【摘要】：鉍基鈣鈦礦結(jié)構(gòu)電子材料由于其獨(dú)特的介電、鐵電、壓電等方面的性能而備受關(guān)注,其中,鐵酸鉍(BiFeO_3,BFO)是唯一室溫下同時(shí)具有鐵電序和反鐵磁序的多鐵材料,表現(xiàn)出良好的電磁學(xué)特性、半導(dǎo)體特性、阻變特性和氣敏性能等;此外,鈦酸鉍鈉(Bi_(0.5)Na_(0.5)TiO_3,BNT)則是一種具有優(yōu)良壓電性能的材料,通過與鈦酸鉍鉀(Bi0.5K0.5TiO3,BKT)等按一定比例復(fù)合,在構(gòu)成準(zhǔn)同型相界(MPB)基礎(chǔ)上改性,會(huì)表現(xiàn)出高的電致應(yīng)變性能和優(yōu)良的介電調(diào)諧性能等。因此,本論文以BiFeO_3和Bi_(0.5)Na_(0.5)TiO_3基材料為研究對象,采用固相反應(yīng)法、溶膠凝膠法和水熱法等方法,對其進(jìn)行A位離子取代或復(fù)合改性,并研究了取代復(fù)合對其鐵電、壓電、介電調(diào)諧、電致應(yīng)變以及氣敏等性能的影響規(guī)律。采用固相反應(yīng)法制備了A位La取代的BiFeO_3(Bi1-xLaxFeO3,BLF)陶瓷,研究取代比例對其電學(xué)非線性的影響。在不同氣氛下對BLF進(jìn)行熱處理并測試分析電學(xué)性能,發(fā)現(xiàn)BLF電導(dǎo)機(jī)制屬于p型空穴導(dǎo)電機(jī)制,熱處理氣氛的氧分壓越高導(dǎo)電性越好。BLF存在非線性伏安特性,當(dāng)外電場超過一定閾值之后,電流大幅增加,電阻明顯減小,非線性系數(shù)隨La取代量的減少而增加,隨溫度的升高而增加,隨熱處理氣氛氧分壓的增加而增加,經(jīng)過氧氣退火處理的BLF非線性系數(shù)最高。指出這種阻變效應(yīng)來源于其鐵電疇與疇壁處的微觀電子異質(zhì)結(jié)構(gòu),鐵電疇與疇壁的導(dǎo)電性存在差異而導(dǎo)致疇壁處存在整流效應(yīng)。采用溶膠凝膠法制備了A位Ba取代的BiFeO_3(Bi0.9Ba0.1FeO2.95,BBFO10)粉體,研究了其對幾種典型揮發(fā)性氣體的氣敏性能。BBFO10比純BFO的氣體探測靈敏度有大幅提高,并具有快速的響應(yīng)恢復(fù)速度、良好的氣體選擇性和長期穩(wěn)定性。實(shí)驗(yàn)得出由于BBFO10比BFO粉體的比表面積大,在氣敏反應(yīng)過程中與氣體分子接觸吸附的面積增大,有利于提高反應(yīng)敏感度。另外由于二價(jià)Ba2+離子部分取代三價(jià)Bi3+離子,使得BBFO10中氧空位濃度增加,也有利于提高BBFO10的氣敏性能。采用水熱法和微波水熱法制備了BiFeO_3和A位Ce取代的BiFeO_3(Bi0.9Ce0.1FeO3,BCFO)粉體,研究了其磁學(xué)特性。微波水熱法制備的BFO表現(xiàn)出順磁性,而水熱法制備的BFO和BCFO-H表現(xiàn)為弱鐵磁性,Ce的部分取代明顯提高了BCFO的磁學(xué)性能,這是由于內(nèi)外層軌道雜化電子遷移以及離子半徑的差異使BFO的螺旋調(diào)制結(jié)構(gòu)發(fā)生變化而導(dǎo)致。制備了(1-x)(0.8BNT-0.2BKT)-xNaNbO3(BNKT-xNN)陶瓷,研究了其應(yīng)變、鐵電和介電性能隨組分和溫度的變化規(guī)律。結(jié)果表明,隨著NN含量的增加,BNKT-xNN逐漸從非遍歷性弛豫鐵電體轉(zhuǎn)變?yōu)楸闅v性弛豫體,表現(xiàn)為鐵電相-弛豫相轉(zhuǎn)變溫度TF-R從室溫以上逐漸降至室溫以下,壓電系數(shù)d33大幅下降,電滯回線從飽和回線變成瘦腰狀,應(yīng)變S-E曲線由蝴蝶形轉(zhuǎn)變?yōu)檠啃�。非遍歷性弛豫體組分在電場作用下發(fā)生不可逆相變,從贗立方相轉(zhuǎn)變?nèi)较?升溫至TF-R溫度以上應(yīng)變大幅增加。屬于遍歷性弛豫體組分的BNKT-0.04NN在室溫下的電致應(yīng)變0.445%、Smax/Emax值可達(dá)810 pm/V,大應(yīng)變來源于電場激發(fā)的遍歷性弛豫相與鐵電相之間可逆相變。研究了BNKT-xNN陶瓷的介電調(diào)諧性能、熱釋電性能及導(dǎo)電機(jī)制,材料均表現(xiàn)出顯著的介電非線性調(diào)諧性能,且隨著NN含量的不同其介電調(diào)諧行為表現(xiàn)不同,作為非遍歷弛豫體的組分在場致相變前后介電調(diào)諧行為由非線性轉(zhuǎn)變?yōu)榫�性關(guān)系,遍歷性弛豫體的組分則始終保持非線性關(guān)系。BNKT-xNN的導(dǎo)電機(jī)制屬于n型電子導(dǎo)電機(jī)制,其電導(dǎo)率隨熱處理氧分壓濃度的降低而增加,其電導(dǎo)激活能隨熱處理氧分壓濃度的降低而降低。研究了(1-x)(0.8BNT-0.2BKT)-xBiMg2/3Nb1/3O3(BNKT-xBMN)陶瓷的應(yīng)變、鐵電和介電性能隨組分和溫度的變化規(guī)律。BNKT-x BMN的物相為贗立方相,作為非遍歷性弛豫鐵電體的BNKT-0BMN在室溫下表現(xiàn)為典型的鐵電體特征,在電場作用下發(fā)生不可逆相變。BNKT-0.02BMN為遍歷性弛豫鐵電體,電致應(yīng)變值可達(dá)0.431%,在較低的電場強(qiáng)度40 kV/cm下,Smax/Emax即可高達(dá)862 pm/V,具有較高的場致應(yīng)變效率,因而適合實(shí)際應(yīng)用。
[Abstract]:Bismuth based perovskite structure electronic materials have attracted much attention due to their unique dielectric, ferroelectric and piezoelectric properties. BiFeO_3 (BFO) is the only ferroelectric and antiferromagnetic material at the same time at room temperature. It shows good electromagnetics, semiconductor properties, resistance and gas sensitivity. In addition, titanic acid Sodium bismuth (Bi_ (0.5) (0.5) Na_ (0.5) TiO_3, BNT) is a kind of material with excellent piezoelectric properties. By combining with potassium bismuth titanate (Bi0.5K0.5TiO3, BKT) in a certain proportion and on the basis of the quasi Homo phase boundary (MPB), it will show high electrostrain properties and excellent dielectric tuning properties. Therefore, this paper is based on BiFeO_3 and Bi_ (0.5) Na_. (0.5) TiO_3 based material was used as the research object. By solid phase reaction, sol-gel method and hydrothermal method, A bit ion substitution or compound modification was carried out, and the effects of substitution composite on its ferroelectric, piezoelectricity, dielectric tuning, electrostrain and gas sensitivity were studied. The BiFeO_3 (Bi) of A position La substitution was prepared by the solid state reaction method. 1-xLaxFeO3, BLF) ceramics, study the effect of the substitution ratio on its electrical nonlinearity. Heat treatment and test the electrical properties of BLF under different atmospheres. It is found that the BLF conductance mechanism belongs to the P cavity conduction mechanism. The higher the oxygen partial pressure in the heat treatment atmosphere is, the better the conductivity is, the better the.BLF is in the nonlinear volt ampere characteristic, when the external electric field exceeds a certain threshold. After the increase of the current and the decrease of the resistance, the nonlinear coefficient increases with the decrease of the La substitution, increases with the increase of the temperature, and increases with the increase of the oxygen partial pressure in the heat treatment atmosphere. The nonlinear coefficient of the annealing treatment is the highest. It is pointed out that this resistance effect comes from the micro electronic heterogeneity at the ferroelectric domain and the domain wall. Structure, the conductivity of ferroelectric domain and domain wall is different, which leads to the existence of rectifying effect at the domain wall. The BiFeO_3 (Bi0.9Ba0.1FeO2.95, BBFO10) powder, which is substituted by A bit Ba, is prepared by sol-gel method. The gas sensing performance of several typical volatile gases is investigated and the sensitivity of the gas detection is significantly higher than that of pure BFO, and it is fast and fast. The response recovery speed, good gas selectivity and long-term stability are obtained. It is found that the area of BBFO10 is larger than the BFO powder, and the area of the contact with the gas molecules increases in the gas sensitive reaction. It is beneficial to increase the sensitivity of the reaction. In addition, the two valence Ba2+ ion division is used to replace the trivalent Bi3+ ion, which makes the oxygen vacancy in BBFO10. The increase in concentration also helps to improve the gas sensitivity of BBFO10. The BiFeO_3 (Bi0.9Ce0.1FeO3, BCFO) powders of BiFeO_3 and A sites were prepared by hydrothermal method and microwave hydrothermal method. The magnetic properties of the BiFeO_3 (Bi0.9Ce0.1FeO3, BCFO) powders were studied. The BFO prepared by the microwave hydrothermal method showed paramagnetic, while the BFO and BCFO-H prepared by hydrothermal method were weak ferromagnetic and Ce partly replaced. The magnetic properties of BCFO are obviously improved. This is due to the variation of the hybrid electron migration and the difference in the ionic radius of the internal and external orbit. The (1-x) (0.8BNT-0.2BKT) -xNaNbO3 (BNKT-xNN) ceramics are prepared. The changes of the strain, ferroelectric and dielectric properties with the components and temperature are studied. With the increase of NN content, BNKT-xNN gradually transforms from non ergodic relaxor ferroelectrics to ergodical relaxor, which shows that the phase transition temperature of ferroelectric phase TF-R decreases from room temperature to room temperature, and the piezoelectric coefficient d33 drops sharply, the hysteresis loop becomes thin waist, and the strain S-E curve is transformed from butterfly shape to bud shape. The irreversible phase transition of the ergodical relaxor component occurs under the action of the electric field. The transformation of the three square phase from the pseudopotential phase to the temperature above TF-R increases significantly. The electrostrain of the BNKT-0.04NN at room temperature is 0.445%, the Smax/Emax value is up to 810 pm/V, and the large strain is derived from the ergodical relaxation phase excited by the electric field. The dielectric tuning properties, the pyroelectric properties and the conduction mechanism of BNKT-xNN ceramics have been studied. The dielectric tuning properties of the materials are significant, and the dielectric tuning behavior is different with the different NN content, and the dielectric tuning behavior of the non ergodic relaxor components before and after the presence of the phase transition is not. The linear transformation is linear, and the group principle of ergodicity relaxor always maintains the nonlinear relation of the nonlinear relation.BNKT-xNN, which is n electron conduction mechanism, and its conductivity increases with the decrease of the concentration of oxygen partial pressure in heat treatment, and its conductance activation energy decreases with the decrease of the concentration of oxygen partial pressure in heat treatment. (1-x) (0.8BNT-0.2BKT) -xBiMg2/3N The strain, ferroelectric and dielectric properties of b1/3O3 (BNKT-xBMN) ceramics vary with the composition and temperature. The phase of.BNKT-x BMN is pseudopotential phase. As a non ergodical relaxor ferroelectric body, BNKT-0BMN exhibits a typical ferroelectric characteristic at room temperature. The irreversible phase transition.BNKT-0.02BMN is a ergodical relaxor ferroelectrics under the action of the electric field. The strain rate can reach 0.431%. Under the low electric field intensity of 40 kV/cm, Smax/Emax can reach up to 862 pm/V and has higher field strain efficiency, so it is suitable for practical application.
【學(xué)位授予單位】：西北工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TQ174.1;TB34

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