CN1880269A - 半透明pca陶瓷、陶瓷放电管和制备方法 - Google Patents

半透明pca陶瓷、陶瓷放电管和制备方法 Download PDF

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CN1880269A
CN1880269A CNA2006100996412A CN200610099641A CN1880269A CN 1880269 A CN1880269 A CN 1880269A CN A2006100996412 A CNA2006100996412 A CN A2006100996412A CN 200610099641 A CN200610099641 A CN 200610099641A CN 1880269 A CN1880269 A CN 1880269A
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G·C·魏
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Abstract

通过在含有含蒸气相碳的分压的氮气氛中烧结掺杂有MgO烧结助剂的氧化铝粉末来制造适用于在金属卤化物灯用陶瓷放电管使用的半透明多晶材料。烧结的多晶氧化铝具有含铝、氧和氮的晶界相。认为A1－O－N晶界相的形成在烧结中有助于氮从残余气孔中输运。优选地，在流动的超高纯氮下于碳元素炉中烧结PCA。

Description

半透明PCA陶瓷、陶瓷放电管和制备方法
技术领域
本发明涉及一种半透明PCA陶瓷、陶瓷放电管及其制备方法。
背景技术
半透明多晶氧化铝(PCA)陶瓷使得现在的高压钠(HPS)灯和陶瓷金属卤化物灯成为可能。这些应用中的电弧放电管必须能经受在工作着的灯中产生的高温和压力，并抵抗填充材料的化学侵蚀。
在HPS灯中，放电管是如图2所示的管状，虽然对于陶瓷金属卤化物灯来说，放电管可以从圆柱形形状到近球形形状(凸出的)。在欧洲专利申请EP0587238A1和美国专利US 5936351中分别给出了这些类型放电管的例子。凸出形状的放电管如图1所示。具有半球端的凸出形状产生更均匀的温度分布，这导致灯填充物对PCA的腐蚀下降。
过去，在将多晶氧化铝(PCA)烧结成半透明的一些关键因素包括(1)高纯粉末，(2)低浓度的MgO烧结助剂，和(3)在含H2的气氛中进行烧结。在文献中已经报道了不能使用空气、N2、He和Ar气氛，但H2、O2或真空确实可以实现半透明性。这是由于气体在晶格和晶界中的可溶性，使残存的气体扩散到表面上。在真空环境中，或在于PCA中溶解或快速扩散的气氛中，烧结过程不受动力学方面的限制，从而获得无孔的显微结构。后面的工作表明可以在离解氨(25％N2-75％H2)和甚至CO气氛中烧结半透明氧化铝。已报道在含有低至2％氢的N2-H2气氛中进行氧化铝的烧结。由于成本和安全因素，理想的是消除加入氢气的需要且只使用氮气。然而仅N2气氛并不能制造半透明PCA。
发明内容
已经发现在碳元素炉中(carbon-element furnace)于氮气气氛下可以将多晶氧化铝烧结为半透明。当在本文中使用时，半透明指的是在约400nm到约700nm的可见光波长区域至少92％的总透射率。优选地，根据本发明放电管的总透射率至少为95％。
在碳元素炉中的烧结结果与使用W元素、Mo护罩或氧化铝管马弗炉的烧结结果显著不同。在碳元素炉中于N2下烧结的PCA的显微结构分析表明形成了被认为是促进氨从残存的气孔中输送的晶界Al-O-N相。认为形成晶界Al-O-N相源自氨气氛和含蒸气相碳的物质，特别是C、CO和CO2的结合。例如，通过以下反应可以继续形成氧氮化铝(Al7O9N或Al23O27N5)：
估计氧化铝烧结温度下的碳分压约为10-9atm。优选地，炉气氛应含有约1×10-12atm到约1×10-7atm的碳。炉气氛也可含有CO、CO2、H2、CH4和C2H2的分压。特别是，估计烧结过程中这些气体的分压为：10-3到10-4atm的PCO；10-6到10-7atm的PCO2；10-3atm的PH2，10-10atm的PCH4和10-7atm的PC2H2。尽管优选的是在碳元素炉中烧结PCA，但也可通过其它方式，例如在其它类型的炉子中使用石墨托盘或放置其它碳源来产生相似的烧结气氛。然而，在含有W和Mo组分的炉中会更难以控制气氛，因为这些金属容易吸收碳。
应该指出的是，预计来自碳炉组分脱气的氢分压10-3atm比先前已知的在氮-氢混合气体气氛中将氧化铝烧结成半透明所需的氢分压小不止一个数量级。优选地，在含有少于约0.2％体积H2的氮气氛中烧结PCA放电管。更优选地，炉气氛含有约1×10-9atm的碳和约1×10-3到约1×10-4atm的CO。
使用相对纯氮气源来形成炉气氛。优选地，氮气源应含不多于约0.005％体积的全部杂质。更优选地，氮气是氮为99.999％体积的超高纯级。烧结温度可从约1800℃到约2000℃，烧结时间可从约1小时到约70小时。更优选地，在约1850℃到约1950℃下烧结放电管约4小时到50小时，最优选地，在约1900℃下烧结约10小时。
附图说明
图1是现有技术的凸出形状放电管的截面图。
图2是现有技术的HPS放电管的截面图。
图3是在碳元素炉中于N2下烧结的PCA管抛光截面的背散射电子图。
图4是图3抛光截面的氮布局图。深色区域表明存在氮。
具体实施方式
为了更好的理解本发明及其其它和另外的目的、优点和可能，参考下面的说明和附加的权利要求以及上述附图。
图1是常规凸出形状电弧放电管的截面图。电弧放电管21具有由多晶氧化铝构成的陶瓷体23。陶瓷体23限定了放电腔25并具有两个从放电腔25沿相反方向向外延伸的毛细管27。放电腔壁的典型厚度约为0.8mm。该毛细管用于容纳电极组件(未显出)，并将其密封于其中，该电极组件为放电管提供电力以引发并并维持放电腔内的电弧。
图2是HPS灯用常规放电管的截面图。放电管50具有由PCA构成的管状体53。将由PCA构成的环形塞60密封在管状体53的每一端，从而限定放电室51。环形塞中孔隙用以容纳典型由铌导线构成的电极组件，而该铌导线与钨电极连接。在将钠/汞齐和缓冲气体添加到放电室51中后，将铌导线熔接密封在该孔隙中。
由高纯细碎的铝氧化物(氧化铝)粉末形成的陶瓷放电管可通等静压、挤压、浇注成型、凝胶成型或注射成型进行固结。通常在固结前向氧化铝粉末中加入MgO掺杂剂。例如，在欧洲专利EP0650184B1(注浆成型)、美国专利US6,399,528(凝胶成型)、国际专利申请No.WO2004/007397A1(注浆成型)和欧洲专利申请EP1053983A2(等静压)中描述了制造放电管用生坯陶瓷体的各种方法的细节。
本发明的烧结方法制造了半透明PCA陶瓷，其在晶界处具有第二含氮相。该相包括铝、氧和氮，并认为其是氧氮化铝。认为此第二相促进氮从残余孔中的扩散，这使得不必添加至少2％的氢而在N2气氛中就能将PCA烧结成半透明。在下面的实施例中更详细地描述了烧结方法和制得的半透明PCA。然而，应该理解的是，本发明无论如何也不限于此具体的实施例。
实施例
优选使用高纯度(99.97％纯度)Al2O3粉末作为起始粉末来形成多晶氧化铝放电管。形成方法可包括等静压、挤压、注射成型、凝胶成型和注浆成型。对于直管，等静压或挤压是优选的。对于较复杂的形状，可使用注射成型、凝胶成型或注浆成型。优选的氧化铝粉末是由Baikowski生产的CR30F和CR6。CR30F含有～80％的α-Al2O3和～20％的γ-Al2O3，而CR6为100％的α-Al2O3。微晶尺寸为约0.05微米，且对于CR30F具有30m2/g平均比表面积，对于CR6具有6m2/g平均比表面积。对于这两类，报道的平均粒径为约0.5微米。烧结助剂如MgO、Y2O3和ZrO2是优选的。需要MgO以将PCA烧结成半透明。优选地，MgO的量为约100ppm到约1000ppm。可通过将氧化铝粉末与烧结助剂前体的水溶液混合而用烧结助剂掺杂氧化铝粉末。为了形成生坯形状，将该粉末与适合的粘结剂材料如聚乙烯醇、聚乙二醇、甲基纤维素或蜡混合。在空气中于850-1350℃下预烧结该形状1-4小时以除去粘结剂。制得可变大小(瓦特数)和它们毛细管的放电管。
在流动超高纯(UHP)级(99.999％)氮气的一种气氛下于碳元素炉(Centor Company，型号M10)中实现烧结。更优选地，UHP级氮气含有＜1ppm的CO或CO2、＜2ppm的O2、＜3ppm的H2O和＜0.5ppm的总碳氢化合物。炉是含有石墨元素和碳纤维绝缘材料的水平炉。将预烧结的PCA零件放置在具有或不具有耐火架子(setter)粉末的氧化铝舟中。使用两种耐火架子粉末：氧氮化铝和氧化铝。炉中气体流速相当于约0.02m/s的线性气体速度。通过以约8-16℃/min的速率加热到达烧结温度(～1800-1920℃)。在烧结温度下的保持时间是4-40小时。
优选使氧氮化铝耐火架子粉末层形成氧氮化铝分压，这样便保持了晶界氧氮化铝相，而这接下来会促进气孔内部捕获的氮的扩散。包埋在粉末层中的PCA元件比不包埋在该层中的元件能烧结成显著高的透射率。可通过使用(1)氧氮化铝粉末、(2)在碳炉中于流动氮下将逐渐形成氧氮化铝的氧化铝粉末、或(3)在碳炉中将反应形成氧氮化铝的氮化铝和氧化铝粉末的混合物来实现氧氮化铝粉末层。
烧结元件的总透射率包括将微型白炽灯或光学光纤源放置在烧结元件内部，测量透过球体的漫射光和该球体上全部漫射光的总量。测量的波长范围从约400nm到约700nm。下表提供在碳元素、碳纤维绝缘体炉中于流动的N2中烧结的各种PCA元件。
  编号   样品   烧结助剂   烧结周期   总透射率
  1   150W毛细管   200ppmMgO400ppmZrO220ppmY2O3   1900℃-4小时1890℃-4小时1900℃-6小时   93.0％
  2   150W毛细管   200ppmMgO400ppmZrO220ppmY2O3   1900℃-4小时1890℃-4小时1900℃-18小时   94.5％
  3   150W凸出   200ppmMgO400ppmZrO220ppmY2O3   1900℃-4小时1900℃-48小时   96.7％
  4   150W毛细管   200ppmMgO400ppmZrO220ppmY2O3   1900℃-4小时1890℃-40小时   98.0％
  5   400W毛细管   500ppmMgO   1910℃-40小时1920℃-10小时   93.0％
  6   250W HPS管   200ppmMgO400ppmZrO220ppmY2O3   1910℃-40小时1920℃-10小时   93.0％
  7   35W凸出   500ppmMgO   1910℃-40小时1920℃-30小时   92.0％
  8   70W HPS管   500ppmMgO350ppmY2O3   1920℃-10小时(Al7O9N耐火架子粉末)   94.0％
  9   70W HPS管   500ppmMgO350ppmY2O3   1920℃-10小时(Al2O3耐火架子粉末)   92.0％
通过光学显微镜和具有能量分散X-射线分析(EDXA)的扫描电子显微镜(SEM)观察根据本发明方法烧结的PCA显微结构。这样烧结表面上的颗粒形貌受到劈裂阶的高度刻蚀，这使得难以测量粒径。表面的SEM/EDXA表明了PCA中存在氮，这说明了在表面形成氮氧化铝。
图3是在碳元素炉中于N2下烧结的PCA管抛光截面的背散射电子图像。图4是通过电子探针分析的相同抛光截面的氮布局图。深色区域说明存在氮并清晰的说明在氧化铝颗粒晶界上存在含氮相的薄层。
尽管已经说明并描述了目前认为是本发明的优选实施方案，但在本发明中进行各种改变和修正对本领域技术人员而言是显而易见的而不背离如附加权利要求限定的本发明范围。

Claims (20)

1.一种由多晶氧化铝组成的烧结半透明陶瓷制品，该氧化铝包含一定量的MgO并具有含铝、氧和氮的晶界相。
2.根据权利要求1所述的陶瓷制品，其特征在于，晶界相是氧氮化铝。
3.根据权利要求3所述的陶瓷制品，其特征在于，多晶氧化铝中MgO的量是约100ppm到约1000ppm。
4.一种含由半透明多晶氧化铝组成的陶瓷体的陶瓷放电管，该氧化铝含一定量的MgO并具有含铝、氧和氮的晶界相。
5.根据权利要求4所述的陶瓷放电管，其特征在于，晶界相是氧氮化铝。
6.根据权利要求4所述的陶瓷放电管，其特征在于，多晶氧化铝中MgO的量是约100ppm到约1000ppm。
7.根据权利要求4所述的陶瓷放电管，其特征在于，放电管具有至少95％的总透射率。
8.一种烧结半透明陶瓷体的方法，该方法包括：
(a)将由掺杂有MgO的氧化铝组成的陶瓷体放在包括有碳源和由总杂质浓度不超过约0.005％体积的氮气源所形成的氮气氛的炉中；
(b)在约1800℃到约2000℃的温度下烧结陶瓷体以形成烧结的半透明陶瓷体。
9.根据权利要求8所述的方法，其特征在于，在烧结过程中炉气氛含有约1×10-12atm到约1×10-7atm的碳。
10.根据权利要求8所述的方法，其特征在于，在烧结过程中炉气氛含有少于约0.2％体积的H2。
11.根据权利要求9所述的方法，其特征在于，在烧结过程中炉气氛含有约1×10-3atm到1×10-4atm的CO。
12.根据权利要求9所述的方法，其特征在于，在烧结过程中炉气氛含有少于约0.2％体积的H2。
13.根据权利要求8所述的方法，其特征在于，烧结陶瓷体约1小时到约70小时。
14.根据权利要求8所述的方法，其特征在于，在约1850℃到约1950℃的温度下烧结陶瓷体约4小时到约50小时。
15.根据权利要求8所述的方法，其特征在于，在约1900℃下烧结陶瓷体约10小时。
16.根据权利要求8所述的方法，其特征在于，炉是碳元素炉，碳源是炉的一个或多个构件。
17.根据权利要求16所述的方法，其特征在于，在烧结过程中炉气氛含有约1×10-12atm到约1×10-7atm的碳。
18.根据权利要求17所述的方法，其特征在于，在烧结过程中炉气氛含有少于约0.2％体积的H2。
19.根据权利要求18所述的方法，其特征在于，在约1850℃到约1950℃的温度下烧结陶瓷体约4小时到约50小时。
20.一种烧结半透明陶瓷体的方法，该方法包括：
(a)将由掺杂有约100ppm到约1000ppm的MgO的氧化铝组成的陶瓷体放置在含有氮气氛的碳元素炉中，该氮气氛由总杂质量不超过约0.005％体积的氮气源形成；
(b)在约1800℃到约2000℃的温度下烧结陶瓷体约1小时到约70小时以形成烧结的半透明陶瓷体，在烧结过程中炉气氛含有约1×10-12atm到约1×10-7atm的碳和少于约0.2％体积的H2。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102333496A (zh) * 2009-05-20 2012-01-25 专利和商业发展公司 多晶陶瓷正牙构件
CN103360037A (zh) * 2012-03-27 2013-10-23 精工爱普生株式会社 透光性氧化铝及透光性氧化铝制造方法
TWI653210B (zh) 2014-07-04 2019-03-11 鉅亨電子材料元件有限公司 多晶系透明陶瓷基板之製造方法

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006160595A (ja) * 2004-06-10 2006-06-22 Ngk Insulators Ltd 透光性セラミックス、その製造方法および発光容器
EP1805119B1 (en) * 2004-10-01 2015-07-01 Ceranova Corporation Polycrystalline alumina articles and methods of manufacture
US7362053B2 (en) * 2005-01-31 2008-04-22 Osram Sylvania Inc. Ceramic discharge vessel having aluminum oxynitride seal region
KR20060130506A (ko) * 2005-06-14 2006-12-19 도시바 라이텍쿠 가부시키가이샤 고압 방전램프, 고압 방전램프 점등장치 및 조명장치
US20070072762A1 (en) * 2005-09-29 2007-03-29 Osram Sylvania Inc. Method of Making Ceramic Discharge Vessels Using Stereolithography
US20080283522A1 (en) * 2007-05-14 2008-11-20 Shuyl Qin Translucent polycrystalline alumina ceramic
US7678725B2 (en) * 2007-05-14 2010-03-16 General Electric Company Translucent polycrystalline alumina ceramic
JP4983545B2 (ja) * 2007-10-30 2012-07-25 東ソー株式会社 高靭性透光性アルミナ焼結体及びその製造方法並びに用途
DE102007061514A1 (de) * 2007-12-20 2009-06-25 Osram Gesellschaft mit beschränkter Haftung Elektrode für eine Hochdruckentladungslampe und Verfahren zu ihrer Fertigung
US20090211514A1 (en) * 2008-02-26 2009-08-27 Lehigh University Single crystal conversion process
US7833922B2 (en) * 2009-01-08 2010-11-16 Battelle Energy Alliance, Llc Method of forming aluminum oxynitride material and bodies formed by such methods
CN102515720A (zh) * 2011-12-08 2012-06-27 西安交通大学 一种透明氧化铝陶瓷的制备方法
JP6349100B2 (ja) * 2014-02-14 2018-06-27 株式会社アテクト アルミナ焼結体及びその製造方法
US9287106B1 (en) 2014-11-10 2016-03-15 Corning Incorporated Translucent alumina filaments and tape cast methods for making
JP6585620B2 (ja) * 2014-11-28 2019-10-02 日本碍子株式会社 アルミナ焼結体及び光学素子用下地基板
CN111308288B (zh) * 2020-03-06 2021-11-26 西南交通大学 一种考虑油中水分的油纸绝缘局部放电发展阶段的判断方法
CN112232680B (zh) * 2020-10-19 2021-11-09 三峡大学 基于Copula函数的流域氮代谢环境风险评价方法
CN115196964B (zh) * 2021-04-14 2023-07-25 河南科技大学 一种含钠的氧化钼陶瓷溅射靶材制备方法

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3026210A (en) 1961-01-03 1962-03-20 Gen Electric Transparent alumina and method of preparation
GB1252851A (zh) 1969-08-27 1971-11-10
US4031177A (en) 1969-10-31 1977-06-21 Compagnie Generale D'electroceramique Process for the manufacture of articles of translucent alumina
JPS56169182A (en) * 1980-05-29 1981-12-25 Sumitomo Electric Industries Ceramic material sintering method
JPS59121158A (ja) * 1982-12-27 1984-07-13 日本碍子株式会社 多結晶透明スピネル焼結体の製造法
US4797238A (en) 1985-11-27 1989-01-10 Gte Laboratories Incorporated Rapid-sintering of alumina
US4762655A (en) 1985-11-27 1988-08-09 Gte Laboratories Incorporated Method of sintering translucent alumina
US4778778A (en) * 1987-06-03 1988-10-18 Keramont Advanced Ceramic Products Corporation Process for the production of sintered aluminum nitrides
US4948538A (en) 1988-10-11 1990-08-14 Gte Laboratories Incorporated Method of making translucent alumina articles
US5096862A (en) * 1990-08-09 1992-03-17 Minnesota Mining And Manufacturing Company Transparent ceramic composite article comprising aluminum oxide and aluminum magnesium oxynitride
US5442478A (en) * 1990-10-30 1995-08-15 The Regents, University Of California Electrochromic device using mercaptans and organothiolate compounds
DE69331991T2 (de) 1992-07-09 2002-09-19 Toto Ltd Struktur von abtichtungsteil einer bogenröhre und verfahren zur herstellung derselben
EP0587238B1 (en) 1992-09-08 2000-07-19 Koninklijke Philips Electronics N.V. High-pressure discharge lamp
US5342564A (en) * 1992-12-31 1994-08-30 Valenite Inc. Rapid sintering method for producing alumina-titanium carbide composites
US5391339A (en) * 1992-12-31 1995-02-21 Valenite Inc. Continuous process for producing alumina-titanium carbide composites
ATE155452T1 (de) * 1993-12-10 1997-08-15 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Hochdruckentladungslampe mit keramischer entladungsröhre, dafür geeigneter keramischer körper und verfahren zu seiner herstellung
US5682082A (en) * 1996-07-29 1997-10-28 Osram Sylvania Inc. Translucent polycrystalline alumina and method of making same
US5631201A (en) * 1996-07-29 1997-05-20 Osram Sylvania Inc. Translucent polycrystalline alumina and method of making same
DE19645960A1 (de) 1996-11-07 1998-05-14 Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh Keramisches Entladungsgefäß
CA2308933C (en) 1999-05-19 2008-07-22 Ngk Spark Plug Co., Ltd. Translucent polycrystalline ceramic and method for making same
JP4723055B2 (ja) * 1999-05-19 2011-07-13 日本特殊陶業株式会社 アルミナ焼結体及びその製造方法並びに焼結アルミナ部材及び発光管
US6399528B1 (en) 2000-09-01 2002-06-04 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Porous aluminum oxide structures and processes for their production
WO2004007397A1 (en) 2002-07-10 2004-01-22 Koninklijke Philips Electronics N.V. Transparent polycrystalline aluminium oxide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102333496A (zh) * 2009-05-20 2012-01-25 专利和商业发展公司 多晶陶瓷正牙构件
CN103360037A (zh) * 2012-03-27 2013-10-23 精工爱普生株式会社 透光性氧化铝及透光性氧化铝制造方法
TWI653210B (zh) 2014-07-04 2019-03-11 鉅亨電子材料元件有限公司 多晶系透明陶瓷基板之製造方法

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US7247591B2 (en) 2007-07-24
CA2537785A1 (en) 2006-11-26
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US20070194503A1 (en) 2007-08-23
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