Niobate materials

Typical electrostrictive materials include such compounds as lead manganese niobate lead titanate (PMN PT) and lead lanthanium 2irconate titanate (PLZT). Electrostriction is a fourth-rank tensor property observed in both centric and acentric insulators (14,15). 

Certain glass-ceramic materials also exhibit potentially useful electro-optic effects. These include glasses with microcrystaUites of Cd-sulfoselenides, which show a strong nonlinear response to an electric field (9), as well as glass-ceramics based on ferroelectric perovskite crystals such as niobates, titanates, or zkconates (10—12). Such crystals permit electric control of scattering and other optical properties. 

Only certain types of crystalline materials can exhibit second harmonic generation (61). Because of symmetry considerations, the coefficient must be identically equal to zero in any material having a center of symmetry. Thus the only candidates for second harmonic generation are materials that lack a center of symmetry. Some common materials which are used in nonlinear optics include barium sodium niobate [12323-03-4] Ba2NaNb O lithium niobate [12031 -63-9] LiNbO potassium titanyl phosphate [12690-20-9], KTiOPO beta-barium borate [13701 -59-2], p-BaB204 and lithium triborate... 

Lithium Niobate. Lithium niobate [12031 -64-9], LiNbO, is normally formed by reaction of lithium hydroxide and niobium oxide. The salt has important uses in switches for optical fiber communication systems and is the material of choice in many electrooptic appHcations including waveguide modulators and sound acoustic wave devices. Crystals of lithium niobate ate usually grown by the Czochralski method foUowed by infiltration of wafers by metal vapor to adjust the index of refraction. 

Because of very high dielectric constants k > 20, 000), lead-based relaxor ferroelectrics, Pb(B, B2)02, where B is typically a low valence cation and B2 is a high valence cation, have been iavestigated for multilayer capacitor appHcations. Relaxor ferroelectrics are dielectric materials that display frequency dependent dielectric constant versus temperature behavior near the Curie transition. Dielectric properties result from the compositional disorder ia the B and B2 cation distribution and the associated dipolar and ferroelectric polarization mechanisms. Close control of the processiag conditions is requited for property optimization. Capacitor compositions are often based on lead magnesium niobate (PMN), Pb(Mg2 3Nb2 3)02, and lead ziac niobate (PZN), Pb(Zn 3Nb2 3)03. 

The contribution to the stress from electromechanical coupling is readily estimated from the constitutive relation [Eq. (4.2)]. Under conditions of uniaxial strain and field, and for an open circuit, we find that the elastic stiffness is increased by the multiplying factor (1 -i- K ) where the square of the electromechanical coupling factor for uniaxial strain, is a measure of the stiffening effect of the electric field. Values of for various materials are for x-cut quartz, 0.0008, for z-cut lithium niobate, 0.055 for y-cut lithium niobate, 0.074 for barium titanate ceramic, 0.5 and for PZT-5H ceramic, 0.75. These examples show that electromechanical coupling effects can be expected to vary from barely detectable to quite substantial. 

The piezoelectric behavior of both quartz and lithium niobate has been studied in a series of careful, systematic investigations. (See Graham and coworkers [65G01, 70101, 75G04].) The experimental arrangement is shown Fig. 4.2. The impactor, preferably the same material as the piezoelectric sample (but perhaps another standard material), is accelerated to a preselected... 

The measured relationships between piezoelectric polarization and strain for x-cut quartz and z-cut lithium niobate are found to be well fit by a quadratic relation as shown in Fig. 4.4. In both materials a significant nonlinear piezoelectric effect is indicated. The effect in lithium niobate is particularly notable because the measurements are limited to much smaller strains than those to which quartz can be subjected. The quadratic polynomial fits are used to determine the second- and third-order piezoelectric constants and are summarized in Table 4.1. Elastic constants determined in these investigations were shown in Chap. 2. 

Lithium niobate is strongly ferroelectric, yet the material behavior under elastic shock loading is apparently fully described by nonlinear piezoelec-... 

The determination of piezoelectric constants from current pulses is based on interpretation of wave shapes in the weak-coupling approximation. It is of interest to use the wave shapes to evaluate the degree of approximation involved in the various models of piezoelectric response. Such an evaluation is shown in Fig. 4.5, in which normalized current-time wave forms calculated from various models are shown for x-cut quartz and z-cut lithium niobate. In both cases the differences between the fully coupled and weakly coupled solutions are observed to be about 1%, which is within the accuracy limits of the calculations. Hence, for both quartz and lithium niobate, weakly coupled solutions appear adequate for interpretation of observed current-time waveforms. On the other hand, the adequacy of the uncoupled solution is significantly different for the two materials. For x-cut quartz the maximum error of about 1%-1.5% for the nonlinear-uncoupled solution is suitable for all but the most precise interpretation. For z-cut lithium niobate the maximum error of about 8% for the nonlinear-uncoupled solution is greater than that considered acceptable for most cases. The linear-uncoupled solution is seriously in error in each case as it neglects both strain and coupling. 

In this book those ferroelectric solids that respond to shock compression in a purely piezoelectric mode such as lithium niobate and PVDF are considered piezoelectrics. As was the case for piezoelectrics, the pioneering work in this area was carried out by Neilson [57A01]. Unlike piezoelectrics, our knowledge of the response of ferroelectric solids to shock compression is in sharp contrast to that of piezoelectric solids. The electrical properties of several piezoelectric crystals are known in quantitative detail within the elastic range and semiquantitatively in the high stress range. The electrical responses of ferroelectrics are poorly characterized under shock compression and it is difficult to determine properties as such. It is not certain that the relative contributions of dominant physical phenomena have been correctly identified, and detailed, quantitative materials descriptions are not available. 

Since niobates and tantalates belong to the octahedral ferroelectric family, fluorine-oxygen substitution has a particular importance in managing ferroelectric properties. Thus, the variation in the Curie temperature of such compounds with the fluorine-oxygen substitution rate depends strongly on the crystalline network, the ferroelectric type and the mutual orientation of the spontaneous polarization vector, metal displacement direction and covalent bond orientation [47]. Hence, complex tantalum and niobium fluoride compounds seem to have potential also as new materials for modem electronic and optical applications. 

Another method of raw material decomposition is based on the fluorination of the raw material by the hydrofluoride method. No published data exists on hydrofluoride decomposition of columbite or tantalite concentrates. The interaction can, nevertheless, be discussed based on available information on the decomposition of lithium tantalate, LiTaC>3, and lithium niobate, LiNb03, using the hydrofluoride method [113,118,122]. 

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