臺灣博碩士論文加值系統

壓電材料廣泛用於驅動器、超音波換能器、感測器、諧振器、濾波器、蜂鳴器等電子元組件中。壓電材料包含有壓電陶瓷、壓電單晶體、壓電高分子材料和複合材料等。其中壓電陶瓷具有製造簡單成本低廉的特點。尤其鋯鈦酸鉛 (PZT)系壓電陶瓷既有優異的壓電特性，一直佔據壓電材料的大部分市場。近年來、隨著環保意識的提高，許多對人體和環境有害的物質逐步被禁用，其中鉛被列為限制使用的有害物質之一。因此，無鉛壓電陶瓷的研發技有迫切的需要。
無鉛壓電陶瓷的研究，十年幾來主要集中於鈮酸鈉鉀(KNN)和鈦酸鉍鈉(NBT)，其中，以KNN系壓電陶瓷具有高相轉換溫度(Tc~420oC)、高機電耦合因數、壓電常數，引起了廣泛的關注。鑒於KNN的重要性與發展潛力，本研究是以MO-method和BO-method這兩種固態反應製程，以 (Li,K,Na)(Nb,Ta)O3, (Li,K,Na)(Nb,Ta,Sb)O3為研究對象，改變Li、K、Na的比例，從微觀結構、晶體結構、介電常數、溫度穩定、壓電特性、MBP兩相共存區等作深入研究、探討與比較，並就兩種製程之可靠性與老化的機制做進一步的探討，本研究結果可以歸納如下：
 傳統氧化物合成法燒結Lix(KyNa1-y)1-x(Nb0.9Ta0.06Sb0.04)O3無鉛壓電陶瓷，探討晶體結構，介電常數與壓電性，經由XRD得知為鈣鈦礦結構，在x=0.06與y=0.485有正交相與四方相兩相共存，同時由A位置少量Li+的置換，產生晶體結構異常使的壓電性增加。在本研究中最佳的壓電性在x=0.06與y=0.485，此時機電耦合係數kp=42.8%、壓電常數d33=218pC/N與介電常數εr=1280，介電損tanδ=2.9%。
 傳統的氧化物合成法(MO model)，製備Lix(K0.5Na0.5)1-x(Nb0.8Ta0.2)O3 (LKNNT-x)無鉛壓電陶瓷。研究Li+含量對LKNNT-x的影響，Li+的含量從0增加到5atm%，晶體結構從(x=0.03)正交相(orthorhombic)轉變成(x=0.04)四方相(tetragonal)結構，在x=0.03到0.04間存在正交相與四方向的兩相共存區。如同MPB一樣在此區中有較高的壓電性，與介電特性，即kp(%)=43.1、kt(%)=39.4、d33=223pC/N。由研究得知少量Li+，會幫助燒結、提高密度、壓電性(kp、kt、d33等)降低介電損tanδ與增加Tc。
 本論文提出的的B位置氧化物前驅反應合成法(BO-method)，因B位置材料先行反應成固溶體，原料粉體有高的活性與擴散性，有較寬廣燒結溫度，燒結後陶瓷體緻密性較好，由研究顯示相同組成，以MO-method製備的陶瓷體的每一個晶粒組成差異大，傾向於弛緩體，以BO-method製備的陶瓷體的每一個晶粒組成差異小傾向於鐵電體，壓電特性有很大的提升，同樣在MPB附近，Li+含量在0.03mole%，有最好的壓電性質，BO-method製備的Lix(K0.5Na0.5)1-x(Nb0.8Ta0.2)O3 (LKNNT-x)無鉛壓電陶瓷kp(%)=49.7、kt(%)=43.2、d33=246pC/N。同時有穩定的溫度特性，老化速度只有MO-method的一半。
 本研究除了傳統氧化物合成法還發展出同樣具有簡單、方便與便宜的B位置氧化物前驅反應合成法，經比較各種特性發現，B位置氧化物前驅反應合成法制備的陶瓷體，有燒結範圍較寬廣，降低燒結溫度，提高密度，改善化學反應的均質性，提升晶粒的均勻性，提高壓電性等效果。因此，此法可以推廣到一般的商品化壓電陶瓷的生產製程上，以提高產品的壓電特性。

Perovskite PZT family piezoelectric ceramics have been widely used as the actuators, sensors, transducers, filter, buzzer and other electronics devices due to their excellent piezoelectric properties. However, PZT can cause environmental pollution. Therefore, lead-free piezoelectric ceramics have become important issues for replacing the lead-based piezoelectric ceramics.
The lead-free piezoelectric ceramics research, mainly concentrates the materials system in sodium potassium niobate (KNN) and bismuth sodium titanate (NBT) for the past ten years. Especially, the KNN-based ceramics with high Curie temperature (Tc~420oC) and high electromechanical coupling factor have aroused the widespread interest in alternative to PZT-based materials. As above-mentioned the good properties of KNN-based ceramics, Lix(K0.5Na0.5)1-x(Nb0.8Ta0.2)O3 (LKNNT) and Lix(KyNa1-y)1-x(Nb0.9Ta0.06Sb0.04)O3 (LKNNTS) piezoelectric ceramics are selected and prepared by the conventional mixed-oxide method (MO method) and B-site oxides precursor method (BO method) respectively. In this study, two different fabricated processes (BO and MO methods) are simultaneously conducted. And, the microstructures and piezoelectric properties are systematically investigated and compared on the LKNNT and LKNNTS materials system. The following topics are studied and summarized in this dissertation.


 The lead-free Lix(KyNa1-y)1-x(Nb0.9Ta0.06Sb0.04)O3 (x=0~0.08, y=0.47~0.50) piezoelectric ceramics have been prepared by MO method. The variation of Li+, causing the lattice distortion, will improve the piezoelectric and dielectric characteristics. The best composition is obtained from x = 0.06 and y = 0.485, and the optimum characteristics are: kP = 42.8 %, d33 = 218pC/N, εr = 1280, tanδ = 3%, and Tc = 340oC at the optimum sintering temperature 1090oC.
 The lead-free Lix(K0.5Na0.5)1-x(Nb0.8Ta0.2)O3 (x=0~0.05) piezoelectric ceramics were prepared by MO method. The influence of Li content of LKNNT ceramics is systematically studied. It is found that the ceramics with x=0 and x=0.03 have an orthorhombic structure, whereas as x ≧0.04 the ceramics exhibits a tetragonal structure. The ceramics with x = 0.03 to x = 0.04 shows the coexistence of the orthorhombic and tetragonal phase and high piezoelectric properties. Li have the effect of enhancing the ceramic sinter-ability, density, and piezoelectric properties. The best composition is obtained from x = 0.03, the optimum characteristics are: kp(%) = 43.1、kt (%) = 39.4、d33 = 223pC/N.
 The lead-free Lix(K0.5Na0.5)1-x(Nb0.8Ta0.2)O3 (x=0~0.05) piezoelectric ceramics were prepared by BO method. Because the B-site oxides were reacted in advance, it has the high activeness and the diffusibility, the broad sintering temperature in the solid-state reaction processing. Therefore, the ceramic compactness is good, and has the identical kind of composition as compared to the MO method. The piezoelectric characteristics are promoted, presenting the optimum characteristics kp(%) of 49.7, kt (%) of 43.2, d33 of 246pC/N. The BO-method preparation also has the potential in the stable temperature characteristic, and the low aged speed than those preparing by MO method.
 The majority of commercialized piezoelectric product is fabricated by the MO method manufacture because of easy mass production. In my dissertation, the piezoelectric characteristics are obtained using the modified MO method. The broad sintering temperature, the enhancement in the density, the improvement chemical reaction uniformity and grain uniformity present the good physical properties, comparing to the MO method. Thus, the BO-method may promote piezoelectricity characteristic in properties over the commercialized piezoelectric ceramics.

第一章 諸論.......................................................1
1.1 PZT鉛系壓電陶瓷.............................................2
1.2 無鉛壓電陶瓷.................................................4
1.3 研究動機....................................................14
1.4 論文架構....................................................15
第二章 壓電理論...................................................17
2.1 介電性......................................................17
2.2材料的壓電效應................................................25
2.3 壓電方程式..................................................27
2.4鐵電材料與磁滯曲線............................................30
2.5弛緩體與擴散模型..............................................31
2.6 鈣鈦礦結構的容忍因子..........................................34
2.7 壓電材料的本質與外質效應......................................35
2.8 摻雜物對壓電材料的影響........................................35
2.9 傳統氧化物合成法與B位置前驅反應合成法...........................36
第三章 實驗步驟與參數測量.........................................38
3.1 前言.......................................................38
3.2 Lix(KyNa1-y)1-x(Nb0.9Ta0.06Sb0.04)O3無鉛壓電陶瓷的製備......38
3.3 Lix(K0.5Na0.5)1-x(Nb0.8Ta0.2)O3無鉛壓電陶瓷的以MO與BO製備....39
3.4 基本性質測量................................................45
3.5 材料電性測量................................................45
第四章 傳統氧化物合成法與B位置前驅反應合成法Lix(K0.5Na0.5)1-x(Nb0.8Ta0.2)O
的介電與壓電特性之可靠性分析.......................................50
4.1 前言.......................................................50
4.2 實驗步驟與試片的製作.........................................51
4.3 實驗的結果與討論.............................................52
4.4 MO與BO製程的比較與改善.......................................62
4.5 可靠性分析..................................................71
4.6 結論.......................................................78
第五章 無鉛壓電陶瓷Lix(KyNa1-y)1-x(Nb0.9Ta0.06Sb0.04)O3的特性......80
5.1 實驗步驟與試片製做...........................................80
5.2 物理特性...................................................81
5.3 Li的含量對LKNNTS的影響......................................84
5.4 LKNNTS的壓電特性............................................87
5.5 結論.......................................................90
第六章 結論與未來的研究方向........................................91
6.1結論........................................................91
6.2 未來的研究方向..............................................92
參考文獻........................................................94

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