding strength and toughness of certain spider
and lepidopteran silks[1] has aroused considerable interest in
recent years,[2] with research focusing primarily on the rela-
tionship between molecular structure and mechanical proper-
ties.[3] Environmental conditions such as ambient humidity,[4]
acidity,[5] and UV radiation[6] all affect the mechanical proper-
ties of native silks to some degree.[7] Pronounced differences
in mechanical properties were also observed when conditions
such as the speed or temperature at spinning were varied[8] or
when the silk was (or had been) submerged in solvents such
as water, urea solution, or a range of alcohols, where it con-
tracts in varying degrees.[9]
silk studies, the golden silk spider Nephila edulis. All silk had
[*] Prof. Z. Shao, Y. Yang, Dr. X. Chen, Dr. P. Zhou
Department of Macromolecular Science and
The Key Laboratory of Molecular Engineering of Polymers
of the Ministry of Education
Fudan University
Shanghai 200433 (P. R. China)
E-mail: zzshao@fudan.edu.cn
Dr. D. Porter, Dr. D. P. Knight, Prof. F. Vollrath
Department of Zoology, University of Oxford
South Parks Road, Oxford OX1 3PS (UK)
[**] This work is supported by the National Natural Science Foundation
of China (NSFC, No. 20244005), the Science and Technology Devel-
opment Foundation of Shanghai, the China-UK Science and Tech-
nology Research Foundation. For funding FV, DK and DP thank the
British EPSRC (grant GR/NO1538/01) and BBSRC (S12778) as well
as the European Commission (grant G5RD-CT-2002-00738) and the
AFSOR of the United States of America (grant F49620-03-1-0111).
84  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adma.200400344
ing spinning and during testing. Thus the mechanical proper-
ties of silks produced and tested under very specific
conditions can be used as windows to look into the interac-
tion of production conditions and silk mechanics (studied by
varying the extrusion conditions[8]) as well as the details of the
silk fine structure (examined by varying the testing condi-
tions[9]). Both are not without some importance to the spiders
as they can affect the performance of the web. Spiders are ec-
totherms, and ambient temperature has a strong effect on spi-
der behavior and life history,[10] in addition to affecting the
material spun under those conditions. Climate further affects
the material properties of silk and the engineering of the
whole web,[2a,11] because webs are typically spun in the early
morning, when humidity is high while temperature is low.
Hence we may assume that evolution has led to a set of design
criteria for silk that allow the material to function well over a
range of temperatures (from ca. 0 C to 30 C), humidities
(from ca. 20 to 100 RH (relative humidity)), and spinning
speeds (from ca. 1 mm s1 to ca. 1000 mm s1). However, what
about the properties outside that range? Moreover, as men-
tioned above, the inter-relation of environmental conditions
and silk behavior can provide insights into the structurefunc-
tion relationship.
Hence we posed, firstly, the question of whether a major
spider silk, i.e., a silk that is normally used for lifelines and
important supporting web-components, can perform outside
the range of temperatures under which it evolved. Secondly,
we were interested in the light that mechanical performance
would shed on the structure of the material if we tested our
silks under as wide a temperature regime as possible (i.e., 60
to +150 C). Clearly, this would not only provide data of
purely scientific value but also data of considerable commer-
cial interest, as spider silk is often billed as a material with a
great future. To study these questions (i.e., to examine the
mechanical properties of a major spider silk over a wide tem-
perature range), a dynamic mechanical thermal analyzer
(DMTA) was used to measure both static and dynamic
mechanical properties of single spider-silk threads. We mea-
sured the strain response of single-thread filaments (ca. 6 lm
in diameter) of a principal dragline fiber from the large
orb-weaving spider that has become the benchmark of spider-
been collected under the same control silking conditions of
20 mm s1 at 25 C. Figure 1 shows the data thus collected.
Figure 1a clearly demonstrates that, at 15 C, the DMTA
used in this experiment produces stressstrain curves for the
single and fine silk filaments that closely resemble curves col-
lected on our extremely sensitive, custom-built, rapid-re-
sponse stressstrain gauge from the same kind of silk.[8,9a] This
control experiment ensured that the machine was adequate to
our requirements, although this DMTA is normally used to
study the dynamic mechanics of more robust polymer fi-
bers.[12] We concluded that this method is an accurate and
powerful tool to survey the stretching properties of silk fibers
under a regime of well-controlled temperatures.
Adv. Mater. 2005, 17, No. 1, January 6
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a) b)

c) d)

Figure 1. The tensile properties of single filaments of major ampullate silk of the golden silk spider Nephila edulis measured by a dynamic mechanical
thermal analyzer at different temperatures. a) Stressstrain curves of spider silk at selected temperatures. Influence of the temperature on the mechan-
ical properties: b) initial modulus, c) breaking strength, and d) elongation at break. The measurement at each condition was performed at least 5
times, and the data were averaged.

We observed that increasing the temperature up to 150 C mer/silk protein blends,[14] or thick bundles of silk fila-
produced remarkably little change in the tensile behavior. ments.[15] To analyze in detail the effect of temperature on the
Surprisingly, cooling down to 60 C from room temperature mechanical behaviors of natural silk we tested single filaments
produced an increase of strength while the elongation to frac- of the Nephila spider dragline silk on the DMTA. A represen-
ture doubled. This means that at low temperatures our spider tative scan of the dynamic mechanical properties of such silk
silk can outperform the toughest (i.e., most energy absorbent) is displayed in Figure 2.
synthetic polymer fibers. Figures 1b1d show detailed mea-
surements on the effect of temperature on the tensile proper-
ties of single spider-silk fiber. Tensile strength decreased with
increasing temperature, comparable to most polymeric mate-
rials as well as even high-performance polymeric fibers such
as PPTA (Kevlar) and HBA/PET (hydroxybenzoic acid/poly-
(ethyleneterephthalate)) copolyester fibers.[13] However, (and
this is highly unusual for any of these fibers) in our silk, the
elongation at break decreased with increasing temperature up
to 70 C. Accordingly, our static mechanical measurements
suggest that the combination of high tensile strength and high
extensibility give the natural spider silk remarkable toughness
at low temperature. Gosline et al. demonstrated that the
strength and toughness of spider silk would be enhanced at
high strain rates.[3h] Their observation might arise from a simi-
lar phenomenon to ours, since for viscoelastic processes low Figure 2. Typical dynamic mechanical curves of Nephila edulis spider
dragline silk. From 66 C to 60 C, the phenomenon of E generally in-
temperatures are equivalent to high strain rates. creasing with temperature may be an experimental artifact and the slop-
Dynamic mechanical analysis has previously been used to ing baseline of tan d between 0 C and 360 C can be explained by the dif-
study either films of regenerated silk protein or films of poly- ferent creep abilities of spider silk with changing temperature.

Adv. Mater. 2005, 17, No. 1, January 6 http://www.advmat.de  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 85
COMMUNICATIONS
Usually, silk protein is regarded as a biological representa-
tive of the nylon family, Nylon 2.[2b] Hence the thermal me-
chanical relaxation behavior of spider silk can be addressed
similarly to those of commercial polyamides.[16] Figure 2
shows that the tan d curve (giving the ratio of loss modulus E
to storage modulus E) displayed a small peak at about
70 C. This suggests a structural sub-transition at this point[15a]
probably due to the relaxation of hydrocarbonhydrocarbon
interactions.[16] A slight fluctuation was also seen at approxi-
mately 20 C; one reason for this may be related to the phase
transition of water. This interpretation is supported by the ob-
servation that taking a sample to about 110 C in the DMTA
resulted in a slight diminution of the fluctuation when a sec-
ond warming scan was carried out after re-cooling to 100 C.
The increase of storage modulus up to a maximum occur-
ring at approximately 60 C correlated with the data obtained
by statistical measurements. A transition of initial modulus
and elongation at break values was found to occur around
70 C (Figs. 1b,d). This could indicate an increase in the intrin-
sic stiffness of individual molecular chains or, alternatively, a
stronger interaction between chains with an increase in tem-
perature from 66 to 60 C, or a combination of both. Tsukada
et al.[17] also observed a slight increase of E from 30 to 60 C
in tussah silk fibers (albeit in bundles not single fibers) and
suggested that at that temperature there might be some rear-
rangement of the molecules in the amorphous regions during
the heating process, resulting in a strengthening of the inter-
chain interactions. Nevertheless, this phenomenon may simply
be caused by artifacts during the experiment since a single
thread of spider silk is normally thinner than 6 lm. Still, the
exact mechanism remains to be understood.
There were two main peaks on the tan d curve: a large one
at 198 C and a small at 309 C. The large one we assigned to
the breakdown of intermolecular hydrogen bonds in the non-
crystalline section of spider-silk fiber, indicating that this frac-
tion of the material had begun to enter the rubber state. It has
been suggested that the lattice of hydrogen bonds holding
together the b-sheet crystalline component of spider silk
breaks down at ~200 C.[15a] However, we think it more likely
that the crystal phase breakdown or melting occurs at a much
higher temperature, and imparts the high temperature stabil-
ity of silk fibers; Nephila dragline silk shows excellent heat re-
sistance, failing mechanically only at 371 C.
The mechanical properties of spider dragline silk have been
modelled by Termonia[3a] as a matrix composed of poorly
ordered amorphous flexible rubber-like chains reinforced by
hard crystals. As a revision of this model, we suggest that, be-
low 198 C, the non-crystalline segments are orientated with
respect to the thread[8,18] and held together by hydrogen bonds
that are broken when this critical temperature is reached.
Thus, the molecular chains separate and become disordered
to give the rubber state. However, in such a state, the crystal-
line part of the silk still exists and provides multivalent cross-
links. This interpretation explains two observations: firstly,
spider silk showed a considerable storage modulus above
198 C; and secondly, the storage modulus increased slightly
86  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de
as the temperature increased above 290 C, probably as the
result of an annealing process that improved the hitherto im-
perfect[19] crystalline structure before its destruction. There-
fore, it is reasonable to consider that the relaxation peaks of
spider silk at 198 C and 309 C can be attributed to the break-
ing down of hydrogen bonds in the disordered glassy phase
and the subsequent partial crystallization of the silk,
respectively.
It will be interesting to examine the mechanisms of failure
at low temperatures. Fractographic studies of spider silks had
previously been performed on the spiders Nephila clavipes
and Argiope trifasciata but only at room temperature and
after stretching.[15a,20] Un-stretched spider silk broken at very
low temperatures had not been studied before. Figure 3 shows
the fractured surface of a Nephila edulis spider-silk fiber bro-
ken in liquid nitrogen. The fractured part frequently showed
evidence that it stretched during the fracture process
(Figs. 3a,b). This leads to the remarkable conclusion that,
unlike most other polymeric materials, the fracture of spider
silk is ductile and therefore tough rather than brittle, even at
liquid-nitrogen temperatures. In contrast, silkworm silk gave a
very coarse transverse break in liquid nitrogen, clearly reveal-
ing its microfibril structure (Fig. 3d).
After spider silk had fractured in liquid nitrogen, the outer
layer of the broken silk often showed wrinkles (Fig. 3c).
These might arise from the different degrees of contraction of
skin and core of the silk, comparable to the behavior during
the super-contraction when silk is immersed in water or other
organic solvents.[9] During the period when the broken silk fi-
ber is taken from the liquid nitrogen and is being mounted on
the scanning electron microscopy (SEM) stubs, the moisture
in the air would have condensed on the fiber, which might
have led to super-contraction. Spider silk has a skincore
structure,[3e] and a difference in the contraction in these com-
ponents may contribute to this effect.
Although both spider and silkworm silk appear to be large-
ly constructed from nanofibrils,[21] and both show a similar
b-sheet secondary structure,[22] only silkworm silk exhibited a
microfibrillar structure when fractured in liquid nitrogen
(Fig. 3d). This difference may correlate with a greater
tendency of silkworm silk to fasciculate into bundles of nano-
fibrils when homogenized (Knight, unpublished observa-
tions). Both observations may indicate a weaker bonding of
nanofibrils to the inter-nanofibrillary matrix in Bombyx (silk-
worm) compared to spider silk.
Future work will attempt to link the dynamic mechanical
characteristics of silks to their low-temperature toughness.
The tan d peak at 70 C is large enough and broad enough to
suggest that the associated relaxation process may encourage
a local yield mechanism that promotes a tough failure
mechanism.
In summary, major ampullate silk from the spider Nephila
edulis showed remarkable toughness at very low temperatures
(60 to 0 C) that had not been observed in most synthetic
fibers. Below 0 C, it had a high initial modulus (~14 GPa),
good tensile strength (~1.5 GPa) and high extensibility
Adv. Mater. 2005, 17, No. 1, January 6

a)
b)
Figure 3. The morphology of single filaments of silks fractured in liquid nitrogen. a) Profile, b) front view of cross-section, c) inclined plane of broken
Nephila edulis spider silk; d) front view of broken Bombyx mori silkworm silk, which was drawn back into the embedding epoxy resin.
(~40 %). This correlates with the tough fracture behavior in
liquid nitrogen inferred from our SEM observations. Further-
more, and highly unusual, the elongation at break decreased
with increasing temperature and reached a minimum around
70 C. Meanwhile, dynamic mechanical measurements on the
same silk (using the same instrument) have showed relaxation
processes associated with different molecular-level interac-
tions in the silk: hydrocarbonhydrocarbon, wateramide, and
amideamide, as well as possible crystallization at higher tem-
peratures. In addition, the failure temperature of dynamic
measurement of the spider silk (371 C) was higher than silk-
worm silk (308 C). Thus, remarkably, spider silk retains quite
exceptional mechanical properties over a temperature range
from at least 66 Cand probably down to liquid nitrogen
temperaturesup to about 100 C. This temperature depen-
dence of mechanical properties of spider silk (as opposed to
that of other polymers) adds to the other remarkable proper-
ties of this accomplished material[7a] and demonstrates the po-
tential usefulness of such a super-fiber in harsh environments.
Experimental
Single dragline silk filaments were forcibly reeled from the major
ampullate glands of the Australian golden silk spider Nephila edulis.
The technique is described in detail elsewhere [8,9a]. For these experi-
ments the reeling rate was 2.0 cm s1. For the fracture experiments,
spider silk threads were embedded directly in epoxy resin without
treatment. After polymerization for 1 day at room temperature the
resin bars were cooled in liquid nitrogen for 10 min and then frac-
tured. A Philips XL30 scanning electron microscope was used to ob-
serve the fracture surfaces of silks at 2025 kV.
Adv. Mater. 2005, 17, No. 1, January 6 http://www.advmat.de
COMMUNICATIONS
c)
d)
A dynamic mechanical thermal analyzer (DMTA IV; Rheometric
Scientific Inc.; Piscataway, NJ, USA) was used to measure both static
and dynamic mechanical properties of single spider silk threads. Sam-
ples were prepared as described previously [23]. Using single threads
instead of bundles of fibers for dynamic mechanical thermal analysis
prevents uncertainty in interpretation resulting from lack of unifor-
mity of strain and from threads slipping past each other. To determine
the diameter of silk fibers, a different part of the same thread used in
dynamic mechanical thermal analysis measurement was mounted
directly on SEM stubs and viewed at a magnification of about 3000
after sputtering with gold. At least three diameter measurements were
recorded and averaged for each sample. The mean diameter of major
ampullate filaments was 6.2 0.4 lm in the present study. For static
measurements the strain rate was 0.05 % s1, temperature range from
60 C to 150 C, and temperature control 0.5 C. For dynamic mea-
surements the frequency was 1 Hz, strain 0.6 %, temperature range
from 100 C to 370 C, and temperature ramp 5 Cmin1.
Received: March 8, 2004
Final version: June 18, 2004
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88  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adma.200400598
Effects of Carbon Nanotubes on Grain
Boundary Sliding in Zirconia
Polycrystals**
By Maren Daraktchiev,* Bertrand Van de Moortle,
Robert Schaller, Edina Couteau, and Lszl Forr
Mechanical properties of zirconia polycrystals decrease
drastically at high temperature. This is due to thermally acti-
vated grain boundary (GB) sliding which leads to plastic or
even super-plastic deformation.[15] As GB sliding is a source
of energy dissipation in the material, mechanical loss mea-
surements[6,7] are well suited to study such a mechanism. They
reveal, in general, a mechanical loss peak, which evolves into
an exponential increase at higher temperatures.[811] When in-
tergranular glassy films or/and amorphous pockets are pre-
sented in polycrystalline ceramics, the mechanical loss[12,13]
and creep rate are higher.[5,14,15] We show that introducing
carbon nanotubes (CNTs) in zirconia, in particular, drastically
reduces GB sliding and consequently the mechanical loss at
high temperatures. The nanotubes were observed at the grain
boundaries by high-resolution transmission electron microsco-
py (HRTEM) and were related to the reduction of superplas-
tic flow through the boundaries, which should improve the
material creep resistance.
The mechanical loss, tan(u), spectrum associated with the
brittleductile transition in fully tetragonal zirconia polycrys-
tals stabilized by 3 mol-% yttria (3Y-TZP) is presented in
Figure 1. As measured as a function of temperature, the
mechanical loss angle tan(u) shows an exponential increase
accompanied by a steep shear modulus (G) decrease above
1200 K.
High-temperature plastic deformation of polycrystalline
zirconia is associated with GB sliding, and consequently it
seems reasonable to link the mechanical loss spectrum with
[*] Dr. M. Daraktchiev[+]
Institut des Matriaux (IMX)
Ecole Polytechnique Fdrale de Lausanne (EPFL)
CH-1015 Lausanne (Switzerland)
E-mail: maren.daraktchiev@epfl.ch
Dr. B. Van de Moortle, Dr. R. Schaller, Prof. L. Forr
Institut de Physique de la Matire Complexe (IPMC)
Ecole Polytechnique Fdrale de Lausanne (EPFL)
CH-1015 Lausanne (Switzerland)
Dr. E. Couteau
DSM Nutritional Products, R&D Chemical Process Research
P.O. Box 3255, CH-4002 Basel (Switzerland)
[+] Present Address: Department of Earth Sciences, University of
Cambridge, Downing Street, Cambridge CB2 3EQ, UK.
[**] This work was supported by the Swiss National Science Foundation
and in part by the TOP NANO 21 Program. The authors would like
to thank L. Gremillard for his assistance in TEM observations,
B. Guisolan for technical help and Thomas Lagrange for critically
reading the manuscript. The CLYME (Consortium Lyonnais de Mi-
croscopie Electronique) were grateful acknowledged for the micro-
scope access.
Adv. Mater. 2005, 17, No. 1, January 6