The volatilization of alkali ions in (K,Na)NbO3 (KNN) ceramics was inhibited by doping them with alkaline earth metal ions. In addition, the grain growth behavior changed significantly as the sintering duration (ts) increased. At 1,100 °C, the volatilization of alkali ions in KNN ceramics was more suppressed when doped with alkaline earth metal ions with smaller ionic size. A Ca2+-doped KNN specimen with the least alkali ion volatilization exhibited a microstructure in which grain growth was completely suppressed, even under long-term sintering for ts = 30 h. The grain growth in Sr2+-doped and Ba2+-doped KNN specimens was suppressed until ts = 10 h. However, at ts = 30 h, a heterogeneous microstructure with abnormal grains and small-sized matrix grains was observed. The size and number of abnormal grains and size distribution of matrix grains were considerably different between the Sr2+-doped and Ba2+-doped specimens. This microstructural diversity in KNN ceramics could be explained in terms of the crystal growth driving force required for two-dimensional nucleation, which was directly related to the number of vacancies in the material.
The grain growth behavior in the (1-x)K0.5Na0.5NbO3-xCaZrO3 (KNNCZ-x) system is studied as a function of the amount of CZ and grain shape. The (1-x)K0.5Na0.5NbO3-xCaZrO3 (KNNCZ-x) powders are synthesized using a conventional solid-state reaction method. A single orthorhombic phase is observed at x = 0 – 0.03. However, rhombohedral and orthorhombic phases are observed at x = 0.05. The grain growth behavior changes from abnormal grain growth to the suppression of grain growth as the amount of CaZrO3 (CZ) increases. With increasing CZ content, grains become more faceted, and the step-free energy increases. Therefore, the critical growth driving force increases. The grain size distribution broadens with increasing sintering time in KNNCZ-0.05. As a result, some large grains with a driving force larger than the critical driving force for growth exhibit abnormal grain growth behavior during sintering. Therefore, CZ changes the grain growth behavior and microstructure of KNN. Grain growth at the faceted interface of the KNNCZ system occurs via two-dimensional nucleation and growth.
NKN [(Na,K)NbO3] is a candidate lead-free piezoelectric material to replace PZT [Pb(Zr,Ti)O3]. A single crystal has excellent piezoelectric-properties and its properties are dependent of the crystal orientation direction. However, it is hard to fabricate a single crystal with stoichiometrically stable composition due to volatilization of sodium during the growth process. To solve this problem, a solid solution composition is designed (Na,K)NbO3-Ba(Cu,Nb)O3 and solid state grain growth is studied for a sizable single crystal. Ceramic powders of (Na,K)NbO3-M(Cu,Nb)O3 (M = Ca, Sr, Ba) are synthesized and grain growth behavior is investigated for different temperatures and times. Average normal grain sizes of individual specimens, which are heat-treated at 1,125 oC for 10 h, are 6.9, 2.8, and 1.6 m for M = Ca, Sr, and Ba, respectively. Depending on M, the distortion of NKN structure can be altered. XRD results show that (NKN-CaCuN: shrunken orthorhombic; NKN-SrCuN: orthorhombic; NKN-BaCuN: cubic). For the sample heat-treated at 1,125 oC for 10 h, the maximum grain sizes of individual specimens are measured as 40, 5, and 4,000 m for M = Ca, Sr, and Ba, respectively. This abnormal grain size is related to the partial melting temperature (NKN-CaCuN: 960 oC; NKN-SrCuN: 971 oC; NKN-BaCuN: 945 oC).
Single crystals, which have complexed composition, are fabricated by solid state grain growth. However, it is hard to achieve stable properties in a single crystal due to trapped pores. Aerosol deposition (AD) is suitable for fabrication of single crystals with stable properties because this process can make a high density coating layer. Because of their unique features (nano sized grains, stress inner site), it is hard to fabricate single crystals, and so studies of grain growth behavior of AD film are essential. In this study, a BaTiO3 coating layer with ~ 9 μm thickness is fabricated using an aerosol deposition method on (100) and (110) cut SrTiO3 single crystal substrates, which are adopted as seeds for grain growth. Each specimen is heat-treated at various conditions (900, 1,100, and 1,300℃ for 5 h). BaTiO3 layer shows different growth behavior and X-ray diffraction depending on cutting direction of SrTiO3 seed. Rectangular pillars at SrTiO3 (100) and laminating thin plates at SrTiO3 (110), respectively, are observed.
Pb(Zr,Ti)O3 (PZT) is used for the various piezoelectric devices owing to its high piezoelectric properties. However, lead (Pb), which is contained in PZT, causes various environment contaminations. (K,Na)NbO3 (NKN) is the most well-known candidate for a lead-free composition to replace PZT. A single crystal has excellent piezoelectric-properties and its properties can be changed by changing the orientation direction. It is hard to fabricate a NKN single crystal due to the sodium and potassium. Thus, (Na,K)NbO3-Ba(Cu,Nb)O3 (NKN-BCuN) is chosen to fabricate the single crystal with relative ease. NKNBCuN pellets consist of two parts, yellow single crystals and gray poly-crystals that contain copper. The area that has a large amount of copper particles may melt at low temperature but not the other areas. The liquid phase may be responsible for the abnormal grain growth in NKN-BCuN ceramics. The dielectric constant and tan δ are measured to be 684 and 0.036 at 1 kHz in NKN-BCuN, respectively. The coercive field and remnant polarization are 14 kV/cm and 20 μC/cm2.
Grain-growth behavior in the 95Na1/2Bi1/2TiO3-5BaTiO3 (mole fraction, NBT-5BT) system has been investigated with the addition of Na2CO3. When Na2CO3 is added to NBT-5BT, the growth rate is higher than desired and grains are already impinging each other during the initial stage of sintering. The grain size decreases as the sintering temperature increases. With the addition of Na2CO3, a liquid phase infiltrates the interfaces between grains during sintering. The interface structure can be changed to be more faceted and the interface migration rate can increase due to fast material transport through the liquid phase. As the sintering temperature increases, the impingement of abnormal grains increases because the number of abnormal grains increases. Therefore, the average grain size of abnormal grains can be decreased as the temperature increases. The phenomenon can provide evidence that grain coarsening in NBT-5BT with addition of Na2CO3 is governed by the growth of facet planes, which would occur via mixed control.
The grain growth behavior of (NBT-5BT) has been investigated with respect to the grain shape. The powder compacts of NBT-5BT were sintered at 1200 for various times. The corresponding equilibrium shape was a round-edged cube with flat {100}-faces. Abnormal grains were not observed in the specimens sintered for 1 to 12 h but abnormal grains appeared when sintered for 24 h. Before the formation of abnormal grains, a valley was observed in the measured grain size distribution of NBT-5BT, showing that the grain size distribution was a combination of two unimodal distributions. The present result suggests that the grain growth in NBT-5BT was governed by the growth of facet planes which would occur via 2-dimansional nucleation and growth
Densification behavior and grain growth of tool steel powder compacts during pressureless sintering, sinter forging, and hot isostatic pressing were investigated. Experimental data were compared with results of finite element calculations by using the constitutive model of Abouaf and co-workers and that of McMeeking and co-workers. Densification and deformation of tool steel powder compacts were studied by implementing power-law creep, diffusional creep, and grain growth into the finite element analysis. The shape change of a powder compact in the container during hot isostatic pressing was also studied. The theoretical models did not agree well with experimental data in sinter forging, however, agreed well with experimental data in hot isostatic pressing.
BaTiO3세라믹에서 미세구조를 조절하기 위하여 Ba/Ti비 변화에 따른 소결거동 및 비정상 입자성장에 대하여 연구하였다. 본 연구에서 사용한 BaTiO3분말은 BaCO3와 TiO2를 이용하여 일반적인 고상반응법으로 제조하였다. Ba/Ti비가 감소할수록(과잉 TiO2가 증가할수록)소결 시작온도가 낮아졌으며 치밀화가 증진되었다. 이것은 과잉 TiO2양이 증가할수록 하소된 분말의 크기가 감소되었기 때문으로 판단되며, 공융액상 형성으로 인한 액상소결에 의한 것이 아님을 알 수 있었다. 또한 과잉 TiO2양이 증가할수록 입자성장이 강력하게 억제되었으며, 이는 Ti-rich 이차상이 입자성장을 억제시킴을 의미한다. 따라서 이러한 이차상의 불균일한 분포로 인하여 비정상 입자성장이 일어나는 것으로 판단되었다.