TWI747890B - 陶瓷材料、變阻器，以及製備該陶瓷材料和該變阻器的方法 - Google Patents

陶瓷材料、變阻器，以及製備該陶瓷材料和該變阻器的方法 Download PDF

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TWI747890B
TWI747890B TW106108703A TW106108703A TWI747890B TW I747890 B TWI747890 B TW I747890B TW 106108703 A TW106108703 A TW 106108703A TW 106108703 A TW106108703 A TW 106108703A TW I747890 B TWI747890 B TW I747890B
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ceramic material
varistor
content
ceramic
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TW106108703A
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TW201800363A (zh
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王永力
伍建新
易文斌
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德商Ｅｐｃｏｓ Ａｇ集團股份公司
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    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
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Abstract

揭示陶瓷材料，其包含ZnO作為主要組成分，及添加劑係選自於包含含Al3+之溶液、含Ba2+之溶液、及含金屬元素的至少一個化合物之群組，其中該金屬元素係選自於包含Bi、Sb、Co、Mn、Ni、Y、及Cr之群組。進一步揭示包含含有經燒結之陶瓷材料的陶瓷體之變阻器。也提供製備該陶瓷材料和該變阻器的方法。

Description

陶瓷材料、變阻器，以及製備該陶瓷材料和該變阻器的方法
本發明係有關於陶瓷材料及包含涵括經燒結的陶瓷材料之陶瓷體的變阻器。又復，本發明係有關於製備該陶瓷材料之方法及製備包含由該經燒結的陶瓷材料製成之陶瓷體的變阻器之方法。
隨著變電所容量的增加及地下車站的發展，要求電力傳輸及功率變換裝置的尺寸縮小。結果，需要較小尺寸及/或較簡單結構的氣體隔離之配電裝置(GIS)電湧變阻器以因應該趨勢及減少SF6及外殼材料的消耗。此種要求需要新一代的關鍵性組件，亦即金屬氧化物變阻器(MOV)，用於特定保護電壓其高度須顯著地減低。
為了滿足MOV的高度減低，須改良製成MOV的陶瓷材料之數種性質。
本發明之目的係提供具有改良性質欲使用於 變阻器的陶瓷材料及提供含有由此種陶瓷材料所製成的變阻器。進一步目的係提供製備該陶瓷材料和該變阻器的方法。
此等目的係以獨立請求項1之陶瓷材料，以獨立請求項9之變阻器及以請求項11及13之方法予以滿足。進一步具體例為附屬請求項之主旨。
依據至少一個具體例，提供一種陶瓷材料包含ZnO作為主要組成分，及添加劑係選自於包含含Al3+之溶液、含Ba2+之溶液、及含金屬元素之至少一個化合物之群組，其中該金屬元素係選自於包含Bi、Sb、Co、Mn、Ni、Y、及Cr之群組。
須瞭解「陶瓷材料」為以只須經燒結來變成陶瓷之方式製備的組成分之組成物。由陶瓷材料製成的本體可稱作坯體。當陶瓷材料被燒結時形成陶瓷，其具有取決於陶瓷材料之組成的性質。
添加至主要組成分ZnO的添加劑可包含含有金屬元素的一種化合物，或數種化合物其各自含有一種金屬元素，其中於各種化合物中之金屬元素可不同。舉例言之，可以有含鉍化合物、含銻化合物、及含鈷化合物作為陶瓷材料中之添加劑。
須瞭解添加劑含Al3+之溶液及含Ba2+之溶液為添加至主要組成分ZnO的起始劑物料。另外，此等添加劑可分別地定名Al3+及Ba2+，當製備陶瓷材料時其係以含Al3+之溶液及含Ba2+之溶液的形式添加。
依據一個具體例，陶瓷材料中之添加劑之含量為
Figure 106108703-A0202-12-0003-8
5mol%。須瞭解全部添加劑一起的含量為
Figure 106108703-A0202-12-0003-9
5mol%。比較具有典型為5mol%至7mol%之添加劑含量的先前技術陶瓷，此乃減低之添加劑含量。陶瓷材料中之添加劑的含量低，結果導致經燒結陶瓷中之二次相含量低，其加強有效ZnO相及ZnO-ZnO晶粒邊界，結果導致變阻器陶瓷之更高的體積效率。
依據一個具體例，於陶瓷材料中，c1為Co3O4中之Co的當量含量，m為Mn3O4中之Mn的當量含量，s為Sb2O3中之Sb的當量含量，c2為Cr2O3中之Cr的當量含量，a為Al3+之含量，y為Y2O3中之Y的當量含量，b1為Bi2O3中之Bi的當量含量，n為NiO中之Ni的當量含量，b2為Ba2+之含量，及z為ZnO之含量及其為：0.40mol%
Figure 106108703-A0202-12-0003-10
b1
Figure 106108703-A0202-12-0003-11
0.55mol%，1.10mol%
Figure 106108703-A0202-12-0003-12
s
Figure 106108703-A0202-12-0003-13
1.90mol%，0.50mol%
Figure 106108703-A0202-12-0003-14
c1
Figure 106108703-A0202-12-0003-15
0.80mol%，0.20mol%
Figure 106108703-A0202-12-0003-16
m
Figure 106108703-A0202-12-0003-17
0.30mol%，0.70mol%
Figure 106108703-A0202-12-0003-18
n
Figure 106108703-A0202-12-0003-19
1.20mol%，0.25mol%
Figure 106108703-A0202-12-0003-20
y
Figure 106108703-A0202-12-0003-21
0.45mol%，0.00mol%
Figure 106108703-A0202-12-0003-22
c2
Figure 106108703-A0202-12-0003-23
0.10mol%，0.003mol%
Figure 106108703-A0202-12-0003-24
a
Figure 106108703-A0202-12-0003-25
0.006mol%，及0.005mol%
Figure 106108703-A0202-12-0003-26
b2
Figure 106108703-A0202-12-0003-27
0.015mol%。
作為含金屬元素之化合物選擇前述氧化物之 情況下，b1也對應於Bi2O3之含量，s也對應於Sb2O3之含量，c1也對應於Co3O4之含量，m也對應於Mn3O4之含量，n也對應於NiO之含量，c2也對應於Cr2O3之含量，及y也對應於Y2O3之含量。
此外，(c1+5c2+2s+4y-m-250a)(1-z)/b1可被稱作組成因數F及其適用0.27
Figure 106108703-A0202-12-0004-28
F
Figure 106108703-A0202-12-0004-29
0.43。陶瓷材料中不同添加劑的含量之關係負責於陶瓷材料之燒結期間晶粒大小的控制及晶粒邊界生成的可能性，以便達成經燒結的陶瓷的超高變阻器梯度(E1mA)自480V/mm(含)至640V/mm(含)。變阻器梯度為每毫米的特性變阻器電壓。
添加劑含量與變阻器梯度間之交互關係藉由同時地且適當地針對期望的變阻器梯度改變相關元素而使得經燒結的陶瓷中之變阻器無活性相，例如，尖晶石相Zn7Sb2O12變最小化。結果，經燒結陶瓷的體積效率可藉由更有效的ZnO-ZnO晶粒邊界予以提升。
此外，至少一個化合物可選自於含金屬氧化物、金屬碳酸鹽、金屬乙酸鹽、金屬氮化物及其混合物之群組。該至少一個化合物可選自於含Bi2O3、Sb2O3、Co3O4、Mn3O4、NiO、Y2O3、及Cr2O3之群組。舉例言之，含金屬元素之全部化合物可以是各自含有不同金屬元素的金屬氧化物。
此外，含Al3+之溶液及含Ba2+之溶液可以是選自於包含氮化物、乙酸鹽、水合物、及其混合物之群組。舉例言之，含Ba2+之溶液可以是Ba(CH3COO)2溶液及含Al3+ 之溶液可以是硝酸鋁Al(NO3)3溶液。陶瓷材料中之Ba2+含量係經調整以減少由陶瓷材料製成的陶瓷之高溫功率損失及/或漏電流，及改良含有由陶瓷材料製成的陶瓷體之變阻器的I/V曲線之非線性度。
依據一個具體例，陶瓷材料具有1020℃(含)至1060℃(含)之燒結溫度。此種減低的燒結溫度要求較少能量。以環保觀點視之此點為優異，且使其能快速製造含有由陶瓷材料製成的陶瓷之變阻器裝置。又復，Bi2O3之氣化於熱力學上受遏制，結果導致Bi2O3的較低揮發性，同時減少可能的組成偏差及可能藉燒結誘生的非同質性。
陶瓷的同質性結果導致操作期間由陶瓷材料製成的變阻器中電流分布的同質性，此點對變阻器裝置的能量容量具有關鍵重要性。
如此，依據前述具體例，以ZnO為主的陶瓷材料可使用於能夠用在氣體隔離放電器(GIS)中之金屬氧化物變阻器(MOV)。由陶瓷材料製成的陶瓷之超高變阻器梯度使得放電器裝置能夠微縮化及設計簡化。又復，陶瓷顯示減低的高溫功率損耗，防止熱散逸，即便於惡劣熱耗散條件下亦復如此。
此外，提供一種變阻器其包含涵括依據前述具體例之經燒結的陶瓷材料的陶瓷體。因陶瓷材料之組成故，變阻器可被稱作金屬氧化物變阻器(MOV)。變阻器可具有480V/mm(含)至640V/mm(含)之變阻器梯度E1mA。如此，提供變阻器的超高梯度。此種變阻器例如可使用於精 簡GIS放電器。
因於變阻器中使用依據前述具體例中之一者的陶瓷材料故，變阻器具有數種優異性質。舉例言之，因陶瓷材料之組成故，可大大地減少陶瓷體中之二次相的數量。
於習知變阻器陶瓷中，晶粒大小係由尖晶石相(Zn7Sb2O12)控制，該尖晶石相於變阻器反應中實際上不具活性。燒結期間尖晶石相的形成自陶瓷材料之組成中消耗了相當大量ZnO(1mol Sb2O3對應於7mol ZnO)。因此，針對含有2mol% Sb2O3的組成物，由尖晶石相將攝取約14mol% ZnO，及於最終陶瓷中有至多86mol% ZnO將可用於形成變阻器晶粒邊界。尖晶石相之含量高也減低了ZnO晶粒邊界的連結性。結果，體積效率強力受限制，特別當須藉增加尖晶石相以縮小晶粒大小而達成較高變阻器梯度時尤為如此。
於陶瓷材料內導入的Y2O3可於燒結期間與Bi2O3、Sb2O3、及小量ZnO(可媲美Sb2O3之用量)反應及形成極細小粒子(直徑小於1微米)，其比尖晶石更有效地遏制晶粒生長。如此，超高變阻器梯度可以陶瓷材料中Sb2O3之減低含量達成，例如，低抵1.2mol% Sb2O3達成。Sb2O3(或最終陶瓷中之尖晶石相)及其它添加劑整體之減低含量(
Figure 106108703-A0202-12-0006-30
5mol%)導致含有由陶瓷材料製成的陶瓷之變阻器的高體積效率。
此外，由陶瓷材料製成的變阻器之陶瓷體具 有取決於裝置設計的於190℃之期望的高溫功率損耗PCOV，及優異的陡度s7(為位準固定梯度E10kA對變阻器梯度E1mA之關係：E10kA/E1mA)，特別陡度s7為
Figure 106108703-A0202-12-0007-31
1.5。此等性質也適用於欲使用在具有縮小的尺寸及惡化的熱耗散條件之GIS放電器中之變阻器的陶瓷。
如此，MOV之高度降低可藉陶瓷材料之使用而予滿足，原因在於變阻器梯度相當地增高且同時MOV之高溫功率損耗減低故。
須瞭解於陶瓷材料之脈絡中述及的特徵也適用於變阻器，及於變阻器之脈絡中述及的特徵也適用於陶瓷材料。
又，提供製備依據前述具體例中之一者的陶瓷材料之方法。該方法具有下列製備步驟：稱重、混合及球磨添加劑之第一部分，添加ZnO及添加劑之第二部分，形成均質料漿，及噴乾該料漿而形成陶瓷材料之顆粒。添加劑之第一部分可以是含金屬元素的至少一個化合物，其中該金屬元素係選自於包含Bi、Sb、Co、Mn、Ni、Y、及Cr之群組，及該添加劑之第二部分可以是含Al3+之溶液及含Ba2+之溶液中之至少一者。
舉例言之，將添加劑Bi2O3、Sb2O3、Y2O3、Co3O4、Cr2O3、Mn3O4、及NiO或具有等量金屬元素的其它類型之氧化物、碳酸鹽、乙酸鹽、氮化物經稱重、混合及例如於水中球磨而獲得期望的粒徑分布。主要組成分ZnO可以粉末形式添加及例如，連同呈氮化物、乙酸鹽或水合 物形式的含Al3+之溶液及含Ba2+之溶液一起導入系統內。為了形成均質料漿，可進一步導入額外水及若干有機物諸如，例如黏結劑、分散劑、消泡劑，及可形成具有期望黏度及密度的均質料漿。料漿之噴乾經進行以獲得具有期望直徑、流動性及可壓縮性之顆粒用於隨後方法步驟。
此外，提供變阻器之製法包含下列製備步驟：形成含有依據前述具體例中之一者製備的陶瓷材料之陶瓷體，及施加電極層，其中該陶瓷材料係於1020℃(含)至1060℃(含)之溫度燒結而形成陶瓷體。
陶瓷體之形成可包含下列進一步步驟：乾壓以前述方法製備的陶瓷材料之顆粒，將陶瓷材料脫脂及燒結陶瓷材料，及其中該等步驟係在燒結之前進行。
舉例言之，提供從以前述方法製備的陶瓷材料之顆粒形成的經界定尺寸之圓柱體形狀之生坯部件，其中該等經界定尺寸可取決於進一步特徵化方法。至於變阻器梯度E1mA、位準固定梯度E10kA、漏電流密度JS之特徵性質，生坯部件之維度可以是直徑15.6毫米及厚度1.8毫米。為了驗證能量變阻器，直徑可以是130毫米至155毫米及厚度可以是22毫米。生坯部件可以是自顆粒乾壓，接著於空氣中於約500℃去脂而去除有機組成分。然後生坯部件可於1020℃至1060℃燒結1至3小時而獲得緊密均勻的變阻器陶瓷體。
例如鋁或銀層之電極層可施加至陶瓷體的頂面及底面上。鋁例如可藉斯庫普(Schoop)法施用，其中該 等熔融金屬小滴濺鍍至固體表面上而形成電極。銀例如可藉濺鍍施用。
此外，於陶瓷體之側表面上可施加隔離層。舉例言之，藉噴霧及退火可施加高度隔離的釉料塗覆層。釉料塗覆層可包含玻璃。退火可於約510℃之溫度進行。隔離層之施用可於電極層之施用之前進行。
陶瓷材料、變阻器以及製備該陶瓷材料和該變阻器的方法將藉實施例及圖式進一步解說如後。
10‧‧‧陶瓷體
20‧‧‧電極層
30‧‧‧隔離層
A‧‧‧富含Y-Bi相
B‧‧‧富含Bi液相
C‧‧‧尖晶石Zn7Sb2O13相
F‧‧‧組成因數
E1mA‧‧‧變阻器梯度
s7‧‧‧陡度
JS‧‧‧漏電流密度
第1圖顯示一變阻器之剖面圖；第2圖顯示變阻器梯度E1mA對組成因數F之相依性；第3圖顯示由陶瓷材料製成的陶瓷之一個具體例的顯微結構照片；第4圖顯示數種電氣性質對Ba2+含量之相依性。
相同的、相似的或表觀上相等的元件於圖式中具有相同號碼或元件符號。圖式中元件的特徵及比例並未按比例繪製。反而，為求更佳地呈現及/或為求更明白瞭解數個元件可不成比例地放大呈現。
第1圖顯示依據一個具體例一變阻器之剖面圖。其含有陶瓷體10、電極層20及隔離層30。為了製備變阻器，首先形成陶瓷體10。
為了達成此目的，固態添加劑原料諸如Bi2O3、Sb2O3、Y2O3、Co3O4、Cr2O3、Mn3O4、及NiO(或具有等量金屬元素的其它類型之氧化物、碳酸鹽、乙酸鹽、氮化物)經稱重、混合及於水中球磨而獲得期望的粒徑分布。然後主要組成分ZnO可以粉末形式及連同(以氮化物、乙酸鹽或水合物表示)的含Al3+之溶液及含Ba2+之溶液一起導入系統內。進一步導入額外水及若干有機物(例如黏結劑、分散劑、消泡劑)以形成具有期望黏度、密度、或固體含量的均質料漿。然後藉料漿之噴乾法製造具有期望直徑及粒徑分布、堆積密度、流動性及可壓縮性的顆粒。
含有陶瓷材料顆粒之進一步形成的圓柱形生坯部件的大小取決於進一步特徵化方法：舉例言之，用於電氣特徵化，直徑15.6毫米及厚度1.8毫米的圓錠形生坯部件自顆粒乾壓，接著於約500度於空氣中脫脂而去除有機組成分。然後圓錠於1040℃燒結歷時3小時以獲得緊密陶瓷體。頂面及底面例如使用銀藉濺鍍而被金屬化。
用於如第1圖中顯示的能量變阻器，生坯部件之側表面藉噴霧及退火塗覆有以一層高度隔離釉料而形成隔離層30。頂面及底面經研磨以去除污染釉料及獲得期望的高度及表面品質。頂面及底面例如藉斯庫普法使用鋁全然金屬化。
於後文中，顯示陶瓷材料及其製成的陶瓷之數個實施例。
表1中描述之試樣E01至E43解釋於經界定 之製程條件下添加劑含量與變阻器梯度E1mA間之交互關係。於經界定的各個組成分包括ZnO及其它添加劑之範圍以內，變阻器梯度強力地取決於最具相關性的添加劑組成分Bi2O3、Sb2O3、Y2O3、Co3O4、Cr2O3、Mn3O4、NiO及Al3+之相對含量。相依性可由E1mA與組成因數F間之線性關係表示，其中F為Co3O4(c1)、Mn3O4(m)、Sb2O3(s)、Cr2O3(c2)、Al3+(a)、Y2O3(y)、Bi2O3(b1)、及ZnO(z)之含量的函數：F=(c1+5c2+2s+4y-m-250a)(1-z)/b1
為了獲得期望的變阻器梯度，例如E1mA為480V/mm(含)至640V/mm(含)，添加劑之含量須經調整使得因數F為0.26，較佳地為0.27(含)至0.43(含)。
試樣E01至E43係如就第1圖所述製備，其中直徑15.6毫米及厚度1.8毫米之圓錠形生坯部件係自顆粒乾壓，接著於約500℃於空氣中脫脂而去除有機組成分。然後圓錠於1040℃燒結歷時3小時以獲得緊密陶瓷體。
為了試樣之特徵化，圓錠於頂面及底面例如使藉銀濺鍍而被金屬化。金屬化部件之電氣性質經特徵化，及然後標準化至直徑125毫米及高度18毫米之能量變阻器以用於公平比較。
變阻器梯度E1mA係以低DC電流測量，其獲得於直徑125毫米之陶瓷圓錠上方的1mA電流密度(或約10微安培/平方厘米)。位準固定梯度E10kA係使用8/20微秒之放電波測量，及獲得於直徑125毫米之陶瓷圓錠上方的 1kA電流密度(或約100安培/平方厘米)。陡度s7係等於E10kA/E1mA。於室溫及於170℃之漏電流密度JS係於0.75E1mA係於DC電場下測量。
表1顯示各個實施例E01至E43之組成，其中ZnO對添加劑之含量比係以mol%、因數F及變阻器梯度E1mA表示。可知用於0.27至0.43間之因數F，變阻器梯度係於480V/mm至640V/mm之期望範圍內。若因數F分別地係大於或小於0.43及0.27，則無法達成變阻器梯度的期望範圍(實施例E03、E06至E08、E18、E23及E24)。
Figure 106108703-A0202-12-0013-1
變阻器梯度對組成因數F之相依性也顯示於第2圖中，其中可明白地瞭解E1mA與F間之交互關係。
表示法F反映出個別組成分影響變阻器梯度的效果，變阻器梯度實際上係由燒結期間晶粒大小及晶粒邊界生成的潛力決定。晶粒成長主要係由二次相，如於第3圖中可知尖晶石相Zn7Sb2O12及富含Y-Bi相，的形成及分布加以控制。於第3圖中，顯示範圍試樣E15陶瓷的顯微結構。A顯示富含Y-Bi相，B顯示富含Bi之液相，及C顯示尖晶石相Zn7Sb2O12。
尖晶石相係以2微米至4微米之晶粒大小予以特徵化，而富含Y-Bi相具有直徑次微米的遠更小的尺寸。結果，用於達成期望的變阻器梯度，Y2O3的導入比較Sb2O3的效果獲得加倍效果。尖晶石相的形成消耗大量ZnO而不利於高體積效率。藉由導入1mol% Sb2O3，約7mol%之ZnO將由尖晶石相攝取，及有效變阻器體積分量(ZnO晶粒)須減少如此大量。相反地，富含Y-Bi相晶粒具有小含量之ZnO且對體積效率的影響小。據此，藉由協力合作地改變其它添加劑之含量，使得因數F落入於某個尺規以內(例如，E12、E22、及E33至E42之組成)可達成具有減低之Sb2O3含量(例如，1.1mol%至1.2mol%)的超高梯度變阻器陶瓷。
試樣E44至E46連同試樣E15及E25列舉於表2，及顯示Ba2+含量對高溫漏電流JS及陡度特性s7之影響。
Figure 106108703-A0305-02-0018-1
表2中列舉的組成全部皆具有相同的添加劑用量，但Ba2+之含量除外。ZnO及添加劑之含量係以mol%表示。製備方法及電氣特性針對實施例E01至E43描述者為相同。作為Ba2+-含量b2之函數的基本電氣性質係於第4圖中作圖。此處，Ba2+之含量b2係對高溫漏電流Js、陡度s7及變阻器梯度E1mA作圖。圖4中之圓圈為試樣之個別測量值，方框為散射之統計學表示型態(例如，中值、平均值、最小值、最小值等值，取決於作圖中之定義)。顯然，低達0.0060%之微量Ba2+可有效地減低高溫漏電流密度JS，此點對裝置操作中之能量容量具有關鍵重要性。進一步提高b2導致甚至更低的漏電流，但當b2超過0.0150%時陡度s7甚至更惡劣。
於表3中連同試樣E10、E15及E19一起列舉的試樣E47至E49，係從分別地與E10、E15及E19相同組成製備，但於脫脂及燒結前生坯部件之尺寸為直徑150毫米及高度25毫米。如此，於表3中，試樣編號(實施例)、組成、直徑D及厚度T係連同變阻器梯度E1mA、陡度s7、高溫漏電流JS及高溫功率損耗Pcov一起列舉。
Figure 106108703-A0202-12-0016-3
脫脂及燒結條件係與實施例E01至E46中之小型圓錠相同。然後噴霧一層玻璃材料至試樣之側表面上，接著於510℃退火以獲得緊密且高度隔離的釉料塗層。然後在兩個主要側邊上的部件經研磨至期望的厚度，例如18毫米。鋁金屬化例如藉斯庫普法提供於頂面及底面上用於電氣接觸。基本電氣性質經特徵化(替代JS，高溫功率損耗Pcov係於190℃於50Hz-E10kA之AC場/2.75幅值下測量)且與實施例E10、E15及E19之小型圓錠作比較。基本上，小型圓錠之變阻器梯度E1mA可以約5%之些微偏移值良好地再現，而因尺寸效應故陡度s7遷移至較低值。針對具有較低JS之材料可預期較低的Pcov，原因在於兩者皆係源自於相同的物理效應(高溫電阻)故。
因而可顯示以ZnO為主的陶瓷材料可使用於能夠用在氣體隔離放電器中之金屬氧化物變阻器。此等材料之超高變阻器梯度乃放電器裝置的微縮化及設計簡化所必需。
本發明之保護範圍並不限於上文中舉出的實施例。本發明係於各種新穎特性及各種特性之組合中具體實施，其特別地包括於申請專利範圍中陳述的任何特徵之 每種組合，即便此種特徵或此種特徵之組合並未明確地陳述於申請專利範圍中或實施例中亦復如此。
10‧‧‧陶瓷體
20‧‧‧電極層
30‧‧‧隔離層

Claims (13)

  1. 一種陶瓷材料，其包含- ZnO作為一主要組成分，及- 添加劑，其係選自於包含含Al3+之溶液、含Ba2+之溶液、及含一金屬元素之至少一個化合物之一群組，其中該金屬元素係選自於包含Bi、Sb、Co、Mn、Ni、Y、及Cr之群組，其中c1為Co3O4中之Co的當量含量，m為Mn3O4中之Mn的當量含量，s為Sb2O3中之Sb的當量含量，c2為Cr2O3中之Cr的當量含量，a為Al3+之含量，y為Y2O3中之Y的當量含量，b1為Bi2O3中之Bi的當量含量，n為NiO中之Ni的當量含量，b2為Ba2+之含量，及z為ZnO之含量，且其為0.40mol%
    Figure 106108703-A0305-02-0021-2
    b1
    Figure 106108703-A0305-02-0021-3
    0.55mol%，1.10mol%
    Figure 106108703-A0305-02-0021-4
    s
    Figure 106108703-A0305-02-0021-5
    1.90mol%，0.50mol%
    Figure 106108703-A0305-02-0021-6
    c1
    Figure 106108703-A0305-02-0021-7
    0.80mol%，0.20mol%
    Figure 106108703-A0305-02-0021-8
    m
    Figure 106108703-A0305-02-0021-9
    0.30mol%，0.70mol%
    Figure 106108703-A0305-02-0021-10
    n
    Figure 106108703-A0305-02-0021-11
    1.20mol%，0.25mol%
    Figure 106108703-A0305-02-0021-12
    y
    Figure 106108703-A0305-02-0021-13
    0.45mol%，0.00mol%
    Figure 106108703-A0305-02-0021-14
    c2
    Figure 106108703-A0305-02-0021-15
    0.10mol%，0.003mol%
    Figure 106108703-A0305-02-0021-17
    a
    Figure 106108703-A0305-02-0021-18
    0.006mol%，及0.005mol%
    Figure 106108703-A0305-02-0021-19
    b2
    Figure 106108703-A0305-02-0021-20
    0.015mol%。
  2. 如申請專利範圍第1項所述之陶瓷材料，其中該陶瓷材料中之該等添加劑之該含量為
    Figure 106108703-A0305-02-0021-21
    5mol%。
  3. 如申請專利範圍第1或2項所述之陶瓷材料，其中(c1+5c2+2s+4y-m-250a)(1-z)/b1=F及0.27
    Figure 106108703-A0305-02-0022-22
    F
    Figure 106108703-A0305-02-0022-24
    0.43。
  4. 如申請專利範圍第1或2項所述之陶瓷材料，其中該至少一個化合物係選自於含金屬氧化物、金屬碳酸鹽、金屬乙酸鹽、金屬氮化物及其混合物之群組。
  5. 如申請專利範圍第1或2項所述之陶瓷材料，其中該至少一個化合物係選自於含Bi2O3、Sb2O3、Co3O4、Mn3O4、NiO、Y2O3、及Cr2O3之群組。
  6. 如申請專利範圍第1或2項所述之陶瓷材料，其中該含Al3+之溶液及該含Ba2+之溶液為選自於包含氮化物、乙酸鹽、水合物、及其混合物之群組。
  7. 如申請專利範圍第1或2項所述之陶瓷材料，其具有含1020℃至含1060℃之燒結溫度。
  8. 一種變阻器，其包含含有如申請專利範圍第1至7項中任一項所述之經燒結的陶瓷材料之陶瓷體(10)。
  9. 如申請專利範圍第8項所述之變阻器，其具有含480V/mm至含640V/mm之一變阻器梯度E1mA。
  10. 一種製備如申請專利範圍第1至7項中任一項所述之陶瓷材料的方法，其包含下列製備步驟- 稱重、混合及球磨添加劑之第一部分，- 添加ZnO及添加劑之第二部分，- 形成均質料漿，及- 噴乾該料漿而形成該陶瓷材料之顆粒。
  11. 如申請專利範圍第10項所述之方法，其中該添加劑之第一部分為含有一金屬元素的至少一個化合物，其中該金屬元素係選自於包含Bi、Sb、Co、Mn、Ni、Y、及Cr之一群組，及該添加劑之第二部分為含Al3+之溶液及含Ba2+之溶液中之至少一者。
  12. 一種製備變阻器的方法，其包含下列製備步驟- 形成含有使用如申請專利範圍第10或11項之方法製備的陶瓷材料之陶瓷體(10)，- 於該陶瓷體上施加電極層，其中該陶瓷材料係於含1020℃至含1060℃之溫度燒結而形成陶瓷體。
  13. 如申請專利範圍第12項所述之方法，其中該陶瓷體之該形成包含下列進一步步驟- 乾壓使用如申請專利範圍第10或11項所述之方法製備的陶瓷材料之顆粒，及- 將該陶瓷材料脫脂。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100463079C (zh) * 2000-04-25 2009-02-18 株式会社东芝 电流-电压非线性电阻体
CN102034581A (zh) * 2009-10-01 2011-04-27 Abb技术有限公司 高场强度变阻器材料

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5325897A (en) * 1976-08-20 1978-03-10 Sanken Electric Co Ltd Oxide voltage nonnlinear resistor
JPS5385400A (en) * 1977-01-06 1978-07-27 Tdk Corp Porcelain composite for voltage non-linear resistor
JPS5726403A (en) * 1980-07-24 1982-02-12 Tokyo Shibaura Electric Co Oxide voltage nonlinear resistance element
JPS57193002A (en) * 1981-05-22 1982-11-27 Matsushita Electric Ind Co Ltd Voltage nonlinear resistance element
JPS5850703A (ja) * 1981-09-21 1983-03-25 株式会社東芝 電圧非直線抵抗体の製造方法
EP0189087B1 (de) 1985-01-17 1988-06-22 Siemens Aktiengesellschaft Spannungsabhängiger elektrischer Widerstand (Varistor)
EP0200126B1 (de) * 1985-04-29 1990-09-26 BBC Brown Boveri AG Verfahren zur Herstellung eines spannungsabhängigen keramischen Widerstandes auf der Basis von ZnO
DE3619620A1 (de) * 1986-06-11 1987-12-17 Siemens Ag Verfahren zur herstellung keramischen zinkoxid-varistormaterials und verwendung des nach diesem verfahren hergestellten materials
EP0289582B1 (en) * 1986-10-16 1992-02-26 Raychem Corporation Method for preparing a metal oxide varistor precursor powder
US5039452A (en) * 1986-10-16 1991-08-13 Raychem Corporation Metal oxide varistors, precursor powder compositions and methods for preparing same
US5143711A (en) 1989-12-05 1992-09-01 Asea Brown Boveri Ltd. Process for manufacturing a precursor powder for use in making a varistor and a powder manufactured in this process
JPH06260304A (ja) * 1993-03-08 1994-09-16 Meidensha Corp 電圧非直線型抵抗体の製造方法
EP0667626A3 (en) * 1994-02-10 1996-04-17 Hitachi Ltd Voltage dependent nonlinear resistance and manufacturing process.
US5807510A (en) * 1995-09-07 1998-09-15 Mitsubishi Denki Kabushiki Kaisha Electric resistance element exhibiting voltage nonlinearity characteristic and method of manufacturing the same
US6344271B1 (en) * 1998-11-06 2002-02-05 Nanoenergy Corporation Materials and products using nanostructured non-stoichiometric substances
TW345665B (en) * 1997-06-23 1998-11-21 Nat Science Council Zinc oxide varistor and multilayer chip varistor with low temperature sintering properties
JPH11340009A (ja) 1998-05-25 1999-12-10 Toshiba Corp 非直線抵抗体
JP2000232005A (ja) 1999-02-09 2000-08-22 Toshiba Corp 非直線抵抗体
JP4282243B2 (ja) 2001-01-22 2009-06-17 株式会社東芝 非直線抵抗体
JP2004022976A (ja) * 2002-06-19 2004-01-22 Murata Mfg Co Ltd 積層型電圧非直線抵抗体、及びその製造方法
JP3908611B2 (ja) * 2002-06-25 2007-04-25 Ｔｄｋ株式会社 電圧非直線性抵抗体磁器組成物および電子部品
JP4292901B2 (ja) 2002-08-20 2009-07-08 株式会社村田製作所 バリスタ
JP2004119762A (ja) 2002-09-27 2004-04-15 Toshiba Corp 電流−電圧非直線抵抗体
JP4915153B2 (ja) * 2005-07-07 2012-04-11 株式会社村田製作所 積層バリスタ
JP2007173313A (ja) 2005-12-19 2007-07-05 Toshiba Corp 電流−電圧非直線抵抗体
US7541910B2 (en) * 2006-05-25 2009-06-02 Sfi Electronics Technology Inc. Multilayer zinc oxide varistor
JP5065624B2 (ja) * 2006-06-06 2012-11-07 株式会社東芝 電流−電圧非直線抵抗体および避雷器
JP2008162820A (ja) * 2006-12-27 2008-07-17 Mitsubishi Electric Corp 電圧非直線抵抗体とその製造方法
JP5150111B2 (ja) * 2007-03-05 2013-02-20 株式会社東芝 ＺｎＯバリスター粉末
JP5163097B2 (ja) * 2007-12-20 2013-03-13 Ｔｄｋ株式会社 バリスタ
JP5212060B2 (ja) * 2008-04-23 2013-06-19 パナソニック株式会社 電圧非直線性抵抗体組成物および積層バリスタ
CN101367649B (zh) * 2008-10-13 2011-08-24 电子科技大学 一种氧化锌压敏电阻介质材料及电阻器制备方法
FR2988777B1 (fr) 2012-03-29 2014-04-25 Snecma Propulsion Solide Integration de pieces d'arriere-corps de moteur aeronautique
CN103030390B (zh) * 2012-12-28 2014-04-16 深圳顺络电子股份有限公司 一种氧化锌压敏电阻材料及制备方法
JP6293474B2 (ja) * 2013-01-18 2018-03-14 株式会社東芝 非直線抵抗塗料、母線および固定子コイル
US9741477B2 (en) * 2013-12-06 2017-08-22 Hitachi Metals, Ltd. Sintered body for varistor, multilayer substrate using same, and production method for these
CN106892653A (zh) * 2015-12-17 2017-06-27 辽宁省轻工科学研究院 氧化锌基压敏陶瓷粉体及其制备方法
CN107473731B (zh) * 2017-08-24 2020-11-03 广西新未来信息产业股份有限公司 一种高能量型压敏电阻及其制造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100463079C (zh) * 2000-04-25 2009-02-18 株式会社东芝 电流-电压非线性电阻体
CN102034581A (zh) * 2009-10-01 2011-04-27 Abb技术有限公司 高场强度变阻器材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
<林國淙>，<ZnO壓敏陶瓷中富Ba晶界相的生成與控制>，<1996.05.15/Chinese Sience Bulletin >，<Volume 41,Issue 9 : 783-786>， <網址:https://reurl.cc/O16G9g> *

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