TWI595515B - 電壓非直線電阻體 - Google Patents

電壓非直線電阻體 Download PDF

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TWI595515B
TWI595515B TW103117727A TW103117727A TWI595515B TW I595515 B TWI595515 B TW I595515B TW 103117727 A TW103117727 A TW 103117727A TW 103117727 A TW103117727 A TW 103117727A TW I595515 B TWI595515 B TW I595515B
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zinc oxide
plane
voltage
voltage non
linear resistor
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TW103117727A
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TW201511044A (zh
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山崎哲
早瀨徹
森本健司
川崎真司
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日本碍子股份有限公司
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Description

電壓非直線電阻體
本發明係關於電壓非直線電阻體。
電壓非直線電阻元件(變阻器元件)係呈電壓非直線電阻體由一對電極夾置構造的元件，屬於當異常電壓時保護電子電路等的元件，廣泛使用於諸如濕度感測器、溫度感測器等各種感測器、以及電力用避雷器等。電壓非直線電阻體的電流電壓特性係如圖2所示。具有優異保護機能的電壓非直線電阻體係圖2中虛線所包圍高電流域中的電壓VH較低。以氧化鋅為主成分的電壓非直線電阻體，已知氧化鋅結晶粒內部的電阻率越小則電壓VH越小，以及藉由摻質的Al、Ga、In等3價離子固溶於氧化鋅中便可降低氧化鋅結晶粒內部之電阻率等。又，亦已知氧化鋅係屬於六方晶系的結晶構造，利用結晶構造在特性上會具有非等向性。
以氧化鋅為主成分的電壓非直線電阻體係有如專利文獻1、2所揭示者。專利文獻1有揭示：使朝c軸方向結晶成長的針狀氧化鋅粒子，配向成形於c軸方向上，再經燒結而成的電壓非直線電阻體，並測定該電壓非直線電阻體的a軸方向及c軸方向之壓敏電壓。專利文獻2有揭示：鑒於a軸方向的導電率較高，而配向(110)面的氧化鋅燒結體。
[先行技術文獻] [專利文獻]
[專利文獻1]日本專利特公平4-48746號公報
[專利文獻2]日本專利特開2002-121067號公報
然而，專利文獻1雖將針狀氧化鋅粒子施行擠出成形而使配向，但針狀氧化鋅粒子在擠出方向與平行面內(專利文獻1的第1圖上面)，(100)面或(110)面到底何種程度配向尚未明確。又，專利文獻1雖記載壓敏電壓(圖2由單點鏈線所包圍平坦區域的電壓)，但相關高電流區域的電壓VH則無記載亦無暗示。另一方面，專利文獻2中，因為配向氧化鋅燒結體的(110)面，因而高電流區域的電壓VH有變小的可能性，但在配向(110)面時必須朝特定方向施加高磁場，因而在製造該燒結體時便需要特殊的設備。
本發明係為解決此種課題而完成，主要目的在於提供：輕易製造高電流區域的電壓較低的電壓非直線電阻體。
本發明的電壓非直線電阻體係以氧化鋅為主成分，依下式所示氧化鋅的(100)面配向度f(100)係0.40以上。
f(100)=I(100)/(I(100)+I(002)+I(101))
其中，I(hk1)係表示(hk1)面的尖峰強度(積分值)。另外，「主成分」係指佔50重量%以上重量比例的成分。
根據本發明的電壓非直線電阻體，因為使氧化鋅的(100)面配向，因而使氧化鋅導電率較高的a軸方向配向。所以，氧化鋅粒內電阻變小，可抑低高電流區域的電壓。又，本發明的電壓非直線電阻體係將使(100)面配向的板狀氧化鋅粒子、與助劑原料的混合物，藉由使用剪切力的手法，形成使(100)面配向的成形體，再藉由對該成形體施行煅燒，便可較容易地製造。
10‧‧‧變阻器元件
12‧‧‧電壓非直線電阻體
14‧‧‧高電阻層
16、18‧‧‧電極
圖1係實施例1及比較例1的X射線繞射圖案圖。
圖2係電壓非直線電阻體的電流電壓特性圖。
圖3係變阻器元件10的切剖示意圖。
本發明的電壓非直線電阻體係以氧化鋅為主成分，且氧化鋅的(100)面配向度f(100)達0.40以上。此情況，因為使氧化鋅導電率較高的a軸方向配向，因而氧化鋅粒內電阻變小，便可抑低高電流區域的電壓。
本發明的電壓非直線電阻體中，下式所示氧化鋅的(002)面配向度f(002)較佳係0.10以下。此情況，因為未使氧化鋅導電率較低的c軸方向配向，因而結果導致氧化鋅粒內電阻變小。
f(002)=I(002)/(I(100)+I(002)+I(101))
本發明的電壓非直線電阻體，就從使產生非直線 性電阻特性的觀點，較佳係含有副成分的鉍(Bi)或鐠(Pr)中之任一者。
本發明的電壓非直線電阻體，亦可含有副成分之Bi、Sb、Co、Mn、Cr、Ni、Si、Al、B、Ag，分別依Bi2O3、Sb2O3、Co2O3、MnO2、Cr2O3、NiO、SiO2、Al3+、B2O3、Ag2O換算計為：Bi2O3：0.1~5.0mol%、Sb2O3：0.02~5.0mol%、CO2O3：0.1~5.0mol%、MnO2：0.1~5.0mol%、Cr2O3：0~1.0mol%、NiO：0.1~5.0mol%、SiO2：0.001~10.0mol%、Al3+：0.001~0.05mol%、Bi2O3：0.0001~0.05mol%、Ag2O：0.001~0.05mol%。
本發明的電壓非直線電阻體，氧化鋅結晶的平均粒徑較佳係3~15μm。
本發明的電壓非直線電阻體，結晶相較佳係由ZnO、Bi2O3及Zn7Sb2O12構成、或由ZnO、Bi2O3、Zn7Sb2O12及Zn2SiO4構成。
本發明的電壓非直線電阻體係可利用於晶片變阻器。
本發明的電壓非直線電阻體係可利用以下的製造方法製造。即，將以氧化鋅為主成分的原料混合物，使用剪切力使氧化鋅的(100)面配向成形而成為配向成形體，再藉由對該配向成形體施行煅燒，亦可獲得本發明的電壓非直線電阻體。
上述製造方法中，原料混合物中的氧化鋅更佳係使(100)面配向的板狀氧化鋅粒子使用達50wt%以上。又，原料混合物較佳係使用以氧化鋅為主成分，且含有副成分之Bi、Sb、Co、Mn、Cr、Ni、Si、Al、B、Ag，分別依Bi2O3、Sb2O3、 Co2O3、MnO2、Cr2O3、NiO、SiO2、Al3+、B2O3、Ag2O換算計為Bi2O3：0.1~5.0mol%、Sb2O3：0.02~5.0mol%、Co2O3：0.1~5.0mol%、MnO2：0.1~5.0mol%、Cr2O3：0~1.0mol%、NiO：0.1~5.0mol%、SiO2：0.001~10.0mol%、Al3+：0.001~0.05mol%、Bi2O3：0.0001~0.05mol%、Ag2O：0.001~0.05mol%的混合物粉末。
上述製造方法中，當使用剪切力成形配向成形體時，可採用例如：薄帶成形、擠出成形、刮漿刀法等。此時，最好將原料混合物施行漿化，再將該漿料經由吐出口成形為薄片狀配向成形體。又，配向成形體較佳係製作氧化鋅的(100)面配向度f(100)達0.50以上者。此種配向成形體更佳係氧化鋅的(002)面配向度f(002)在0.10以下。
上述製造方法中，最好在對配向成形體施行脫脂後材施行煅燒。煅燒最好依900~1200℃實施，最好在大氣中常壓下實施。又，就從延長電壓非直線電阻體壽命的觀點，最好在煅燒後更依400~600℃施行熱處理。又，使用薄片狀配向成形體時，在正式煅燒之前，亦可在積層複數片配向成形體之後更施行沖壓成形。
另外，本發明並不僅侷限於上述實施形態，舉凡在本發明技術範疇內當然均可依各種態樣實施。
[實施例]
[實施例1]
依以下方法製作氧化鋅粉末的原料粉末。使用硝酸鋅六水合物(關東化學股份有限公司製)，製作濃度0.1M的Zn(NO3)2 水溶液。又，使用氫氧化鈉(SIGMA-ALDRICH公司製)製作濃度0.1M的NaOH水溶液。對NaOH水溶液，依體積比1：1混合入Zn(NO3)2水溶液，且一邊攪拌一邊依80℃保持6小時，獲得沉澱物。沉澱物利用離子交換水施行3次洗淨後，經乾燥便獲得由板狀氧化鋅初級粒子凝聚的球狀次級粒子。接著，藉由使用直徑2mm的ZrO2製磨球，並以IPA(異丙醇)為分散媒，施行4小時的球磨機粉碎處理，而將氧化鋅次級粒子粉碎為體積基準D50平均粒徑0.6μm的板狀初級粒子。該板狀初級粒子經利用穿透式電子顯微鏡像及選區電子繞射(selected-area electron diffraction)確認到朝(100)面配向。
將依成為如表1所示組成的方式既定量秤量除Al成分以外的助劑原料，使用直徑5mm的ZrO2製磨球，以水為分散媒，藉由施行16小時的球磨機處理，而粉碎為D50平均粒徑0.6μm。此處，B2O3、Ag2O全量、及Bi2O3、SiO2其中一部分係將由Bi2O3、SiO2、B2O3、Ag2O構成的玻璃料為原料。在經粉碎的混合物中既定量混合入Al3+之硝酸鋁水溶液，經乾燥便成為助劑原料混合粉末。
相對於依成為表1所示組成的方式秤量之板狀氧化鋅初級粒子與助劑原料混合粉末的混合物100重量份，混合 入：黏結劑(聚乙烯丁醛：型號BM-2、積水化學工業股份有限公司製)15重量份、可塑劑(DOP：酞酸二(2乙基己酯)、黑金化成股份有限公司製)6.2重量份、分散劑(製品名RHEODOL SP-O30、花王股份有限公司製)3重量份、及分散媒(2-乙基己醇)。分散媒的量係依漿料黏度成為20000~30000cP的方式調整。將依此調整的漿料利用刮漿刀法，在PET薄膜上依乾燥後的厚度成為24μm方式成形為薄片狀。
利用XRD測定經成形為薄片狀的薄帶片(成形體)之(100)面及(002)面配向度。該測定係藉由使用XRD裝置(Rigaku股份有限公司製、製品名RINT-TTRIII、平行光束光學系統)，測定對薄帶成形體的表面照射X射線時的XRD譜圖而實施。(hk1)面配向度的f(hk1)係依下式計算。本例的配向度f(100)及f(002)值分別係0.55及0.05。
f(hk1)=I(hk1)/(I(100)+I(002)+I(101))
(I(hk1)係試料的(hk1)面之繞射強度(積分值))
所獲得薄帶切斷為直徑20mm的圓形，積層100片的切斷薄帶片，經設置於厚10mm鋁板上之後，施行真空包裝。將該真空包裝在85℃溫水中，依100kgf/cm2壓力施行冷均壓而製作圓盤狀成形體。將所獲得成形體配置於脫脂爐中，依升溫速度25℃/hr、最高溫度450℃、5小時的條件施行脫脂。所獲得脫脂體依大氣中、升溫速度30℃/hr、最高溫度1040℃、5小時的條件施行常壓煅燒。所獲得煅燒體的主成分係ZnO(重量比例94.5重量%)。
在煅燒體的側面塗佈玻璃糊(BL202、CENTRAL GLASS股份有限公司製)，於大氣中，依500℃施行2小時熱處理，使玻璃糊熔執而形成側面高電阻層，便獲得圓盤狀氧化鋅電壓非直線電阻體。該熱處理亦具有電壓非直線電阻體長壽命化的功用。所獲得電壓非直線電阻體的二端面利用相當於#800的SiC紙施行研磨並洗淨。
所獲得煅燒體(圓盤狀氧化鋅電壓非直線電阻體)圓盤上面的(100)面及(002)面配向度、f(100)及f(002)值，分別係0.43、0.01。又，針對同樣製作的煅燒體，垂直於圓盤面且平行於PET薄膜拉出方向面的(002)面配向度f//(002)、及垂直於圓盤面且垂直於PET薄膜拉出方向面的(002)面配向度f⊥(002)值均係0.30，並沒有發現面內方向的c軸配向非等向性。另外，f//(hk1)及f⊥(hk1)的計算式係與f(hk1)相同。
在依如上述獲得 17mm×高1.6mm電壓非直線電阻體經研磨過的二端面(圓盤的上下面)，塗佈In-Ga電極而成為變阻器元件，施行電流-電壓特性測定。相當於2mA/cm2電流值(圖2的平坦區域)的產生電壓係363V/mm，相當於2kA/cm2電流值(圖2的高電流區域)的產生電壓係590V/mm。
圖3所示係實施例1的變阻器元件切剖示意圖。該變阻器元件10係在電壓非直線電阻體12的側面具有高電阻層14，且上下面設有一對電極16、18，上下面的(100)面配向度f(100)數值高。
[比較例1]
依成為表1所示組成的方式既定量秤量氧化鋅、與除Al成分以外的助劑原料，並既定量添加依與實施例同樣施行球磨 機粉碎的助劑原料混合物、及依與實施例同樣製作的板狀氧化鋅初級粒子、以及硝酸鋁水溶液，並添加水分量調整為50wt%，再與微量黏結劑、分散劑及消泡劑一起施行60分鐘的超音波攪拌、及30分中的葉片攪拌而混合後，利用噴霧乾燥機施行造粒而獲得造粒物。造粒物經利用開孔200μm篩施行篩通後，於成形壓力800kgf/cm2下施行單軸加壓成形成為 26mm×高10mm。
所獲得成形體的(100)面及(002)面配向度、f(100)及f(002)值分別係0.35、0.13。
成形體經依與實施例同樣的條件施行脫脂、煅燒後，再與實施例同樣地形成側面高電阻層，獲得氧化鋅電壓非直線電阻體。所獲得電壓非直線電阻體的二端面利用相當於#800的SiC紙施行研磨並洗淨。
所獲得煅燒體的(100)面及(002)面配向度、f(100)及f(002)值分別係0.29、0.15。又，相關同樣製作的煅燒體，垂直於加壓方向且相互正交的二面之(002)面配向度f//(002)、及f⊥(002)值均係0.25，並沒有發現面內方向的c軸配向非等向性。
在依如上述獲得 20mm×高8mm電壓非直線電阻體經研磨過的二端面塗佈In-Ga電極，施行電流-電壓特性測定。相當於2mA/cm2電流值(圖2的平坦區域)的產生電壓係365V/mm，相當於2kA/cm2電流值(圖2的高電流區域)的產生電壓係608V/mm。
實施例1及比較例1所獲得結果整理如表2。又， 圖1所示係實施例及比較例所獲得成形體與煅燒體的XRD圖。相較於實施例1的成形體、燒結體之下，比較例1的成形體、燒結體呈現f(100)較低值的現象，可認為實施例1中，在成形時施加剪切力而容易朝a軸方向配向，相對於此，比較例1並沒有施行此種剪切力的緣故所致。
產業上之可利用性
本發明的電壓非直線電阻體係可利用於濕度感測器、溫度感測器等各種感測器、及電力用避雷器等。

Claims (2)

  1. 一種電壓非直線電阻體，以氧化鋅為主成分，依下式所示氧化鋅的(100)面配向度f(100)係0.40以上；f(100)=I(100)/(I(100)+I(002)+I(101))其中，I(hk1)係表示(hk1)面的尖峰強度(積分值)。
  2. 如申請專利範圍第1項之電壓非直線電阻體，其中，下式所示氧化鋅的(002)面配向度f(002)係0.10以下；f(002)=I(002)/(I(100)+I(002)+I(101))其中，I(hk1)係表示(hk1)面的尖峰強度(積分值)。
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