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Tactile sensors: piezoelectric materials

State of the art of promising research fields

Polymer based interfaces as bioinspired smart skins Advances in Colloid and Interface Science 116 (2005) 165 178

The wide variety of configurations and design options adopted in tactile sensing technology originates from the exploitation of many different transduction effects and materials capable of mechano-electric, mechano-magnetic and mechano-optic conversion. The piezoelectric effect is observable in a wide array of crystalline substances that have asymmetric unit cells. When an external force mechanically strains a piezoelectric element, polarized unit cells shift and align in a regular pattern in the crystal lattice. Discrete dipole effects accumulate, developing an electrostatic potential between opposing faces of the element. Relationships between the force applied and the subsequent response of a piezoelectric element depend on three factors: structure dimensions and geometry, material piezoelectric properties, and mechanical or electrical excitation vector.

Piezoelectricity exists in some naturally occurring crystals such as quartz and rochelle salt, and it can be induced in polymers such as nylon and copolymers of vinylidene fluoride (VDF) with trifluoroethylene (TrFE), or with tetrafluoroethylene (TeFE).

Polymer based interfaces as bioinspired smart skins Advances in Colloid and Interface Science 116 (2005) 165 178

The thermal sensing functionality of skin thermoreceptors can be accomplished in artificial structures by exploiting basically two physical effects: thermoelectricity and pyroelectricity.
The pyroelectric effect consists of the manifestation of a temperature-dependent spontaneous polarisation of a material. This means that a pyroelectric material subject to a temperature change displays a modified amount of electric charges on opposite surfaces. Likewise to piezoelectric sensors, these charges can be harvested by means of two electrodes disposed on the material surfaces. If a material shows pyroelectric properties, it is also piezoelectric.

Pyroelectric properties have been reported for many types of organics, whose use as thermal radiation sensors has been well demonstrated today. PVDF and P(VDFTrFE)) are certainly the most performing representatives of this class. They typically exhibit pyroelectric coefficients of about 25 AC/m2 K and 40 AC/m2 K, respectively. However, these values are one order of magnitude lower than the coefficient (380 AC/m2 K) measured for one of the most relevant ceramics, PZT.

Perspective on the Development of Lead-free Piezoceramics J. Am. Ceram. Soc., 92 [6] 11531177 (2009)

Piezoelectric sensors are widely used to detect stresses, sj, by monitoring the dielectric displacement, based on the following relation:

Di = dijsj
The coefficient d33 is most often used in applications and often referred to as just the piezoelectric coefficient. In accordance to the obtainable strain, S3,max, the piezoelectric coefficient is a complex function of magnitude of the mechanical or electric driving field, bias electric field, frequency, temperature, and pressure

Typical d33 coefficients are on the order of 2 pm/V in SiO2, 20 pm/V in bismuth titanate-based Aurivillius structures, 4200 pm/V in PZT, and 42000 pm/V in relaxorferroelectric single crystals (e.g., Pb(Zn1/3Nb2/3)O3). Next to the magnitude of the piezoelectric coefficient, its low temperature dependence, a high electric resistivity, and a low permittivity are among the key requirements for a successful development of piezoceramic sensors.

Piezoelectric Polymers IEEE ENGINEERING IN MEDICINE AND BIOLOGY MAGAZINE JUNE 1989

Polymers with significant piezoelectric properties possess them because of favorable aspects of their structure that are often enhanced by fabrication techniques. An important aspect is crystallinity, which can be altered materially by the preparation and manipulation of the polymer. The ferroelectric polymers polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), several co-polymers and blends, and composites with ceramics such as PZT have received the greatest attention

Among polymeric materials exhibiting piezoelectric properties, the most used is polyvinylidene fluoride (PVDF). Polyvinylidene fluoride is not piezoelectric in its raw state, but can be made piezoelectric by heating/stretching under an electric field. A thin layer of metallization is applied to both sides of a piezoelectric sheet to collect the charge and permit electrical connections being made.

Piezoelectric Sensors and Sensor Materials Journal of Electroceramics 2:4, 257272, 1998 With reference to the periodic table, there are two major groups of active ions, both of which are near electronic ``crossover'' points where different types of atomic orbitals are comparable in energy and where hybrid bond formation is prevalent. The first group, typified by Ti4+, Nb5+, and W6+, consists of d0 ions octahedrally coordinated to oxygen. For Ti4+, the electronic crossover involves the 3d, 4s, and 4p orbitals, which combine with the sigma and pi orbitals of its six O2neighbors to form the (TiO6)8- complex. The bond energy of the complex can be lowered by distorting the octahedron to a lower symmetry. This leads to molecular dipole moments, ferroelectricity, large dielectric constants, and piezoelectricity. A second group of active elements contributing to polar distortions in ceramic dielectrics are the lone-pair ions having two electrons outside a closed shell in an asymmetric hybrid orbital. Among oxides, the most important of these lone-pair ions are Pb2+ and Bi3+, which are involved in a number of ferroelectrics (PbTiO3, Bi4Ti3O12, PbNb2O6) with high Curie temperatures

Piezoelectric Sensors and Sensor Materials Journal of Electroceramics 2:4, 257272, 1998

The first polycrystalline ferroelectric ceramic was barium titanate (BaTiO3), which has the perovskite structure. it remained the primary electroceramic material until the discovery of lead zirconate titanate (PZT)

Perspective on the Development of Lead-free Piezoceramics J. Am. Ceram. Soc., 92 [6] 11531177 (2009)

If one considers to replace the Pb ion while retaining the good ferro- and piezoelectric properties, one should contemplate ions that have both high polarizability, i.e. a large radius and a high effective number of electrons and possess a lone electron pair in an outer shell. Sb3+ and Te4+ fulfill the second requirement; their polarizabilities, however, are significantly smaller than that of Pb2+. Only Tl+ and Bi3+ meet both the requirements. Of the two, Tl is quite expensive, prohibiting its use on an industrial scale and, even more importantly, its toxicity dwarfs even that of lead. From the atomistic point of view, bismuth-containing compounds thus seem to be the most likely successors to lead-based piezoelectrics.

Lead-Free Piezoelectric Ceramics vs. PZT? IEEE 2006

Compositionally, PZT ceramics lie near a morphotropic phase boundary (MPB) separating tetragonal and rhombohedral phases, at ~ x=0.48 PT. MPB compositions have anomalously high dielectric and piezoelectric properties as a result of enhanced polarizability arising from the coupling between two equivalent energy states, i.e., the tetragonal and rhombohedral phases, allowing optimum domain reorientation during the poling process. Recent reports on lead-free piezoelectrics can be categorized into two main perovskite families: (1)K0.5Na0.5NbO3 (KNN), (2)(2) Na0.5Bi0.5TiO3 (NBT)

Lead-Free Piezoelectric Ceramics vs. PZT? IEEE 2006

In KNN phase diagram morphotropic phase boundary was reported at x~0.5 separating two orthorhombic ferroelectric phases.

The enhancement in piezoelectricity of current KNN ceramics has been achieved by compositionally shifting the TO-T downward to near room temperature with additives such as LiTaO3, LiNbO3, LiSbO3 and SrTiO3

Lead-Free Piezoelectric Ceramics vs. PZT? IEEE 2006 BaTiO3 (BT) has a low Curie temperature (Tc = 120C) causing the working temperature range of this ceramic narrow for actual piezoelectric applications. To increase the Tc of BaTiO3-based ceramics, a binary system of BaTiO3 (Bi0.5K0.5)TiO3 (BKT) was investigated. The Tc of BKT was reported to be about 380C. Analogous to PZT, a morphotropic phase boundary separating ferroelectric tetragonal, and rhombohedral phases exists in the NBT phase diagram Unlike that of the PZT system, the MPB is strongly curve, and prior to the prototypic cubic transformation, a phase transformation to an anti-ferroelectric phase occurs. The consequence of this transformation is a loss of polarization and thus piezoelectric activity.

BNT is one of the important lead-free piezoelectric materials with perovskite structure. The main drawback of this material is its high conductivity. For the pure BNT system, d33 lies in the range of 57 64 pC/N as discovered. It has been reported that BNT-based compositions modified with BaTiO3, BiKTiO3, NaNbO3, BiFeO3, MnO2, Sc2O3, La2O3, CeO2, etc.

Lead-Free Piezoelectric Ceramics vs. PZT? IEEE 2006

Lead-Free Piezoelectric Ceramics vs. PZT? IEEE 2006

Review: environmental friendly lead-free piezoelectric materials J Mater Sci (2009) 44:50495062

Perspective on the Development of Lead-free Piezoceramics J. Am. Ceram. Soc., 92 [6] 11531177 (2009)

Theoretical Study on the Static Performance of Piezoelectric Ceramic-Polymer Composites with 2-2 Connectivity IEEE TRANSACTIONS ON ULTRASONICS, FERROELECTRICS, AND FREQUENCY CONTROL, VOL. 40, NO. 2, MARCH 1993 An older and more time-tested approach has been the incorporation of piezoceramics into composites. Composites provide the capability of utilizing the best aspects of each component in the composite while minimizing the poorest features. Most composite hydrophones consist of two phases: a stiff piezoceramic and a soft polymer. Newnham, et al., established the notation for describing the number of dimensions each phase is physically in contact with itself. There are only ten ways in which two distinct components can be incorporated into a single composite. They are given the notation of 0-0, 1-0, 2-0, 3-0, 1-1, 2-1, 3-1, 2-2, 3-2, or 3-3 [26]. To date, eight different connectivity types of two-phase piezoelectric composites ( piezocomposites) have been studied: 03, 1-3, 2-2, 2-3, 3-0, 3-1, 3-2, and 3-3. In the case of piezocomposites, the first number in the notation denotes the physical connectivity of the active phase and the second number refers to the physical connectivity of the passive phase.

Theoretical Study on the Static Performance of Piezoelectric Ceramic-Polymer Composites with 2-2 Connectivity IEEE TRANSACTIONS ON ULTRASONICS, FERROELECTRICS, AND FREQUENCY CONTROL, VOL. 40, NO. 2, MARCH 1993

Composites with 0-3 connectivity consist of a random array of piezoelectric particles dispersed in a 3-D polymer matrix. The primary advantage of these composites is their ability to be formed into shapes while remaining piezoelectrically active. The composite consists of fine PbTiO3 particles of a very narrow size distribution (centered around 20 mm) embedded in a chloroprene polymer matrix. A typical thickness of a 0-3 composite sheet is 500 mm. Good bonding between the particles and the rubber is necessary to achieve successful poling and subsequent good piezoelectric properties. The use of a polymer with a high thermal coefficient of resistivity makes it possible to pole the composite at elevated temperatures by using the improved ceramic/ polymer resistivity balance to give saturation poling while still retaining the high resistance and low loss at typical operating temperatures

Theoretical Study on the Static Performance of Piezoelectric Ceramic-Polymer Composites with 2-2 Connectivity IEEE TRANSACTIONS ON ULTRASONICS, FERROELECTRICS, AND FREQUENCY CONTROL, VOL. 40, NO. 2, MARCH 1993

The mechanism of the stress transfer in composite structures under a static elastic stress (electric field) can be explained as follows. Due to the difference in their elastic stiffness (piezoelectric properties), the polymer and ceramic phases should deform different amounts under a given stress (electric field). However, the nonslip interface forces the displacements of the two phases to be the same at the interface so that a shear stress is generated through this nonslip bonding. This inhomogeneous shear stress in turn produces additional nonuniform deformations in both the ceramic and the polymer phases, producing enhancement to the response of the active harder ceramic at the expense of the response of the passive softer phase (the effect is the opposite for the converse piezoelectric response). An amplification factor y has been defined, which is the ratio of the effective total stress on the ceramic and the actually applied external stress. This amplification factor y characterizes the effectiveness of the stress transfer in a given composite structure. It is found that the effective piezoelectric constant of the composite not only depends on the volume percentage of the active component, but also strongly depends on the aspect ratio and the configurations.

Preparation and properties of polymer matrix piezoelectric composites containing aligned BaTiO3 whiskers JOURNAL OF MATERIALS SCIENCE 39 (2004) 2997 3001 Composites with 03 connectivity are the easiest to make, simply by blending piezoelectric ceramic powders into polymer matrix. However, they are very difficult to get poled since only a small fraction of the poling electric field is imposed upon the ceramics, while the rest is exerting on the polymer matrix. The primary reason is that polymers normally have much higher electrical resistivity than ceramics. In these composites, powders or fibers are by no means uniformly distributed. There exists a critical volume fraction of the conductive phase, above which the conductivity of the composite increases sharply. This critical value is called percolation threshold (P. T). Extensive research reveals that the particles or fibers form continuous electrical passages at P. T by contacting with one another. The P. T is strongly dependant upon the aspect ratio of the conductive phase. The greater the ratio is, the smaller the P. T is. Piezoelectric whiskers are selected in this work as the active phase and polyvinylidene fluoride (PVDF) as the matrix. Whiskers are acicular single crystals with very low density of defects. the whisker composite has a 03 connectivity, because the active phase is not self-connecting. However, it is different from a typical 03 composite by its high anisotropy. It is also different from a 13 composite in that the active phase is not continuous in any directions.

Although PVDF is piezoelectric, its contribution to piezoelectricity in this composite had been found to be much smaller than the whiskers and could be neglected.