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REVIEW

REVIEW

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Piezoresistivity, Strain, and Damage Self-Sensing of Polymer Composites Filled with Carbon Nanostructures

Francis Avil es,* Andr es I. Oliva-Avil es, and Marco Cen-Puc

Previous and current research on piezoresistivity of polymer composites filled with carbon nanostructures is reviewed. The review covers the use of the coupled electro-mechanical response of these materials to self-sense their strain and damage during mechanical loading. The mechanisms yielding changes in electrical resistance upon mechanical loading in polymer composites filled with carbon nanostructures are first discussed. Published knowledge is then summarized, starting with framework literature on carbon black and graphite and then moving to more recent research on carbon nanotubes, exfoliated graphite, and few-layer graphene sheets. Piezoresistive studies of polymer nanocomposites with aligned carbon fillers are also reviewed. It is aimed that this review contributes in collecting, organizing, and summarizing the knowledge, foundations, and state of the art on the piezoresistive response of polymer composites filled with different carbon allotropes, providing new perspectives and advancing towards the fast development of smart self-sensing carbon filled nanocomposites.

1. Introduction

Piezoresistivity is de ned as the coupling phenomenon between a mechanical stimulus (strain, e, or stress, σ) and a change in electrical resistance (Δ R , where R is the electrical resistance). [1,2] In contrast to piezoelectricity (which goes both ways, mechanical stimulus to generation of electrical potential, and conversely), piezoresistivity causes a change only in electrical resistance (not in electrical potential) and goes only in the mechanical- to-electrical direction. The rst documented report of piezor- esistivity (for metal wires) is ascribed to William Thomson (Lord Kelvin) in 1856. [3] Among the rst sensors which used this principle are probably the strain gages, which became

commercial about 75 years after Thom- son s discovery. Strain gages are typically made of thin metal or semiconducting foils mounted on a backing polymeric lm (typically a polyimide), which are bonded onto a surface to measure the strain of a material or structure. [2] Several decades later, the same basic principle (change in electrical resistance as a response of an external stimulus) was implemented to monitor strain, temperature, moisture, and chemical vapors (among others) using polymer composites lled with conductive llers such as carbon bers, [4,5] graph- ite, [6,7] and carbon black. [8,9] With the rise of nanomaterials and nanotechnology, this concept has evolved to the use of carbon nanostructures such as carbon nanotubes (CNTs) [10,11] and graphene (or graphenic

akes). [12,13] This fast growth has promoted the development of novel materials which offer not only improved mechanical per- formance, but also electrical conductivity and coupled multi- functionality, which enables the development of several kinds of electro-mechanical sensors. [14,15] As seen from Figure 1 , the applications are vast, from development of electromechanical devices, [16,17] to smart textiles, [18] exible electronics, [12] soft robotics, [19] sensors of human motion, [20] and smart materials for in situ monitoring of damage and structural health of advanced composite materi- als. [21,22] Albeit the same basic piezoresistive principle prevails, the mechanisms governing the piezoresistive behavior are quite different and more complex for polymer composites lled with carbon nanostructures than for continuous metallic conductors (such as strain gages), as it will be further explained in the following section.

Dr. F. Avil es, M. Cen-Puc Centro de Investigaci on Científica de Yucatán Unidad de Materiales Calle 43 No.130 32 y 34, Col. Chuburná de Hidalgo, 97205 M erida, Yucatán, Mexico E-mail: faviles@cicy.mx

Dr. A. I. Oliva-Avil es Universidad Anáhuac Mayab Divisi on de Ingeniería y Ciencias Exactas Carretera M erida-Progreso km 15.5 AP 96-Cordemex, CP 97310 M erida, Yucatán, Mexico

15.5 AP 96-Cordemex, CP 97310 M erida, Yucatán, Mexico The ORCID identification number(s) for the author(s)

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adem.201701159.

DOI: 10.1002/adem.201701159

2. Piezoresistivity Mechanisms and Fundamentals of Self-Sensing of Strain and Damage in Polymer Composites Modified with Electrically Conductive Fillers

The piezoresistivity of a metal wire arises from the change in its length and cross-sectional area upon mechanical loading. [1,25] The situation is very different for insulating polymers lled with conductive (carbon) nanostructures, which are not formed by continuous conductors spanning the length of the material, but comprise the summation of discrete (micron-size) elements assembled together to form continuous paths/networks. Since

www.advancedsciencenews.com www.aem-journal.com in these materials the matrix is non-conductive, the only way that current
www.advancedsciencenews.com www.aem-journal.com in these materials the matrix is non-conductive, the only way that current

in these materials the matrix is non-conductive, the only way that

current can ow through the material upon voltage application is through the formation of a network of conductive llers (physically touching each other or not), which contain delocalized electrons, see Figure 2. This phenomenon is known as electrical percolation, and the exact ller concentration where such a network is formed is known as the percolation threshold. [26,27] The concentration of carbon llers required to reach such a percolation threshold depends on many aspects such as the morphology of the ller, its own conductivity, its dispersion state within the matrix and the rheology of the polymer matrix, and may range from 0.01 wt% to less than

10 wt%. [27 29] Once the percolation threshold is reached, the composite becomes electro-conductive and the change of its effective electrical resistance upon loading can be used as a piezoresistive feature to self-sense deformation and dam- age. [30,31] It is nowaday accepted that the electro-mechanical (piezoresistive) sensitivity of this kind of composites is higher for low concentration of llers (just above electrical percolation) than for composites with high ller content (i.e., composites with high conductivity). [29,32,33] This is because for composites with high ller content (high number of conductive pathways, i.e., a densely packed network), the disruption or modication of

a single conductive path (or a few of them) has only a minor

inuence on the effective electrical resistance of the composite, Figure 2 (top); in this gure the initial electrical resistance of the

composite (R ) does not change much when the strain is applied (R R ). In contrast, if the ller content is low (few conductive pathways, that is, a loosely packed network with initial electrical resistance R 0 ), the disruption or modi cation of a single conductive path upon stretching the composite greatly affects R , that is, upon stretching R >> R 0 , Figure 2 (middle). Extrapolat- ing this concept, in theory, a switching device (which switches from conductive to insulating) with initial resistance R 0 could be achieved if only one conductive path would be formed within the insulating matrix, which conceptually represents the maximum piezoresistive sensitivity, as depicted in Figure 2 (bottom). However, in practice, working very close to the electrical percolation threshold generates a noisy electrical signal and serious instrumentation drawbacks, which currently hinders the use of this very low ller concentration regime. To overcome this practical limitation, most of the piezoresistive work on polymer composites uses ller concentrations that are signi cantly above the percolation threshold, where electrical resistances in the range of k ΩM Ω are typically achieved and easily handled. Linear piezoresistivity can be quanti ed by a parameter known as the gage (or gauge) factor, which is a metric of linear piezoresistive sensitivity. The gage factor (GF) is dened as the slope of the linear relationship between the fractional change in electrical resistance (Δ R/ R 0 , where R 0 is the initial electrical resistance corresponding to the unstrained/unloaded state) and the applied uniaxial strain. Typical metallic strain gages used in materials testing have GFs between 2.1 and 2.3. Contrastingly, the inherent piezoresistivity of carbon nanostructures can be quite high. [34 36] For example, landmark works have reported gage factors for individual singlewall carbon nanotubes (SWCNTs) as high as 2900. [34] This is at least two orders of magnitude higher than the sensitivity measured when the nanotubes are embedded in polymer composites, which

a

0

b

a

0

b

c

Francis Avil es is a Scientist at the Materials Department of the Scientific Research Center of Yucatan (CICY for its Spanish acronym), located in M erida, Mexico. He is a Mechanical Engineer with a Master degree in Applied Physics and a PhD in solid body mechanics. He received his PhD in 2005 from Florida Atlantic University, working on the mechanics of composite materials and sandwich structures, and worked as a Research Associate at the Center for Composite Materials of the University of Delaware. He returned to Mexico in 2006 and worked as scientific researcher thereafter. His current research interests focus on the mechanics, electro-mechanics and multifunctional properties of composite materials, piezoresistive and thermoresistive properties of nanostructured polymer composites, carbon nanostructures, and smart materials.

composites, carbon nanostructures, and smart materials. Andr es I. Oliva-Avil es is an early- career professor
composites, carbon nanostructures, and smart materials. Andr es I. Oliva-Avil es is an early- career professor

Andr es I. Oliva-Avil es is an early- career professor at the Division of Engineering and Exact Sciences at the Anahuac-Mayab University, located in M erida, Mexico. He is a Physics Engineer with MS (2010) and PhD (2013) degrees in Applied Physics from the Center of Research and Advanced Studies (CINVESTAV for its Spanish acronym). During his

Ph.D. he spent a year as a research scholar in the

Aerospace and Ocean Engineering Department at Virginia Tech, USA. His research interests focus on the influence of the structure-property relationships of carbon nanostructured polymer composites and on the study of physical properties of smart multifunctional materials.

of physical properties of smart multifunctional materials. Marco Cen-Puc is a Mechatronics Engineer by the Autonomous

Marco Cen-Puc is a Mechatronics Engineer by the Autonomous

University of Yucatan (UADY) in

M erida, Mexico (2013). He received

a MS degree in Polymeric Materials

by the Scientific Research Center of

Yucatan (CICY) in 2016. After obtaining his MS degree he worked as research assistant at the CICY s Materials Department, working with Dr. Francis Avil es on the development of temperature sensors based on carbon nanotube/polymer composites. His interests include the development and instrumentation of sensors as well embedded electronic systems. He is currently working as a part-time professor at the Anahuac Mayab University while he applies for a PhD position abroad.

www.advancedsciencenews.com www.aem-journal.com Figure 1. Applications of piezoresistive polymer nanocomposites based on
www.advancedsciencenews.com www.aem-journal.com Figure 1. Applications of piezoresistive polymer nanocomposites based on
www.advancedsciencenews.com www.aem-journal.com Figure 1. Applications of piezoresistive polymer nanocomposites based on

Figure 1. Applications of piezoresistive polymer nanocomposites based on carbon nanostructures. a) Highly twistable tactile sensing array made from polydimethylsiloxane (PDMS) and carbon black nanoparticles. [23] (Reprinted from ref. [23] , with permission from Elsevier), b) stretchable singlewall CNT/PDMS strain sensor for human motion detection. [20] (Reprinted from ref. [20] , with permission from Nature Publishing Group), c) Organic light-emitting diode on a graphene/polymethyl methacrylate (PMMA) transparent conducting electrode. [24] (Reprinted from ref. [24] , with permission from Nature Publishing Group), d) schematic showing the use of carbon nanotubes in a polymer matrix to self-sense crack propagation and damage in advanced multiscale composites.

evidences that the full piezoresistivity of the carbon nanotube is not transferred to its polymer nanocomposite. This is partly because the applied strain is not fully transferred to the ller. [25] Therefore, in this kind of nanocomposites, the inherent piezoresistivity of the carbon llers and the change in their dimensions upon loading provide only a small contribution to the measured piezoresistivity. [25,37] In polymer composites at relatively low ller contents, piezoresistivity is driven by the change in the ller network con guration upon mechanical loading. The major underlying mechanisms which govern the change in electrical resistance upon loading are schematically represented in Figure 3. They can be grouped into three main aspects which occur upon strain application, viz. reconstruction of the conductive network (creation and destruction of conductive pathways), changes in the contact resistance between conductive llers, and changes in the ller-to- ller interparticle distance. [38 42] As depicted in Figure 3, upon straining the composite new conductive pathways can be created and others destroyed; the ller-to-ller contact resistance also changes upon strain application, since the ller- to- ller contact area and the number of contact points also changes. There is also a very important non-contact scenario, which is governed by the interparticle distance. It is accepted

that upon suf cient energetic excitation (voltage, temperature) the electrons can tunnel or hop over small distances crossing a thin polymeric layer; this (quantum) tunneling resistance depends on the interparticle distance in an exponential fashion. [43 45] The maximum tunneling distance in polymers lled with carbon nanostructures varies depending on the nanostructure and polymer type; the maximum tunneling distance has been theoretical suggested to be close to 2 nm, [40,44,46] although some other studies have considered slightly higher tunneling distances ( 5 nm). [45] The relative in uence of these mechanisms driving the effective measured piezoresistivity in a polymer composite depends on several factors related to the ller itself, to the polymer matrix, and to their interaction and state of dispersion. Several numerical and analytical modeling efforts have advanced towards understanding the piezoresistive effect in polymer composites, including effects such as tunneling, CNT-to-CNT contact, CNT morphology and waviness, agglomeration, inher- ent CNT piezoresistivity and loading conditions. [37,41,45,47 54] From the materials viewpoint, the geometry of the ller and its dispersion within the matrix, the mechanical and rheological properties of the polymer matrix, as well as its electrical permittivity are among the most in uential factors. [54 57]

www.advancedsciencenews.com www.aem-journal.com Figure 2. Relative influence of breaking a few individual conductive
www.advancedsciencenews.com www.aem-journal.com Figure 2. Relative influence of breaking a few individual conductive
www.advancedsciencenews.com www.aem-journal.com Figure 2. Relative influence of breaking a few individual conductive

Figure 2. Relative influence of breaking a few individual conductive pathways in a network with high filler content (top), low filler content (center) and with only one connecting pathway. R 0 a , R 0 , and R 0 c are correspondingly the initial (unstrained) electrical resistances for cases a(top), b(middle), and c (bottom).

b

Tunneling resistance is known to have an exponential depen- dence with the ller-to-ller separation distance and also with the square root of the height of the tunneling barrier. [43] While the ller-to- ller separation distance is controlled by the excluded volume of the ller, its concentration and state of dispersion within the polymer, the tunneling barrier is interpreted as the thin ( < 5 nm) layer of polymer between the llers where the electrons can tunnel or hop. [43,44] Therefore, this tunneling barrier, in turn, is strongly affected by the dielectric properties of the polymer matrix. [43,45,53] Other effects such as the formation of small micro-capacitors also strongly depend on the interparticle distance and on the dielectrical properties of the thin polymer layer separating the conductive llers. The main idea of the micro-capacitor effect is that each two neighboring carbon llers separated by a very thin polymer layer can be considered as a local microscale capacitor, with the llers acting as the two electrodes and the thin polymer layer in between as the dielectric. This effect yields a substantial increase in the intensity of the local electric eld around the llers, which promotes the charge carriers to migrate and accumulate at the interface of the electrodes ( llers), yielding interfacial polarization. [58] Because of the change in interparticle

[ 5 8 ] Because of the change in interparticle Figure 3. Piezoresistive mechanisms in polymer

Figure 3. Piezoresistive mechanisms in polymer composites filled with carbon nanostructures.

distance, this capacitance may also change upon strain application and affect the effective electrical properties of the strained material. Regarding the morphology of the ller, the aspect ratio (length/diameter) is one of the fundamental factors which govern the percolation thres hold and the piezoresistive response of nanocomposites. [27,55,59,60] The in uence of this morphological effect can be explained by using the concept of excluded volume. [61] The excluded volume theory consid- ers that the most relevant parameter in the formation of

randomly packed percolated networks is not the actual volume of the ller itself, but the volume around such a ller in which the center of another object of similar shape cannot penetrate, that is, i ts excluded volume, [62] see Figure 4 . The orientational average excluded volume ( V Exc ) of randomly oriented rods, [63] in nitesimally thin disks, [59] and spheres [62,64] are, respectively,

V

r

Exc ¼

V

d

Exc ¼

V

s

Exc ¼

π

2

L 2 d r þ 2 π d 2 L r þ

r

r

π

2

8

3

d d

2

π

3

d

3

s

4

3

π d

3

r

ð1aÞ

ð1bÞ

ð1cÞ

where the superscripts r, d ,s , stand for rods, disks, and spheres, respectively, L r is the rod s length, d r its diameter, d d is the disk s diameter (lateral size) and d s is the sphere s diameter. For a nanotube, since L r >> d r the rst term of Equation (1a) represents a very close approximation to its excluded volume. Using this approximation (L r >> d r ) the ratio of the excluded volume for rods (Eq. 1a) with respect to that of spheres (Eq. 1c) and disks (Eq. 1c) becomes,

www.advancedsciencenews.com www.aem-journal.com Comparison of excluded volumes between CNTs (cylinders) and graphenic
www.advancedsciencenews.com www.aem-journal.com Comparison of excluded volumes between CNTs (cylinders) and graphenic
Comparison of excluded volumes between CNTs (cylinders) and graphenic platelets (infi- nitely thin disks) through
Comparison of excluded volumes between
CNTs (cylinders) and graphenic platelets (infi-
nitely thin disks) through Equation (2b) requires
further considerations, since graphenic platelets
can vary signi ficantly in lateral size. For the sake
of analysis, let ’ s assume as a lower bound (small
sheets) for the lateral dimension of the graphenic
sheets (d d ) the situation where d d is equal to the
CNT diameter (a few nanometers for SWCNTs
or tens of nanometers for multiwall carbon
nanotubes (MWCNTs), i.e., nanosheets). In this
scenario d r ¼ d d and Equation (2b) becomes,
2
r
V
4
L
Exc
r
¼
ð3a Þ
d
V
π
d
d
Exc

Figure 4. Schematic representation of the concept of excluded volume (area) in a 2D projection. a) 25 identical solid circles covering a squared area, b) 5 cylinders (whose total area approximately equals that of the 25 circles) covering the same squared area.

On the other extreme, considering large graphenic sheets with L r ¼ d d (a few microns, i.e., microsheets) yields,

V

r

Exc

¼

3

L

r

V

s

Exc

4

d

s

2

V

r

Exc

4

L

2

r

d

r

¼

V

d

Exc

π

d

3

d

!

ð2a Þ

ð2b Þ

The comparison betweenthe excluded volume of CNTs andthat of spherical carbon nanoparticles such as carbon black nano- particles or fullerenes can be done in a straightforward manner using Equation (2a). Since the diameter of a carbon nanoparticle (say d s 20 nm) is typically about 2 orders of magnitude smaller than the typicallength of a CNT (say L r ¼ 2 μm), Equation (2a) implies that the excluded volume of carbon nanotubes is about 4 orders of magnitude higher than that of spherical carbon nanoparticles. A schematic of this is depicted in Figure 4 in a bi-dimensional (2D) projection, where the total area covered bythe 25 (black) solid circles (2D projection of spheres) is approximately equal to the total area covered by the 5 elongated entities (2D projection of cylinders); that is, Figure 4a and b have the same area fraction of solid llers.As seen from Figure 4a,there is still roomto t more identical circles among the existent solid ones (these spaces are represented as empty circles with dashed lines, to pictorially provethe point) sothe excluded area (dashed red spaces) is very small in this case; however for the case of cylinders (Figure 4b), assuming that interpenetration is not allowed, there is plenty of free area that cannot be interpenetrated by another cylindrical entity of the same dimensions, since it does not t the space available, that is, there is signicantly more excluded area. Notice also that, at the same area fraction, the solid circles of Figure 4a do not form a single percolated path, while at least a vertical contacting path can be found among the solid cylindrical entities of Figure 4b. This is an important geometrical aspect which explains the signicantly lower percolation thresholds achieved for elongated cylinders (carbon nanotubes) compared to spherical particles (e.g., carbon black). [60,65,66]

V

r

Exc

¼

4

d

r

V

d

Exc

π

d

d

ð3b Þ

For CNT lengths in the order of microns and diameters in the order of tens of nanometers Equation (3a) is much higher than 1, while Equation (3b) is signi cantly lower than 1. This means that the excluded volume of graphene and few layer graphene sheets can be less or more than that of CNTs depending on the proportion between the lateral dimension of the sheets and the CNT length. A high excluded volume means that the network of llers within the composite has many spaces among the llers, that is, that the network is loosely packed (see Figure 4b). This means that the number of conductive paths is small and as such, small changes in the network conguration (upon strain application) are expected to produce large changes in electrical resistance, as explained in connection with Figure 2. Thus, a high excluded volume is expected to promote high piezoresistive sensitivity, and this may be the reason why higher piezoresistive sensitivity has been found for composites with CNTs as llers, as compared to another llers such as spherical carbon particles or akes of smaller lateral dimensions at the same weight fraction. [67] It should be kept in mind, however, that the number of ller- to- ller contact points within the conductive network is also a strong factor which in uences the electrical conductivity and piezoresistivity of this kind of nanocomposites. It is speculated that a relative high number of contact points should yield higher piezoresistive sensitivity, because of the higher changes in contact resistance produced upon straining the composite. Precise calculations of the number of contact points within a network requires specialized statistical calculations, such as those based on molecular dynamics, Montecarlo methods, or other statistical tools. [63,68] According to Wouterse et al. [68] the contact number for uncorrelated elongated spherocylinders depends on several factors such as the ller concentration and aspect ratio. According to these authors, above a critical ller concentration, the contact number for rods increases with increased ller volume fraction. They also found that the effect

www.advancedsciencenews.com www.aem-journal.com of the aspect ratio is nonmonotonic, with the contact number fi rst
www.advancedsciencenews.com www.aem-journal.com of the aspect ratio is nonmonotonic, with the contact number fi rst

of the aspect ratio is nonmonotonic, with the contact number rst increasing for aspect ratios less than six and then decreasing for elongated spherocylinders with aspect ratios above six. For aspects ratios above 80 the contact number is weakly dependent on the aspect ratio but below this aspect ratio the dependence is signi cant. Thus, a compromise may exist between the density of contact points within the conductive network, the excluded volume and the ller concentration. It is also important to bear in mind that the perspective of excluded volume and number of contact points covers only the morphological and statistical packing aspects between llers, and many other aspects such as the rheology of the polymer and its dielectric properties, the waviness of the ller, the ller functional groups and ller/matrix interface (which impacts strain transfer), alignment and dispersion, and the level of strain attained need also to be taken into account when analyzing the piezoresistive response of a carbon lled polymer composite. Finally, it should be pointed out that not all changes in the effective electrical resistance of a composite should be named piezoresistivity. The key issue in piezoresistivity is that the changes in electrical resistance are driven by changes in strain (or stress/pressure) in the material. Many other aspects that occur in advanced polymer composites such as matrix cracking, [31] delamination, [69] or even moisture or temperature variations [70] may also yield changes in the effective electrical resistance of the composite, but those phenomena (albeit interesting) should not be termed piezoresistivity. This is because in those cases the change in electrical resistance is not directly triggered by changes in strain or stress, but by other physical parameter.

3. Polymer Composites Filled with Graphite and Carbon Black

This section covers past and present work on the piezoresistive behavior of polymer composites lled with two of the earliest

carbon allotropes investigated to this aim, viz. carbon black (CB) and graphite. A review of the most relevant results, trends, and ndings regarding the piezoresistive response, strain, and damage sensing of these composites is presented in this section. The inclusion of these two llers to thermosettings, thermoplastics, and elastomers are discussed as a function of their distinctive piezoresistive re- sponse. Furthermore, strain and pres- sure sensing work ranges are identied, and a summary of the piezoresistive sensitivity (GF) for different polymer composites is discussed. A literature survey summarizing the piezoresistive behavior of polymer composites lled with CB and graphite is included in Table A1 of Appendix A. Such a table is organized by ller type and includes thermosetting (TS), thermoplastic (TP) and elastomeric (ES) matrices, as well

as the corresponding ller concentra- tion (wt%) and loading type (tension,

compression or bending). The main features of the piezoresistive response of the material are captured in Table A1 by four parameters, referring to its linear (L) or nonlinear (NL) character, maximum strain sensing capability (e max ), extend of linear piezoresistivity (e L ), and piezoresistive sensitivity (GF). The difference between e L and e max provides an indication of nonlinear piezoresistivity. Carbon black (a black powder produced by the incomplete combustion of carbonaceous or petroleum products) is likely the earliest carbon ller that has been extensively used to produce electro-conductive polymer composites with strain sensing capabilities. In Figure 5 , summary plots of the piezoresistive sensitivity (GF) of CB/polymer (Figure 5a) and graphite/polymer composites (Figure 5b) are presented (data extracted from Table A1). An immediate observation form this table is that, in comparison to other carbon nanostructures such as carbon nanotubes or graphenic akes, the concentration of CB used for piezoresistive applications is notoriously higher. This is a geometrical aspect, since higher ller concentrations are needed to reach electrical percolation for spherical particles than for nanostructures of high aspect ratio, see Figure 4. As seen from Figure 5a, for CB, ES matrices have been more explored than TS and TP polymers. It is also noticed that the CB concentration of TS and TP composites is generally below 15 wt%, while higher concentrations (>30 wt%) are used for ES matrices. In general, the piezoresistive response of CB/polymer composites is nonlinear, see Table A1. Gage factors are customary extracted from the initial part of the piezoresistive curve (i.e., e < 5%), where an approximately linear behavior is observed. The ultimate strain of composites with TS matrices is usually low ( < 6%), while TP and ES composites can sustain larger strains. The majority of the piezoresistive works report uniaxial tension loading, see Table A1, and the majority of the GF reported range between 3 and 15, see Figure 5a. Negative piezoresistivity has also been observed under tension and compression. [38] especially for elastomeric composites. Negative piezoresistivity means that, under uniaxial tensile loading (e>0), the electrical resistance decreases ( ΔR < 0), or that Δ R increases under compression. For TS composites, the family of CB/epoxy under tensile loading is the most investigated one, with ultimate strains below 6% because of the brittleness of epoxy in

strains below 6% because of the brittleness of epoxy in Figure 5. Summary of published gage

Figure 5. Summary of published gage factors for CB and graphite polymer composites. a) CB/polymer composites, b) graphite/polymer composites. Data extracted from Table A1.

www.advancedsciencenews.com www.aem-journal.com tension. [ 7 1 , 7 2 ] The piezoresistivity of CB/TP composites
www.advancedsciencenews.com www.aem-journal.com tension. [ 7 1 , 7 2 ] The piezoresistivity of CB/TP composites

tension. [71,72] The piezoresistivity of CB/TP composites has also been investigated, [73 78] nding positive GFs between 3 and 30, see Figure 5a. Zhao et al. [74] evaluated the tensile piezoresistive behavior of a 13 wt% CB/polypropylene composite and reported a nonlinear increasing piezoresistive behavior. The authors argument that both, formation and breakdown of conductive paths, compete during the loading process, making the curve nonlinear. As seen from Table A1, CB/ES composites made from rubber or polyisoprene are among the most common composites which have been investigated using CB. [73,79 85] Styrene ethylene butylene styrene (SEBS), a thermoplastic elastomer, has also been lled with CB presenting large deformation capabilities and piezoresistive strain sensing. [86,87] Elastomers are by far the most explored polymer matrices for CB likely because of their large stretch ratio, high exibility, and interest of the rubber industry. However, they are also more prone to present time-dependent viscoelastic relaxation and creep, which is captured by the piezoresistive response. [87,88] For elastomeric composites under tension, most of the reviewed literature (Table A1) shows an increase of electrical resistance with increased strain, that is, positive piezoresistivity, following a nonlinear behavior, especially at high strains (above 20%). When the composite is stretched, CB agglomerates are pulled away, disrupting certain conducting paths, with the concomitant increase in R . According to Figure 5, the GFs (extracted from e < e L , which ranges from 4% to 17% depending on the material) for CB/ES composites have been reported above 12. A different piezoresistive behavior under tension has been observed by other authors such as Flandin et al. [8,38] for an ethylene-octene elastomer lled with CB. These authors reported that, under tensile loading, after the increase in R during the rst stages of strain (elastic region) a decrease in R (negative piezoresistivity) occurs at higher tensile strains. The authors claim that for the ethylene-octene (comprising exible chains with fringed micel- lar crystals), the large strains produce new conducting pathways or improves the existent ones by CB reorientation and/or strain- driven agglomerate breakdown. Both positive and negative GFs have also been reported in different works under compression, see Figure 5a. Negative GFs, that is, increase of R with increased compressive strain, have been explained in terms of the destruction of the conductive network under compression, [84,85] while positive GFs have been explained in terms of increased particle volume fraction in the composites due to volume reduction during compression. [73] Wang et al. [89] explored CB/ silicone rubber composites at CB-to-rubber mass ratios varying from 0.08:1 to 0.24:1 (7.4 to 19.4 wt%). These authors report both positive and negative piezoresistivity for the same specimen at different levels of strain, and also depending on the CB concentration, see Figure 6. For example, for CB concentrations above 11.5 wt% they found positive piezoresistivity for all strain/ stress levels tested, but between 9.1 wt% and 10.7 wt% they found both, positive and negative piezoresistivity, see Figure 6. For concentrations of 8.3 wt% and below, however, the piezoresistive behavior turned monotonically negative, see Figure 6. This complex behavior was explained in terms of three main effects caused by the translation and rotation of the CB particles due to compression, viz. reduction of the gap between conductive paths, formation of new conducting paths, and destruction of existing conductive paths. The rst two

mechanisms support positive piezoresistivity, while the latter one explains negative piezoresistivity. Several authors have also explored the piezoresistive behavior of CB/polymer composites under cycling loading, [8,38,72,74 77,85,90] viscoelastic relaxation, [87] and creep, [73,84] and a few of them have pointed out the effect of hysteresis. [72,74,75,77,90] Damage and irreversible phenomena can also be assessed by means of the electrical response of the composite. In this regard, CB/HDPE composite lms under uniaxial tension have shown negligible variations in R for e < 8% (elastic region, according to the authors), and a sudden increase of R for higher strains corresponding to the elastic-to-plastic transition. [76] The authors state that this unique electrical property could be used to identify the elastic and plastic regions, representing a valuable tool for damage assessing. Regarding the use of graphite as a ller material, the piezoresistive behavior of graphite/polymer composites under tension, [91] compression, [6,92 94] and bending [95,96] has also been investigated. Figure 5b summarizes the GFs of graphite/polymer composites for different polymer matrices. In comparison to CB/polymer composites, evaluation of the piezoresistivity of graphite/polymer composites in terms of strain or GFs has been less explored. A great number of the existent works report on sensitivity as a function of applied pressure, that is, calibrating as a pressure sensor. According to our literature survey (see Table A1 and Figure 5b), the great majority of graphite/polymer composites exhibit positive piezoresistivity with the majority of GFs ranging from 7 to 25. From the literature survey conducted, Shevchenko et al. reported the highest GFs for graphite/polymer composites using a polypropylene (PP) matrix under tension, with GFs associated to the linear region of the piezoresistive plots (e < 1%) ranging from 7 (45 wt%) to 100 (12.5 wt%). [91] These authors also presented evidence that the linearity of the graphite/PP piezoresistive curves increases as the graphite volume fraction increases. Serra et al. [96] reported on the piezoresistive behavior of graphite/epoxy composites under bending. The composites were bonded to a rigid substrate (alumina or aluminum) which

were bonded to a rigid substrate (alumina or aluminum) which Figure 6. Piezoresistive response of CB/rubber

Figure 6. Piezoresistive response of CB/rubber composites for different CB loadings. [89] (Reproduced from ref.[89], with permission from Elsevier).

www.advancedsciencenews.com www.aem-journal.com Table 1. Summary of pressure-dependent piezoresistive behavior of polymer
www.advancedsciencenews.com www.aem-journal.com Table 1. Summary of pressure-dependent piezoresistive behavior of polymer

Table 1. Summary of pressure-dependent piezoresistive behavior of polymer composites filled with CB and graphite.

Pressure-dependent piezoresistivity

Filler

wt%

Matrix

L/NL

P max (kPa)

P L (kPa)

S (x10 3 , kPa 1 )

Ref.

Carbon black

20

Natural rubber

NL

2400

1600

0.4

[99]

10.3

PMVS

L

1200

1200

0.07

[100]

10

Silicon rubber

NL

600

80

1.35 to 1.65

[101]

8

Silicon rubber

L

700

700

0.4

[102]

5

Silicon rubber

NL

1000

800

2.5

[103]

0.8

Silicon rubber

NL

1000

500

0.25

[89]

0.16

Silicon rubber

NL

1000

500

0.5

[89]

10

Polyisoprene

NL

400

40

0.5

[104]

10

Polyisoprene

NL

100

40

3

[105]

Graphite

0.5

Epoxy

NL

75 000

13 000

0.05

[106]

20

HDPE

NL

25 000

5000

0.04 to 0.08

[107]

3

Silicon rubber

NL

750

200

1.3

[106]

6.6

Silicon rubber

NL

500

100

0.3

[108]

22.1

Silicon rubber

NL

500

100

1.2

[108]

30

Polyurethane

NL

60

5

63

[98]

Acronyms : HDPE ¼ High density polyethylene, PMVS ¼ poly(methylvinylsilioxane), L ¼ Linear, NL ¼ Nonlinear, P max ¼ Maximum pressure registered by the electrical signal, P L ¼ Maximum pressure corresponding to approximately linear piezoresistivity, S ¼ Pressure-dependent piezoresistive sensitivity.

was directly bent. Authors found that the GF of graphite/epoxy composites bonded to a beam decreases with increased graphite concentration for both alumina and aluminum substrates. Using a similar bending approach, Frazier and Allen [95] reported the piezoresistive behavior of graphite/polyimide composites bonded to a rigid silicon substrate. These authors found that the GF of the composites rst increases with increased graphite concentration, and then decreases, reporting a peak GF of 16.8. It is important to notice that when the piezoresistive material is not directly stretched but bonded to a beam, the stress/strain transfer from the tested beam (substrate) may not be perfect, which would affect the piezoresistive measurement and determination of gage factor. On the other hand, Beruto et al. [93] reported that R decreases with increased compressive strain (i.e., positive piezoresistivity) for graphite/rubber compo- sites, being such changes more signi cant as the graphite concentration decreases and approaches the percolation thresh- old. Chen et al. [94] reported a negative piezoresistivity for a graphite nanosheet/rubber composite under compression, which is also more pronounced as the graphite concentration is closer to the percolation threshold. The authors argument that the mechanism underlying such a negative piezoresistivity is the breakdown of conductive pathways and that the transport mechanism can be understood in terms of the tunneling conduction between conducting particles. Cyclic load- ing [6,91,94,96] and relaxation tests [92,96] have also been explored by a few authors. Regarding irreversible effects, Shevchenko et al. [91] showed that the piezoresistive hysteresis under loading- unloading cycles is reduced with increased number of cycles and by increasing the particle concentration. Lu et al. [6] also reported that the piezoresistive response is different among sequential loading-unloading cycles, being more stable (but less sensitive)

as the number of cycles increases. These authors also highlighted the dependence of the piezoresistive response on the creep behavior of the polymeric matrix and the elastic properties of the llers. [6] Other authors such as Chen et al. [94] have also reported that the hysteresis reduces with increased number of cycles for graphite nanosheets in silicone rubber. For pressure sensors, the piezoresistive behavior of CB-based and graphite-based polymer composites can also be approached in terms of applied pressure (instead of applied strain). To quantify the linear piezoresistive sensitivity as a function of

the linear piezoresistive sensitivity as a function of Figure 7. Summary of published gage factors for

Figure 7. Summary of published gage factors for SWCNT and MWCNT polymer composites. Data extracted from Table A1.

www.advancedsciencenews.com www.aem-journal.com the applied pressure (P), a pressure-dependent piezoresistive coef fi
www.advancedsciencenews.com www.aem-journal.com the applied pressure (P), a pressure-dependent piezoresistive coef fi

the applied pressure (P), a pressure-dependent piezoresistive coef cient S ¼ ( Δ R/R 0 )/ ΔP has been customarily used. [97,98] This coef cient is the pressure analogous of the GF, which is de ned in terms of pressure instead of normalized strain. Table 1 summarizes the most relevant pressure-dependent piezoresistive parameters for several CB and graphite polymer composites. Relatively high ller loadings, usually above 5 wt%, are generally used for these applications, although composites with lower concentrations (<1 wt%) can also be found, see Table 1. Higher loadings of CB and graphite, as compared to other llers such as carbon nanotubes or graphenic akes, are required for pressure sensing applications of these materials due to the corresponding lower excluded volume and aspect ratio of these llers. Elastomeric matrices are undoubtedly the most used ones for pressure sensors due to their suitable exibility and mechanical properties. The applied pressures customarily range from few tents of KPa to nearly 100 MPa. Except for the high value (63 10 3 kPa 1 ) reported by He et al., [98] the magnitude of the reported sensitivity factors in Table 1 ranges from 0.04 10 3 to 3 10 3 kPa 1 . Positive and negative pressure-dependent piezoresistivity has also been observed.

4. Polymer Composites Filled with Carbon Nanotubes

Among the carbon- lled polymer composites, those modi ed with CNTs are undoubtedly the ones that have captured more attention of the scientic community, as evidenced by the numerous publications to date. They range from the early work on buckypaper of Dharap et al. in 2004 [109] to current and ongoing research. [110,111] A brief literature survey summarizing the piezoresistive behavior of polymer composites lled with SWCNTs and MWCNTs is included in Table A1 of Appendix A. Such a table is organized by ller and matrix types and includes the corresponding ller concentration (wt%) and loading type, as discussed in section 3. The literature survey suggests that the majority of published works are on epoxy composites lled with MWCNTs, and substantial work has also been published using a variety of thermoplastic and elastomeric matrices such as thermoplastic-polyurethanes (TPUs) and polydimethylsiloxane (PDMS). By far, the great majority of the piezoresistive works report only tensile loading, being compres- sion and exural loading signi cantly less reported. Figure 7 summarizes the piezoresistive sensitivity (in the form of gage factors) of the SWCNT and MWCNT polymer composites listed in Table A1. Data for buckypapers (BP) is also included for completeness. As seen from this gure, the great majority of GFs for CNT polymer composites are found between 1 and

7, without a particularly distinctive trend between SWCNTs and MWCNTs. However, composites with MWCNTs seem to be more reported, probably because they are easier and

more economical to synthesize in large scale. Notice that the magnitude of the GFs for SWCNT and MWCNT composites in Figure 7 are comparable to those obtained using graphite or carbon black in Figure 5, but as seen from Table A1, those for graphite and carbon black require signi cantly higher ller concentration. Reports on negative gage factors are scarce, but they have also been reported, especially under compressive loading. [112] Particular features of CNT polymer composites with TS, TP, and ES matrices are discussed in the following sections.

4.1. Thermosetting Matrices

Epoxy thermosettings lled with SWCNTs [113] and MWCNTs [48,71,72,110,114 117] are among the most extensively investigated polymers regarding piezoresistivity of polymer composites, compared to other thermosetting polymers such as vinyl ester [112] or polyester. Given their low processing viscosity, a distinctive feature of these polymer composites is their capability of reaching electrical percolation at CNT concentration levels signi cantly smaller than those for thermoplastics or elasto- mers, see Table A1. Because of these, CNT concentrations of 0.3 wt% or below are suf cient to guarantee piezoresistivity in thermosetting composites (see Table A1). This very low ller concentration, alongside with the superior mechanical proper- ties of thermosetting composites, makes them particularly attractive for further developments of advanced multiscale hierarchical composites loaded in tension, compression, or

bending. [31,118 120]

Linear piezoresistivity is quite common for CNT thermoset- ting composites loaded in tension with low ultimate strains (Figure 8a), but nonlinear and even nonmonotonic piezoresis- tivity may also occur for thermosettings or modi ed thermoset- tings with relatively high(within the context of thermosettings) ultimate strains. [71] For this later case, an inversion of the piezoresistive trend (from positive to negative) may occur for certain CNT weight concentrations under relatively large deformations (Figure 8b, see ref. [71]), presum- ably because of polymer inelastic behavior. Negative piezor- esistivity means that the effective (three-dimensional) distance between CNTs is reduced as the polymer is axially stretched,

between CNTs is reduced as the polymer is axially stretched, Figure 8. Piezoresistive response of thermosetting

Figure 8. Piezoresistive response of thermosetting polymer composites. a) Linear response of a 0.3 wt% MWCNT/vinyl ester composite. [121] (Reproduced from ref. [121] , with permission from Elsevier), b) nonlinear and nonmonotonic response of a 0.1 wt% MWCNT/epoxy composite. [71] (Reproduced from ref. [71] , with permission from the American Physical Society).

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www.advancedsciencenews.com www.aem-journal.com and may be caused by matrix plasticity, lateral CNT motion by Poisson ’
www.advancedsciencenews.com www.aem-journal.com and may be caused by matrix plasticity, lateral CNT motion by Poisson ’

and may be caused by matrix plasticity, lateral CNT motion by Poisson s effect and/or three-dimensional CNT network rear- rangement under large strains. [71,111] The CNT weight concentration also affects the piezoresistive response, and is commonly accepted that lower CNT concen- trations yields higher piezoresistive sensitivities. [112,114] This is because lower CNT concentrations yields less redundant paths forming the CNT network, and also the tunneling effect is expected to be more signi cant for CNT concentrations close to percolation. [53] Tensile loading is by far the most commonly investigated loading case, although a few works have also investigated compression [112,121] and bending. [110] Ku-Herrera and Avil es [121] used 25.4 mm long prisms of 12.5 mm square cross section to investigate the piezoresistive response and damage accumula- tion of 0.3 wt% MWCNT/vinyl ester specimens under uniaxial compression loading. They found a nonlinear and nonmono- tonic behavior under monotonic compression loading up to failure (see Figure 9a), with the electrical resistance rst decreasing (positive gage factor) and then increasing (negative gage factor) for relative large strains (e> 2.5%). The transition zone (from positive to negative piezoresistivity) was shown to correlate with polymer yielding, pinpointing that the MWCNT network is not only able to self-sense strain, but also polymer yielding and plasticity. Under cycling compressive loading at incremental strains of magnitude e cyc (Figure 9b), a reversible behavior of ΔR/R 0 was observed for strains below the polymer yield strain, but Δ R/R 0 was irreversible and cumulative for cycling strains above polymer yielding. As seen from Figure 9b, the irreversibility of ΔR/R 0 upon unloading is an indication of plasticity and damage accumulation, which can be quanti ed based on such a permanent electrical response. [121] Regarding exural loading, the scarce studies seem to indi- cate that the piezoresistive response is more sensitive under uniaxial tension than under exural loading, [110] although more research is needed to unveil the reasons for that. The use of piezoimpedance (instead of piezoresistance) is also an interest- ing avenue that has been suggested by very few authors. It is argued that at high frequencies ( 1 MHz) alternating-current measurements (piezoimpedance) are more sensitive than those in direct current (piezoresistance) due to the combined action

of the effective resistance and capacitance that determine the overall electrical response of the material. [110]

4.2. Thermoplastic Matrices

Thermoplastics are generally tougher and more deformable than thermosetting polymers; therefore, piezoresistivity has been extended to larger strain sensing capabilities for CNTcomposites using thermoplastic matrices (see e max listed in Table A1 of appendix A). As seen from Table A1, a large variety of thermoplastic polymers such as polymethyl methacrylate (PMMA), [32,122] polyvinylidene uoride (PVDF), [123 127] polycar- bonate (PC), [128] polyethylene oxide (PEO), [129] polysulfone (PSF) [130] polyethylene terephthalate (PET), [131] and polypropyl- ene (PP) [33,74] have been modied with CNTs to achieve piezoresistive strain sensing capabilities. In general, the gage factors reported for CNT/thermoplastic composites in the elastic regime are similar (or slightly above) than those for thermoset- tings, as pointed out in Figure 7. However, because of their larger deformation capabilities, higher gage factors than those for CNT/thermosetting composites have been found for CNT/ thermoplastic composites in the plastic regime. [55] This larger sensitivity is concomitant with a nonlinear piezoresistive curve, which is usually driven by inelastic deformations. For example, Zetina-Hernández et al. [33] found that for 4 wt% MWCNT/PP composites, the tensile piezoresistive curve attains a gage factor of 3.6 for strains below 1%, and the sensitivity is highly increased (GF 28.9) for larger strains, Figure 10 . An indication of the increased sensitivity with respect to thermosetting polymers is seen in the maximum values of Δ R/ R 0 attained in Figure 10a ( 280%), compared to those in Figure 8a ( 3.3%). The authors further conducted loading-unloading tensile experiments to prove that the transition zone (1% < e < 2%) corresponds to polymer yielding, and that the high gage factors observed for e > 2% correspond to polymer plasticity. Nanni et al. [131] also conrmed that the yield point of the polymer (PET in this case) can be identi ed by a transition zone with reduced sensitivity in the electro-mechanical signal, as seen in Figure 10b. Using 1, 2, and 4 wt% MWCNT/PET composites, they demonstrated a strong correlation between polymer yielding and the electrical resistance, whose particular features

and the electrical resistance, whose particular features Figure 9. Electrical response of a 0.3 wt% MWCNT/vinyl

Figure 9. Electrical response of a 0.3 wt% MWCNT/vinyl ester composite under axial compressive loading. a) Monotonic loading up to failure, b) cycling loading, each cycle reaching a strain e cyc . [121] (Reproduced from ref. [121] , with permission from Elsevier).

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www.advancedsciencenews.com www.aem-journal.com Figure 10. Piezoresistive behavior of CNT/thermoplastic composites. a)
www.advancedsciencenews.com www.aem-journal.com Figure 10. Piezoresistive behavior of CNT/thermoplastic composites. a)
www.advancedsciencenews.com www.aem-journal.com Figure 10. Piezoresistive behavior of CNT/thermoplastic composites. a)

Figure 10. Piezoresistive behavior of CNT/thermoplastic composites. a) MWCNT/PP at 4 wt%. [33] (Reproduced from ref. [33] , with permission from Springer), b) MWCNT/PET at 2 wt%. [131] (Reproduced from ref. [131] , with permission from Elsevier).

depend on the MWCNT concentration. At PET yielding (e 4.2%), the excessive deformation of the polymer causes signi cant rearrangement of the CNT network, pinpointing a local change in trend of the electrical resistance; right after yielding the CNT-to-CNT separation largely increases triggering high values of Δ R/R 0 , see Figure 10b. Given the large deformation and nonlinear behavior of CNT/ thermoplastic composites, electron tunneling has been frequently cited among the major mechanisms driving piezoresistivity in these materials. [55,132] This explanation seems particularly plausi- ble for large deformations, where the CNT-to-CNTseparation is in the order of a few nanometers and the form of the piezoresistive curve is exponential, as described by the tunneling model. [43] The behavior of the electrical resistance under cycling (tensile) loading has also been investigated for CNT/thermoplastic composites. [32,74,128,133] The results suggest that these smart materials are able to self-sense strain, instantaneous, and accumulated damage. Under cycling experiments, the Δ R/R 0 curve accurately follows the applied strain, but only if such strains are elastic. Given the inherent polymer viscoelasticity, the piezoresistive response may become time-dependent. [127] If plasticity, any form of damage, or viscoelastic phenomena occur, the electrical resistance does not exactly follow the cyclic applied strain (see Figure 11) and the extent of such a difference correlates with the amount of inelastic strain and/or accumu- lated damage. As for thermosettings, the capability of self- sensing strain and damage of these composites can be exploited for the development of advanced multiscale hierarchical composites comprising an engineering ber, carbon nanotubes, and a thermoplastic matrix. [21]

4.3. Elastomeric Matrices

Piezoresistivity in elastomeric polymer composites is quite unique because of the extremely large strain sensing capabilities rendered, see e max for different polymers in Table A1. Because of such large strain sensing capabilities, the piezoresistive response of elastomeric composites is customary nonlinear, see for example, Figure 12 . [134] Unlike thermosetting and thermoplastic nanocomposites, the intended piezoresistive applications of elastomeric polymer

composites are more leaned towards low load bearing capacity applications, such as stretchable and wearable strain sensors, sensors of human motion, soft skins, biomedical appli- cations, and exible electronics, among others. [15] The common fea- tures in all these applications are the need of very large strain sensing (typically e>1), while less importance is devoted to their mechanical load bearing capacity. This is contrasting with the aimed applications of ther- mosetting and some thermoplastic carbon-based composites for struc-

tural health monitoring of advanced composites, [21,31,118,119] where the me-

chanical loads are of major concern. Thermoplastic polyur- ethanes, [111,134 138] polydimethylsiloxanes (PDMSs), [20,139 141] silicone rubber, [142] SEBS, [143,144] styrene butadiene styrene (SBS), [145 148] ethylene propylene diene, [149] and natural rubber [67] are among the major elastomers (or thermoplastic elastomers) that have been investigated regarding piezoresistive and strain sensing applications, see Table A1. The typical strain sensing capabilities of these polymers range from e ¼ 50% to a few times its initial length (1x to 3x), although strain sensing capabilities up to 10x (1000%) have been reported, [136] as seen from Table A1. Tunneling is invariable listed as one of the major mechanisms contributing to the piezoresistivity of elastomeric polymer composites, [67,132] especially at large strains. The high nonlinearity of the piezoresistive signal for elastomeric composites is indicated in Table A1 by the null value of e L or by the large difference between e max and e L . This nonlinearity yields a dependence of Δ R/ R 0 with strain, that is, gage factors that are not constant but depend on the strain level. [134,145,146] Therefore, very large piezoresistive sensitivities can be obtained for elastomeric composites in the high deformation regime, see

elastomeric composites in the high deformation regime, see Figure 11. Behavior of the electrical resistance under

Figure 11. Behavior of the electrical resistance under 10 loading- unloading cycles for 3.4 vol% MWCNT/PP composites. [74] (Reproduced from ref. [74] , with permission from Elsevier).

www.advancedsciencenews.com www.aem-journal.com their piezoresistive response. [ 8 7 , 1 4 6 , 1 5
www.advancedsciencenews.com www.aem-journal.com their piezoresistive response. [ 8 7 , 1 4 6 , 1 5
www.advancedsciencenews.com www.aem-journal.com their piezoresistive response. [ 8 7 , 1 4 6 , 1 5 1

their piezoresistive response. [87,146,151 153] In fact, it has been observed that the piezoresistive sensitivity of thermoplastic elastomer composites such as SBS may depend on their strain rate. [146] An important feature of elastomeric composites is that they tend to present signi cant piezoresistive hysteresis under cycling loading, [15,138,154] which is very relevant for any practical implementation. This means that the pathway followed by the ΔR/R 0 versus e curve for loading is different to that for unloading, which has been quanti ed by the normalized area under the loading-unloading Δ R/R 0 versus e curve, and termed piezoresistive hysteresis (H P ), see Figure 14 . According to Lozano-P erez et al., [153] for MWCNT/TPU composites H P also depends strongly on the rigid segment (and MWCNT) content, as seen from Figure 14a and b for 4 wt% MWCNT composites. Notice also from these gures that after unloading, the electrical resistance does not return to the same initial (unloaded) value, which is a form of point hysteresis (as opposed to that of trajectory), of high relevance for any practical implementation. Lozano-P erez et al. [153] also noticed that H P decreases as the material is repeatedly stretched an unstretched, that is, as the number of cycles increases, Figure 14c. This is because the exible and rigid domains of the segmented polyurethanes rearrange during the cyclic deformation process, with the MWCNT network acting as physical cross-linkers.

5. Polymer Composites Filled with Graphenic Sheets

The interest on graphene and its few-layer derivatives has tremendously grown since the landmark work of Geim and Novoselov s group reporting on mechanical isolation of an individual graphene sheet in 2004. [155] Since then, many research efforts have taken advantage of the electrical and electronic properties of this family of graphenic materials (monolayer, few-layer, and multilayer) for the development of electro-mechanical, strain sensing, and other sensory and/or actuating devices. [156 158] Graphene (a monolayer) has excellent physico-chemical properties, such as a very high elastic modulus (200 times stronger than steel), excellent electrical and thermal conductivity, and very large specic surface area. [155,159] The term graphene, strictly speaking, refers to a single layer of sp 2 bonded

Figure 12. Piezoresistive behavior of a 6 wt% MWCNT/TPU nano- composites. [134] (Reproduced from ref. [134] , with permission from John Wiley & Sons).

for example Ref.[111,146] as indicated in Figure 7 and Table A1. For very large strains (typically e>1), the inter-particle distance becomes so high that the tunneling effect is no longer active, yielding a disconnection of the conductive network and a sharp decrease of electrical conductivity, losing the strain sensing capability. [137] It has been shown that the strain at which this electrical transition happens (indicated by a vertical arrow around e 107% in Figure 12) depends on several factors such as the polymer and CNT types, the state of dispersion and the CNT concentration. [134,137] TPU composites are a special case of thermoplastic polyure- thane elastomeric composites that have been used for large strain sensing applications. The microstructure of CNT/TPU composites comprises a phase separation (domains) between the rigid and exible segments of the polymer, with the CNTs preferentially bonded to the urethane groups of the rigid segment (RS) domain. [111,150] Both, the CNT content and the RS content promote a rigid-to- exible phase separation, forming domains. Using MWCNT/TPU composites of 15, 30, and 50 wt% RS content at MWCNTcontents of 2, 4, and 6 wt%, Lozano-Perez et al. [111] showed that the RS content is more in uential than the MWCNT content for achieving phase separation. Since MWCNTs are preferentially dispersed within the RS phase domain, it has been shown that the piezor- esistive response of MWCNT/TPU compo- sites strongly depends on the relative concentration of rigid-to- exible segments and also on the MWCNT content. [111] As seen from Figure 13 , changes in electrical resis- tance above 10,000 times the unstrained electrical resistance at e ¼ 100% were achieved for very exible composites comprising 15 wt % RSs and 4 wt% MWCNTs, while such changes were about 100 times for composites with 30 wt% RSs at the same MWCNT concentration. Elastomers are more prone to present

viscoelastic behavior (relaxation, creep) and hysteresis under cyclic loading, and these time-dependent phenomena are re ected in

and these time-dependent phenomena are re fl ected in Figure 13. Piezoresistive behavior of MWCNT/TPU composites

Figure 13. Piezoresistive behavior of MWCNT/TPU composites at different rigid segment and MWCNT contents. a) 15 wt% RS, b) 30 wt% RS. [111] (Reproduced from ref. [111] , with permission from John Wiley & Sons).

www.advancedsciencenews.com www.aem-journal.com Figure 14. Piezoresistive response and hysteresis under tensile cycling
www.advancedsciencenews.com www.aem-journal.com Figure 14. Piezoresistive response and hysteresis under tensile cycling
www.advancedsciencenews.com www.aem-journal.com Figure 14. Piezoresistive response and hysteresis under tensile cycling

Figure 14. Piezoresistive response and hysteresis under tensile cycling loading for MWCNT/TPU composites at 4 wt% MWCNTs and different RS content. a) First cycle, b) fifth cycle, c) piezoresistive

hysteresis ( H P ) as a function of the cycle number. [153] (Reproduced from ref. [153] , with permission

from Elsevier).

carbon atoms, [160] which can be produced by bottom-up or top- down approaches. [161,162] A host of literature has inaccurately used the term graphene to refer to any member of the graphenic family in a generic way (see Bianco et al. [160] ), downplaying the role of the number of layers and nanostructure in the resulting effective properties of the nanocomposite. Given this issue, international efforts to normalize the terminology of graphene-based materials have suggested the use of a standardized nomenclature which considers the number of graphene layers, average lateral dimensions, and the carbon- to-oxygen ratio as the main parameters for naming such nanostructures. [160,163] This proposed nomenclature will be followed in this review, supporting the international efforts to converge to a standardized nomenclature. Given the dif culty of maintaining thermodynamically stable individual sheets of sp 2 bonded carbon atoms inside a bulk polymer, the two- dimensional forms of carbon ller that have been mostly used in polymer composites are actually few-layer graphene (FLG, 25 layers), multi-layer graphene (MLG, 610 layers) or exfoliated graphite (EG). Their distinction from work to work can be quite dif cult for a review paper, since not only they are frequently not properly named but also their morphological (number of layers, lateral dimensions) and physico-chemical properties are in many instances not provided. This issue prohibits a proper examination of structure-property relationships in this kind of nanocomposites to date. Free standing (single-layer) graphene has been reported as a material with piezoresistive properties, suitable for the develop- ment of electro-mechanical devices and strain sensing applica- tions. [164,165] The GF of suspended single-layer graphene has been reported as high as 151 [35] and GFs of FLG lms with

different thicknesses and conductivities have been reported varying from 10 to 300. [166] However, other authors have also reported much lower GFs for FLG sheets aimed for strain/pressure sensing, viz. 10 to 15 in ref. [167], 1.9 in ref. [164] , and 2.9 to 4.3 in ref. [165] . The high GFs reported for individual graphene or FLG sheets greatly reduce when such a family of graphenic sheets (GSs) are deposited on substrates or used as llers for polymer composites. Pressure and strain sensing devices based on MLGs deposited on silicon membranes have shown GFs of 1.6, [168] while FLG patterns deposited on polymer substrates have reported GFs around 6. [158] A common sensory application given to this family of GSs consists in deposit- ing them over a exible substrate and bonding the lm material (or transfer- ring the GS) to a beam for piezoresistive strain measurement. This procedure has also yielded very high GFs such as 150 [169] and 250. [170] Direct deposition of EG on a

PMMA beam has also reported a GF of 50. [171] Other works about piezoresistive sensors based on GS in the form of isolated membranes, sheets or graphene-paper (GP) bonded to polymeric substrates have shown GFs as high as 546 for the case of a PDMS substrate/beam, as indicated in Table A1. This information is summarized in Figure 15 (labeled as GP, corresponding to 100% weight content), along with the GF of polymer composites lled with a variety of GSs. Regarding polymer composites lled with GSs, the lled composites are either directly tested or bonded to a beam, and such a beam is loaded. Direct testing of GS/polymers has been conducted under tension [61,172 174] and compression load- ing. [175 177] Bonding the GS/polymer composite material to a metallic, polymeric, or composite beam for subsequent testing of the beam has also been reported under tension [178] and, more frequently, bending loading. [179 182] As seen from Table A1 and Figure 15, a variety of polymer matrices have been used for the development of piezoresistive nanocomposites based on GSs, from thermosettings such as epoxy [172,179,183] and vinyl ester, [181] to elastomers such as PDMS, [174,178,182] TPUs, [176,177] and ethylene-butene copolymer (EB). [61] According to the literature review, uniaxial tension has been the most investigated loading scenario for this kind of polymer nanocomposites, followed by bending tests and, less commonly, direct uniaxial compression. As for the case of CNTs, the reported works on polymer nanocomposites lled with graphenic sheets also conclude that the sensitivity of the nanocomposites is in uenced by the ller concentration, with higher sensitivity for lower ller content. [178,180,182] Regarding GS nanocomposites with thermosetting matrices, nonlinear behavior of the piezoresistive curve is observed for the majority of the reviewed publications, which applies for both, tensile and bending tests. This is a bit different to the case of

www.advancedsciencenews.com www.aem-journal.com Figure 15. Summary of published gage factors for polymer composites
www.advancedsciencenews.com www.aem-journal.com Figure 15. Summary of published gage factors for polymer composites
www.advancedsciencenews.com www.aem-journal.com Figure 15. Summary of published gage factors for polymer composites

Figure 15. Summary of published gage factors for polymer composites filled with graphenic sheets. Data extracted from Table A1.

CNT lled composites, where a large linear region is frequently observed for thermosetting polymers. In general, the maximum strain attained for all revised works with thermosetting matrices is e max 3%. The reports available in the literature for thermoplastic matrices lled with the family of GSs are substantially less. Among the few existent reports, a strain sensor using reduced graphite oxide into a polyvinylidene uoride (PVDF) matrix bonded to an aluminum beam and loaded in tension showed a GF of 12.1. [184] PVDF composites using reduced FLG sheets have also been produced and bonded to a exural beam, showing gage factors between 7 to 11 when the composite is bent with the beam. [185] This work also highlighted the in uence of the morphology of the carbon ller, yielding different gage factors for FLG oxide, reduced FLG sheets, and carbon nanohorns. [185] Three-dimensional reduced few layer graphene oxide has also showed excellent exibility and piezoresistive properties when mixed with a polyimide matrix to fabricate sponge materials. [186] Polystyrene has also been used as a matrix for composites lled with GS tested under compression showing self-sensing of strain. [187] Similar to the case of CNTs, GS composites show higher GFs for elastomeric matrices than for any other polymer matrix (see Figure 15). This is expected due the exibility and large straining capabilities of elastomeric polymers, which render high GS mobility. However the piezoresistive behavior of such nano- composites typically exhibit a highly nonlinear (and time- dependent) behavior [61,174 177] along with high e max , see Table A1. Similar to CNT composites, their high deformation capabilities makes them suitable for development of strain sensors for human motion, electrodes for exible electronics, wearable electronics and human/computer interfaces. [188 190] GS/polymer nanocomposites not only have the ability to self- sense strain, but also damage and other irreversible phenomena. This has been more explored for thermosetting polymers, given their higher stiffness and strength, which makes them more suitable for load bearing applications. Zha et al. [172] reported the application of 2.7 wt% amino functionalized GS/epoxy

composites for structural health monitoring under tensile loading. As indicated in Figure 16, the electro-mechanical curve of such nanocomposites showed two zones; the rst one presented a quite linear increment of fractional electrical resistance, while the second one showed abrupt incremental steps of electrical resistance. The rst (linear) region can be correlated to the elastic deformation of the material, while the incremental steps in the second zone are attributed to accumulation of microcracks and permanent damage in the nanocomposite. [172] Proper functionalization of carbon nano- structures is known to improve their dispersion and load transfer with the polymer matrix, but its direct effect on the piezoresistive sensitivity is yet debatable. Similarly, following ideas previously proposed for CNTs, a few other works have extended this concept using graphenic sheets for in-situ structural health monitoring of ber reinforced polymer composites, by adhering the graphenic nanocomposite to tensile or bending beams. [191] Cyclic tests of graphenic composites have also indicated residual changes in electrical resistance after cycling loading, [172,180,191,192] caused by rear- rangement of the conductive pathways during cyclic excursions. An interesting feature observed from comparison of the GFs in Table A1 for graphenic composites to those for CNT composites, is that most GFs for composites using CNTs as llers are below 30 (see Figure 7), whereas those for composites using GSs are overall higher (the span is almost twice, according to the inset in Figure 15). This trend may be explained in terms of the excluded volume, and indicates that the aspect ratio and morphology of conductive llers play a paramount role in the piezoresistive response of nanocomposites, [61,67] as explained in section 2. These data indicate that strain sensitive composite materials with higher sensitivity could possibly be developed by the use of two-dimensional graphenic sheets. As seen from section 2, this of course depends on the relative dimensions of the llers (see Eq. 3), and other factors such as the strain level. However, larger piezoresistive sensitivity has also been achieved for composites with CNTs than with GSs. [67] Another feature observed from Table A1 is that the ller concentration used for such piezoresistive applications is signi cantly higher for GS than for CNT composites. Besides, GS/polymer composites also exhibit noticeable nonlinearity and strain sensing capabilities

noticeable nonlinearity and strain sensing capabilities Figure 16. Electro-mechanical response of 2.7 wt% EG/epoxy

Figure 16. Electro-mechanical response of 2.7 wt% EG/epoxy compo- sites. [172] Reproduced from ref. [172] with permission from Elsevier.

www.advancedsciencenews.com www.aem-journal.com which depend on the deformation level. [ 6 7 , 1 8 0
www.advancedsciencenews.com www.aem-journal.com which depend on the deformation level. [ 6 7 , 1 8 0

which depend on the deformation level. [67,180,191,192] This features may not be desirable for industrial applications, likely requiring implementation of some type of data signal lineariza- tion or compensation to be able to advance towards commercial devices. [193] As a nal remark of this section, a few recent works have been conducted towards the exploration of hybrid architectures combining CNTs and GSs mixed within polymer matri- ces. [67,194,195] According to the initial studies on the piezoresistive response of hybrid nanocomposites, the piezoresistive sensitivity might be controlled by adjusting the CNT-to-GS ratio. [67,195] The use of hybrid CNT-GS llers may also bring about improvements in the ller dispersion and load transfer from the matrix, beneting the mechanical properties of such nanocomposites. [196]

6. Piezoresistivity in Nanocomposites with Aligned Fillers

Aligned carbon-based composites with anisotropic properties are expected to render several advantages over those with randomly oriented llers. [197 199] One way of obtaining such anisotropic properties is by forming directionally aligned nanostructures within the polymer. In general, the formation of aligned structures within polymer matrices can be obtained during the composite formation (e.g., by in ltration, ber drawing, or application of electric or magnetic elds) or after the incorporation of the llers to the matrix (e.g., by stretching or polymer compression). [198] Several attempts to align CB, [200,201] CNTs, [202 209] and more recently, graphenic platelets, [210] have been reported, although prefect alignment at the macro- and nanoscales is yet a challenge. For the case of CNTs, excellent reviews regarding the formation of CNT assemblies with controlled orientation [211] and directional alignment of CNTs within polymers can be found elsewhere. [198] As a generally accepted outcome, the effective properties of the composite material (e.g., mechanical, thermal, electrical) become anisotropic upon alignment, that is, are strongly inuenced by the ller orientation. Since the intensity of the magnetic elds required to align CNTs within polymers seems to be unpractically

high, [212,213] application of alternating current electric elds arises as a more suitable option. [214 217] The electric eld approach relies on the electric dipole moment induced on the CNTs due to the different electrical properties of the CNTs and surrounding medium. The induced moments promote CNT-to-CNT inter- actions, where forces and torques tend to orient and interconnect the CNTs. [218,219] This strategy has been applied, for example,toalignMWCNTs in dissolved polysulfone, [217] as well as to align SWCNTs in photo-polymerizable resins. [215,220] Figure 17 shows examples of polymer compo- sites with evident mesoscopically aligned struc- tures conformed by CNTs, wherethe application of an alternating current electric eld was used. As seen from both gures, preferential align- ment of CNT bundles has been achieved at the

meso-scale, but certain degree of misalignment is yet visible. To date, alignment at the

macroscale in polymer composites with evidence of perfect individual CNT alignment at the nanoscale is yet a challenge. The effect of ller alignment on the piezoresistive response of carbon-based polymer composites has been scarcely explored, with the majority of published studies focusing on MWCNTs. [72,117,131,217,221] For aligned nanocomposites, the piezoresistive response has been studied in the direction of CNT alignment (axial) and perpendicular to it (transverse). Table 2 summarizes the piezoresistive characteristics of different types of aligned CNT arrays and CNT/polymer composites with aligned CNTs, where the GFs were reported in at least two directions, viz. axial, transverse (shortened as Tran in such a Table), and/or randomly oriented. As seen from this table, tensile testing is undoubtedly the most commonly implemented technique to explore the alignment effect on the piezoresistive response, although bending experiments have also been reported. For the case of SWCNTs, most of the reports deal with high SWCNT density systems without matrix, that is, in the form of buckypaper (BP) [140,222] or arrays. [226,227] The highest GF for a SWCNT aligned array (GF ¼ 75, under bending) was reported by Cullinan and Culpepper, [227] where SWCNTs were deposited on a bending beam and aligned by the application of an alternating current electric eld. This response evidences the high intrinsic piezoresistive sensitivity of CNTs when they are directly loaded (a challenging task). The rest of the GFs reported for systems with aligned SWCNTs usually range from 1 to 10, although some of them are not directly loaded but bonded to a beam. [140,222,226] Recently, Sengezer et al. [220] aligned SWCNTs by means of an electric eld in a photopolymerizable blend of acrylate resins, and investigated the piezoresistive response of the nanocomposites along the axial (parallel to alignment) and transverse (perpendicular to alignment) directions during tensile loading. These authors reported higher piezoresistive sensitivity for the transverse direction, see Table 2, which they attributed to the interaction between misaligned and aligned bridging structures, triggered by the Poisson s contraction in the transverse direction. For numerical comparison with existent literature, it is important to keep in mind that the transverse strain (calculated from the axial strain and Poissons ratio) was used to calculate transverse GFs in Sengezer et al. [220] Another factor to bear in mind for comparative purposes is that in their work the load is always applied along the alignment direction

the load is always applied along the alignment direction Figure 17. CNT/polymer composites aligned by electric

Figure 17. CNT/polymer composites aligned by electric fields. a) MWCNT/polysulfone composite, [217] b) SWCNT/acrylate composite. [220] The arrows indicate the direction of the electric field.

www.advancedsciencenews.com www.aem-journal.com Table 2. Summary of piezoresistive behavior of aligned CNT arrays and
www.advancedsciencenews.com www.aem-journal.com Table 2. Summary of piezoresistive behavior of aligned CNT arrays and

Table 2. Summary of piezoresistive behavior of aligned CNT arrays and CNT/polymer composites with aligned CNTs.

Filler

SWCNT

MWCNT

wt%

BP

0.03

BP

Array

Array

1.0

43

0.75

5.0

Matrix (or substrate)

PET

Acrylate

PET

Polyimide

Glass fiber/epoxy

PET

Epoxy

PSF

PC

Gage factor

Loading type

Alignment method

Axial

Tran

Random

Ref.

T

Mechanical draw

7.2

N/A

1.3

[222]

T

Electric field

2

10

N/A

[220]

B

Magnetic field

2.1

4.5

2.3

[223]

T

Stretching

20

N/A

3

[224]

T

CVD

8

1.3

N/A

[225]

T

Extrusion

3.9

4.6

N/A

[131]

T

Stretching

0

0.25

N/A

[117]

T

Electric field

1.5

N/A

0.7

[217]

T

Injection molding

3.7

6.2

2.6

[221]

Acronyms : T ¼ Tensile, B ¼ Bending, ¼ Bonded to a beam or to a larger tensile specimen, N/A ¼ Not available, BP ¼ Buckypaper, PC ¼ Polycarbonate, PSF ¼ Polysulfone, PET ¼ Polyethylene terephthalate, CVD ¼ Chemical vapor deposition.

and the con guration of the longitudinal and transverse electrodes are changed; different electrode con gurations could originate a different piezoresistive response per se. For the case of MWCNTs, the piezoresistive response of several arrays of aligned MWCNTs [223 225,228,229] and aligned MWCNT/polymer composites [72,117,131,217,221] have also been reported. In general, GFs of aligned MWCNTs and MWCNT composites range from 0.04 to 20. Thermosetting (epoxy) and thermoplastic (poly- sulfone and polycarbonate) polymers have been used as host matrices for aligned MWCNT networks with concentrations ranging from 0.02 [72] to 67 wt%. [117] As a general outcome, all the studies conrm that the piezoresistive sensitivity becomes anisotropic by aligning the CNTs, see Table 2. Some authors have found higher GFs for the alignment direction than for the randomly distributed case, [217,221,222,224] which may be explained by the better strain transfer and increased contact resistance along the aligned direction. To illustrate this, Figure 18 shows the tensile piezoresistive response of a 200 μm thick MWCNT/PSF composite lm loaded along the alignment (axial) direction, compared to the response of a lm with randomly oriented CNTs. [217]

of a fi lm with randomly oriented CNTs. [ 2 1 7 ] Figure 18. Piezoresistive

Figure 18. Piezoresistive response of MWCNT/PSF composite films with aligned and randomly oriented CNTs.

Only a few authors have compared the piezoresistive response of CNT/polymer composites along both the alignment (axial) and transverse directions, [117,131,220,221] generally nding that the GF in the transverse direction is higher than that in the axial direction, see Table 2. It is hypothesizedthat the reasons forthis arethe signicant change in CNT-to-CNT lateral contact and the breakdown of the few conductive misaligned pathways bridging the aligned ones upon strain application.However,more systematic studies are still needed to better elucidatethesemechanisms, andto investigate how several factors such asthe ller concentration, polymer rheology, alignment degree, CNT length, functionalization, and loading conguration, affect the electromechanical response of polymer nanocomposites with aligned carbon llers.

7. Concluding Remarks and Perspectives

The use of carbon-based polymer nanocomposites for develop- ing smart piezoresistive materials which are capable of sensing their own elastic strain, plasticity, and damage has been reviewed. Upon reaching percolation, polymer composites which are otherwise electrically insulating materials present an electrical conductivity whose changes as a function of strain can be employed for self-sensing of strain and damage. Carbon materials such as graphite, carbon black, carbon nanotubes, and lately few- and multi-layer graphene are ideal candidates to act as polymer llers to such an aim. The coupled electromechanical response of such polymer nanocomposites depend on several factors related to the ller (nanostructure architecture, dimen- sions, number of layers, functional groups), to the polymer matrix (dielectric constant, processing viscosity) and to the ller dispersion within the matrix. From the geometrical aspects of the ller, the excluded volume is one of the key parameters that in uences the piezoresistive sensitivity of polymer composites. It is expected that loosely connected networks with low ller concentrations, high excluded volume and high number of ller- to- ller contact points render higher piezoresistive sensitivity. Creation and destruction of conductive pathways upon loading, change in contact resistance and change in tunneling resistance are believed to be the main mechanisms governing the

www.advancedsciencenews.com www.aem-journal.com piezoresistive response of these smart materials. The use of
www.advancedsciencenews.com www.aem-journal.com piezoresistive response of these smart materials. The use of

piezoresistive response of these smart materials. The use of piezoimpedance and piezocapacitance for strain and damage sensing in this kind of polymer composites is also an interesting approach that deserves further exploration. The current applications of thermosetting and thermoplastic piezoresistive materials are expected to provide the automotive, aerospace, transportation and energy industries with the next generation of smart materials. Especially for thermosetting polymers, the applications of these nanocomposites are rapidly evolving towards self-sensing of strain and damage in ber-reinforced multiscale hierarchical composites, for virtually every industrial application of composites which demand high load bearing capacity and self-sensing. The applications of carbon lled elastomeric materials, on the other hand, focus more on sensors for human motion, soft skins, smart wearable sensors and robotics, whose main requisite is large deformations. However, aspects such as nonlinearity, cycling reproducibility, undesired viscoelastic response, and hysteresis, are practical issues that need to be resolved towards further development of commercial devices based on these materials. Because of their elongated geometry, carbon nanotubes stand today as ideal candidates for llers in this kind of piezoresistive materials. Controlling the morphology an orientation of the carbon nanotube networks, for example, by aligning them in a preferential direction, may render tailored piezoresistive sensitivi- ties. However, the higher surface area of two-dimensional

graphenic platelets and the possibility of their top-down synthesis in large scales are features whichmakethem also very attractive for piezoresistive applications. As a futuretrend, hybrid combinations of one dimensional carbon nanotubes and two-dimensional graphenic plateletsmay become optimaltopological combinations for piezoresistive strain sensing applications, but the optimization of the hybrid architecture is yet to come.

Appendix A: Compendium of Piezoresistive Behavior of Carbon Filled Polymer Composites

The main piezoresistive features of about 90 works are collected in the parameters listed in Table A1. Such a table is organized by ller type and includes thermosetting (TS), thermoplastic (TP) and elastomeric (ES) matrices, as well as the correspond- ing ller concentration (wt%) and loading type (tension, compression or bending). The main features of the piezor- esistive response of the material are captured by four parameters, referring to its linear (L) or nonlinear (NL) character, maximum strain sensing capability ( e max ), extend of linear piezoresistivity ( e L ) and piezoresistive sensitivity (GF). The difference between e L and e max provides an indication of nonlinear piezoresistivity. All concentrations are reported in weight (wt%), so all values originally reported in volume concentration (vol%) were converted to weight (and thus,

Table A1. Summary of piezoresistive behavior and gage factors of polymer composites filled with carbon nanostructures.

Filler

Carbon black

Graphite

Piezoresistivity

wt%

Matrix (or substrate)

Loading type

L/NL

e max (%)

e L (%)

GF

Ref.

0.5

Epoxy

T

NL

6

1

6

[71]

12

Epoxy

T

NL

4

1

27.7

[72]

50.8

HDPE

C

L

50

50

3.2

[73]

13.4

PP

T

NL

3

1.5

6.6

[74]

5.2

PP

T

L

3

3

30

[75]

9.2

HDPE

T

NL

25

15

10

[76]

12.6

HDPE

T

NL

90

35

4.5

[77]

3

PVDF

T

NL

9

5

3

[78]

33

Natural rubber

T

NL

90

7

17

[79]

30.6

Natural rubber

T

NL

250

100

12

[80]

10

Polyisoprene

T

NL

40

10

15

[82]

9.0

Silicone rubber

C

NL

25

2.5

3.6

[83]

50

Silicone rubber

C

NL

25

2.5

4.4

[83]

7.0

Silicone rubber

C

NL

7

4

6.7

[84]

50.2

Silicone rubber

C

NL

50

13

4.2

[73]

35

Natural rubber

C

L

16.7

16.7

2.7

[85]

16.7

Epoxy

B

N/A

N/A

N/A

22

[96]

18

Polyimide

B

NL

N/A

N/A

16.8

[95]

12.5

PP

T

NL

0.6

0.3

135

[91]

37.5

HDPE

C

NL

35

5

14

[92]

Piezoresistivity

Filler

wt%

Matrix (or substrate)

Loading type

L/NL

e max (%)

e L (%)

GF

Ref.

 

27.6

HDPE

C

NL

10

7

7

[6]

49.4

Silicone rubber

C

NL

15

3

44

[93]

3.1

Silicone rubber

C

NL

0.5

0.3

16.7

[94]

SWCNT

BP

PDMS

T

NL

280

40

0.82 (0 < e < 0.4)

[20]

BP

Epoxy

T

NL

0.95

0.6

2.2

[232]

BP

R-Epoxy

T

NL

15

3

0.60

[232]

BP

PET

T

L

2.0

N/A

1.0

[140]

BP

PDMS

T

NL

30

N/A

5.0 (0.2< e < 0.3)

[140]

BP

N/A

T

L

1.0

1.0

1.25

[233]

BP

PET

T

L

0.65

N/A

1.30 to 7.19

[222]

0.2

Epoxy

B

NL

3.0

1.0

3.6

[113]

0.5

PMMA

B

L

0.13

0.13

5.2

[122]

10

PMMA

B

L

0.13

0.13

0.95

[122]

2.0

PVDF

B

L

0.25

0.25

6.2

[123]

2.0

PVDF

B

L

0.6

0.6

4.43

[124]

8.0

TPU

T

NL

60

20

0.05 to 0.10 ( e < 0.2) 3 to 4.5

[137]

1.0

SBS

T

L

5

5

[145]

MWCNT

BP

Epoxy

T T T T

NL

1.07

0.6

0.85

[232]

BP

R-Epoxy

NL

30

7

0.70

[232]

BP

TPU

NL

400

0

4 to 69 5 to 44 3.4 to 4.3 3.8 (4.9) 22.4 (7.1) 4.2

[135]

BP

TPU

NL

12

0

[234]

0.1

Epoxy

T

NL

6.0

1.5

[71]

5.0

Epoxy