This paper reviews the experimental studies of displacive phase transitions in solids. Primary emphasis is upon inelastic light scattering and neutron scattering; related infrared reflectivity measurements, as well as x-ray and EPR analyses are also summarized. Several prototype structures are considered in detail: (1) the rocksalt IV-VI semiconductors PbTe, SnTe, and GeTe; (2) the ferroelectric perovskites exemplified by PbTi${\mathrm{O}}_{3}$ and BaTi${\mathrm{O}}_{3}$; (3) perovskites which exhibit cell-doubling transitions, such as LaAl${\mathrm{O}}_{3}$, SrTi${\mathrm{O}}_{3}$, and KMn${\mathrm{F}}_{3}$; (4) crystals having the $\ensuremath{\alpha}$-quartz structure, including Ge${\mathrm{O}}_{2}$, Si${\mathrm{O}}_{2}$, and AlP${\mathrm{O}}_{4}$; (5) the "improper ferroelectrics" ${\mathrm{Gd}}_{2}$${(\mathrm{M}\mathrm{o}{\mathrm{O}}_{4})}_{3}$ and ${\mathrm{Tb}}_{2}$${(\mathrm{M}\mathrm{o}{\mathrm{O}}_{4})}_{3}$; (6) the V-VI-VII semiconductors typified by SbSI; (7) the hydrogen-bonded ferroelectrics of the K${\mathrm{H}}_{2}$P${\mathrm{O}}_{4}$ family; (8) Jahn-Teller systems such as DyV${\mathrm{O}}_{4}$ and RbCo${\mathrm{F}}_{3}$, in which structural distortions occur as secondary effects; (9) order-disorder systems such as NaN${\mathrm{O}}_{2}$ and the ammonium halides (N${\mathrm{H}}_{4}$Cl, N${\mathrm{H}}_{4}$Br), in which no "soft mode" occurs in the spectral region ($\ensuremath{\omega}g{10}^{11}$ Hz) probed by ir, Raman, and neutron spectroscopy; (10) $\ensuremath{\beta}$-tungsten ($A\ensuremath{-}15$) structures such as ${\mathrm{V}}_{3}$Si and ${\mathrm{Nb}}_{3}$Sn, which exhibit high-temperature superconductivity. These crystal categories are used to illustrate several phenomena of current physical interest: Specifically, we discuss harmonic and anharmonic mode coupling; "critical exponents" $\ensuremath{\beta}$ differing from one-half in the temperature dependences of the order parameter $\ensuremath{\phi}(T)={\ensuremath{\phi}}_{0}{(T\ensuremath{-}{T}_{0})}^{\ensuremath{\beta}}$ and of the soft-mode frequency $\ensuremath{\omega}(T)={\ensuremath{\omega}}_{0}{(T\ensuremath{-}{T}_{0})}^{\ensuremath{\beta}}$; and the recently discovered "central" modes centered at zero frequency, which grow in intensity as the transition temperature ${T}_{0}$ is approached from above or below. The review covers the period 1940-1972. A few 1973 works are mentioned for which the author had preprints in 1972 or very early 1973. This review is in no sense a comprehensive survey of ferroelectricity. Readers are referred to the following earlier reviews on that subject: Silverman (1966, 1969), Cochran and Cowley (1967), Blinc (1968), Murzin et al. (1968), Nettleton (1970), and Blinc and Zaks (1972).

Soft-mode spectroscopy: Experimental studies of structural phase transitions

Dynamical aspects of the ferroelectric phase transition in KH 2 PO 4 -type crystals are elucidated on the basis of the coupling between the proton tunneling mode and the optical mode vibration of the [K-PO 4 ] complexes along the c-axis. Two coupled modes are obtained within the framework of a linear theory. The mode in which both systems oscillate in phase is shown to be responsible for the ferroelectric phase transition. The isotope effect in the Curie point is explained qualitatively and the Curie constant is estimated.

Dynamical Theory of the Phase Transition in KH2PO4-Type Ferroelectric Crystals

For a crystal which can become ferroelastic , it is important to know those elements of those linear combinations of elements of mechanical strain tensor each of which, at null stress, is not equal in all the orientation states of the ferroelastic phase and is zero over the whole temperature range in the prototypic phase. These quantities are a kind of state parameters . Also, it is convenient to introduce “spontaneous strain” as a total measure for the `degree' of ferroelasticity. Spontaneous strain should be independent of choice of the rectangular coordinate system, be the same in all the orientation states of the ferroelastic phase, and be zero over the whole temperature range in the prototypic phase. For each of the 94 species of ferroelastics, the set of state parameters is found, its way of changing with each state shift is determined, and the spontaneous strain (satisfying the above conditions) is formulated.

Determination of the State Parameters and Formulation of Spontaneous Strain for Ferroelastics

CRYSTAL STRUCTURE OF THE FERROELECTRIC PHASE OF (GLYCINE)$sub 3$/CENTER DOT/ H$sub 2$SO$sub 4$

Research on sintering of dense ceramic materials has been very active in the past decades and still keeps gaining in popularity. Although a number of new techniques have been developed, the sintering process is still performed at high temperatures. Very recently we established a novel protocol, the “Cold Sintering Process (CSP)”, to achieve dense ceramic solids at extraordinarily low temperatures of <300°C. A wide variety of chemistries and composites were successfully densified using this technique. In this article, a comprehensive CSP tutorial will be delivered by employing three classic ferroelectric materials (KH2PO4, NaNO2, and BaTiO3) as examples. Together with detailed experimental demonstrations, fundamental mechanisms, as well as the underlying physics from a thermodynamics perspective, are collaboratively outlined. Such an impactful technique opens up a new way for cost-effective and energy-saving ceramic processing. We hope that this article will provide a promising route to guide future studies on ultralow temperature ceramic sintering or ceramic materials related integration.

B. C. Frazer

Papers

X‐ray analysis of the ferroelectric transition in KH2PO4