CN101070242A - 透明的多晶氧化铝 - Google Patents

透明的多晶氧化铝 Download PDF

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CN101070242A
CN101070242A CNA2007101095668A CN200710109566A CN101070242A CN 101070242 A CN101070242 A CN 101070242A CN A2007101095668 A CNA2007101095668 A CN A2007101095668A CN 200710109566 A CN200710109566 A CN 200710109566A CN 101070242 A CN101070242 A CN 101070242A
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additive
polycrystalline alumina
alumina component
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M·P·B·范布鲁根
T·A·科普
T·A·P·M·柯斯坦
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Abstract

本发明涉及供例如在照明工业中应用的高度密实的透光氧化铝(矾土)及其构件，为在800℃或更高的温度使用必须得到细小晶粒并使之稳定。本发明还涉及有这样一种陶瓷壁之放电管的电灯。本发明矾土配备一种添加剂并具有平均晶粒大小＝2μm，以及在实际轴向透光度RIT＝30％、优选地＞40％和更优选地＞50％的情况下相对密度高于99.95％，对样品厚度为0.8mm并用λ最好为645nm的单一波长光越过最大0.5°的孔径角进行测量，而且该添加剂包括至少一种Mg、Y、Er和La的氧化物。

Description

透明的多晶氧化铝
本申请是申请号为03816400.0(PCT/IB2003/002874)、申请日为2003年6月25日的发明专利申请的分案申请。
技术领域
本发明涉及在例如照明工业中应用的高度密实透光氧化铝及其构件，为着在800℃或更高的温度使用，必须得到细小晶粒并使之稳定。本发明还涉及具有这样一种陶瓷壁之放电管的电灯。
背景技术
可获得由化学上和热力学上稳定的刚玉相(α-Al2O3)构成的烧结透光矾土陶瓷已有几十年。传统地它们从甚细晶粒不稳定矾土原料粉制成，并通过在＞1600℃的很高温度退火而得到高的烧结密度。因此，该陶瓷微结构是粗的，晶粒大小一般＞15μm。由于这种粗的微结构，甚至在薄的组件中，这些材料仅呈现半透明而非透明。此外，该已知陶瓷有相对低的弯曲强度，通常小于300MPa。
认为一陶瓷组件透明这里系指该陶瓷组件具有至少30％的实际轴向透光度RIT值，越过最大0.5°的孔径角、在0.8mm样品厚度下，并用单色波长λ光来进行此实际轴向透光度RIT的测量。
在文献中，光特性通常使用总的前向透光度(TFT)和轴向透光度(IT)加以表征，而后者则以商业上可得到的分光仪来测量。由于这些有几度的孔径角，这样测量的IT包括大量前向散射光。结果，对散射样品，TFT和IT总会产生比相同样品的RIT值要高很多的值。建立与RIT的任何定量关系是不可能的。然而比较得自于厚度非如上面所规定之0.8mm样品的实际轴向透光度值却可以。对于厚度为d1和RIT值为T1的样品1以及厚度为d2和RIT值为T2的第二个样品，满足方程式
T2＝(1-R*[T1/(1-R)]d2/d1    (1)
式中R是表面反射系数，对于矾土它为0.14(合并在两个表面上的反射)。由于反射损失，所以透光度值，无论RIT、TFT或IT都不可能超过86％的值。
本发明人已证实，对于具有非常小孔隙率以及小孔隙的陶瓷样品，即分别至少小于0.01％和＜100nm，其实际轴向透光度RIT同样品的结构有关。当按上述规定测量时，所得到的RIT可表示为
RIT = ( 1 - R ) exp ( - 3 π 2 GdΔ n 2 2 λ 0 2 ) , - - - ( 2 )
式中R是表面反射系数(对Al2O3为0.14)；d是样品厚度；G是平均晶粒大小；Δn是α-矾土的有效双折射率(0.005)，作为每一主光轴间折射率之差的加权平均计算；而λ0是该单色入射光在真空中的波长。在较高的孔隙率百分数和较大的孔隙尺寸，测量的RIT结果是比以上表达式所预测的显著地更小的值。
有人提议通过应用粉浆浇铸法连同无压预烧结和等温后密实化(HIP)一起，来得到半透明2-5μm细晶粒的烧结产物。对试验样品未作RIT测量，但在平均晶粒大小5μm观测到最大IT为46％(对1mm样品厚度，红外光可见，未给出波长)。
当使晶粒大小缩减到接近亚微米范围时，仅看到很小的改进。以平均晶粒大小0.82μm通过注射成型、预烧结和HIP所制得的密实样品，报导在样品厚度为0.5mm时录得具有IT(对500nm波长)为78％。
这些情况下，矾土的纯度据报告为99.99％。使上述的HIP处理在约1250至1280℃的温度进行，但却导致另外一个困难，因为如果该陶瓷打算用于放电灯，则这样一种放电灯的放电管在自1000至1300℃范围内的温度工作。这些烧结产物在同样高或甚至高于HIP温度之温度的任何专门应用，将不可避免地使上述高纯矾土的微结构变粗。同时，若干添加剂例如MgO和ZrO2已被报导，阻止退火矾土陶瓷中结晶的生长，其确切效果往往是不清楚的。
根据EP 1053983，它涉及平均刻面长度不超过最大光波长λ的半透明多晶陶瓷(对于例如λ＝600nm这是指晶粒大小约为0.6μm，因为刻面长度约为平均晶粒大小的一半)，作为透光烧结矾土陶瓷中烧结掺杂物的仅0.05摩尔％ZrO2添加剂，对其光的透光度、强度和硬度与无ZrO2样品比较均有衰减的影响。对0.5mm薄圆片且λ＜800nm，其所谓的线性透光度的测量值，这种情况下，它可比作实际轴向透光度RIT，同有MgO掺杂物(0.1mol％)无氧化锆微结构的测量值为40％相比，下降至25％。厚度0.5mm之RIT值25％按照方程式(1)便相当于厚度d＝0.8mm的值12％。对无氧化锆微结构，此厚度d＝0.8mm的相应的值为25％。
一种其RIT值至少为30％，对0.8mm的样品厚度，并用波长λ单色光越过最大0.5°的孔径角来测量，并具有可接受的强度的透光Al2O3组件，因此是未知的。那是一个问题。在灯工作环境下，使其中小晶粒结构长期保持的透光多晶矾土的灯的放电管也是未知的。那同样地是个问题。因此，解决这些问题并提供借助它而克服上述限制的组件是本发明的目的。
发明内容
本发明提供具有添加剂的多晶矾土组件，其特征在于该矾土平均晶粒大小≤2μm，而在实际轴向透光度RIT≥30％、优选地＞40％及更优选地＞50％的情况下，相对密度高于99.95％，对0.8mm样品厚度并用λ最好为645nm的单波长光越过最大0.5°的孔径角进行测量，以及特征还在于该添加剂包括至少一种Mg、Y和La的氧化物。
所得到的RIT值＞30％及细晶粒大小≤2μm或最好≤1μm，当该组件高温退火后，在800℃或更高的温度使用时，结果要使之稳定更长时间，是出乎意料的，并且显然同本领域以前的情况不一致。这里，通过很小的晶粒大小与极高的相对密度＞99.95％的结合可做到这一点，意味着一个非常小的残留孔隙率。
本发明矾土组件优选按照此后所述的本发明方法制成。由TM-DAR刚玉粉(平均颗粒粒度0.2μm；日本Boehringer Ingelheim Chemicals厂制)不再加入任何添加剂，在pH＝9，制备固体载荷为41wt.％的水稀浆。在至少一天的超声或至少半天的湿球研磨后，达到高度分散，使用除了矾土或能被氧化的磨损物外，不可能产生污染的研磨珠。然后借助加入掺杂物的纯及细晶粒氧化物粉末，而引入选自Mg、Y和La的氧化物的添加剂或掺杂物。最好掺杂物或添加剂的平均颗粒粒度，选择小于在烧结和HIP处理后所得到的矾土晶粒的大小。另一方面，添加剂或掺杂物可由含有一种或多种元素Mg、Y和La的母体引入。无添加剂的参考样品用同样的方法制备，只是不加入掺杂物。
将这样得到的悬浮液，不用进一步脱气，或者在4巴的压力使用平均孔隙直径为50nm的Millipore亲水膜加以压力浇铸，或者在平均孔隙率约50％及平均孔隙大小约100nm的多孔膜上加以粉浆浇铸。在固结后使成型片于空气中干燥约4个小时，而后于温度80℃的炉中再干燥4个小时以上。于纯氧中，在600℃煅烧干燥的成型片2个小时，以去除杂质。此后，在1150℃至1350℃范围内的烧结温度(Ts)下，烧结该成型片，烧结不是在氧、真空中、就是在加湿的氢(露点0℃)中进行。在1200℃温度和200MPa压力下，接着对密度高于96％的成型片做HIP处理至少2个小时。先以依次更细的金刚石粒而最后为3μm的金刚石粒，将该成型片的两个平均面磨光。成型圆片的最终厚度为0.8mm。
使用波长λ为645nm的红二极管激光器和距被照射样品至少1米的探测器，以确保孔径角为0.5°，来测量这样形成的样品的实际轴向透光度(RIT)。同时也测量总的前向透光度(TFT)。在许多情况下，测量吸收(ABS)、总反射(TR)以及烧结后的密度(ρ)。结果示于表I。
表I
 M8O(ppm) Ts(℃) 烧结气氛  RTT  TFT ABS
 133 1200  O2  54  76  6
 300 1200  O2  55  76  6
 1000 1220  O2  45  72  6
 133 1200  H2  44  65  17
 300 1200  H2  46  67  17
 1000 1220  H2  45  67  16
 Y2O3(ppm) Ts(℃)  ρ(％)  RIT  TFT  ABS
 100 1245  96.5  61.1  76.1  9.6
1250  99.2  58.3  77.0  8.4
1300  100  54.3  76.2  9.2
 400 1285  98.2  62.0  75.8  9.9
1300  99.8  62.4  75.3  10.3
 1000 1300  96.5  66.3  73.7  12.2
1330  99.0  46.1  67.2  16.7
 Er2O3(ppm)-烧结气氛 Ts(℃)  ρ(％)  RIT  TFT  ABS
 50+300ppmMgO_H2 1260  98.3  57.3  76.0
 50+300ppmMgO_O2 1250  98.4  61.0  82.3  2.6
1200 ppmLa2O3烧结温度(℃)_烧结气氛 ρ(％)  RIT  TFT  TR  ABS
1270_O2  98.7  71.3  80.6  15.1  4.3
对加有作为添加剂的La2O3的样品，HIP在1250℃进行6个小时。退火处理(退火时间按小时及退火温度按℃)对晶粒大小结构的影响示于表II。表II中表示为参考的样品由矾土构成，无添加剂或掺杂物。
表II
晶粒大小(微米；μm)
掺杂物(ppm)  1250 ℃  1300℃
 t＝0h  2h  12h  24h  48h  96h  192h  24h  48h  96h
 0 MgO  0.48  0.91  1.09  1.45  1.89
 133MgO  0.47  0.55  0.84  0.94  1.02  1.14  1.41  1.38  1.53  1.80
 300MgO  0.42  0.51  0.57  0.79  1.1  1.06  1.35  2.00
 1000MgO  0.46  1.26  1.53  1.49  1.82
 1250℃  1300℃  1325℃
 t＝0h  192h  48h  24h
 133MgO  0.47  1.41  1.53  1.53
 t＝24h  AfterHip  1225℃  1250℃  1275℃  1300℃  1325℃  1350℃  1400℃  1450℃
 参考  0.48  1.09  1.49  1.89
 1200La2O3  0.33  0.55  0.86  1.82  3.53
 133MgO  0.48  0.67  0.94  0.99  1.41  1.53
 100 Y2O3  0.36  0.64  0.93  1.01  1.62  2.90  4.81
 Ts(℃)  t＝0h；1400℃      6h；1400℃      24h；1400℃      96h；1400℃
 100Y2O3  1250  0.57      1.57      2.90      3.43
 1000Y2O3  1300  0.36      1.35
 50Er2O3+300MgO  1265  0.54      1.66       3.53
 1000MgO  1215  0.46      1.74
 133MgO  1200  0.47       2.98
 参考  1200  0.48       3.53
在另一个通过模拟进行的实验中，已研究了提高温度对晶粒大小的更长期影响。该模拟基于J.Am.Ceram.Soc.73(1990)11，3292-3301中所公开的模型。对具有选自氧化物的添加剂或掺杂物的样品的影响示于表III。
表III
样品与温度  24h  100h  1000h  10.000h
 1200ppmLa2O3
 1100℃  0.33  0.33  0.33  0.39
 1150℃  0.33  0.33  0.34  0.41
 1200℃  0.33  0.34  0.43  0.77
 1250℃  0.36  0.44  0.79  1.67
 100ppmY2O3
 1100℃  0.57  0.57  0.60  0.76
 1150℃  0.58  0.59  0.76  1.38
 1200℃  0.61  0.70  1.22  2.54
 1250℃  0.74  1.04  2.13  4.56
 300ppmMgO+50ppm Er2O3
 1100℃  0.54  0.54  0.57  0.76
 1150℃  0.55  0.56  0.72  1.31
 1200℃  0.58  0.67  1.16  2.42
 1250℃  0.71  0.99  2.03  4.35
在24个小时退火处理后所得到的RIT值示于表IV。该退火处理在不同的以0℃表示的温度进行。
表IV
掺杂物(ppm) 在HIP处理后 1250℃  1275℃  1300℃
 100Y2O3  58  54  38
 1000Y2O3  66  68  61
 300MgO+50Er2O3  56  51  33
 1200 La2O3  71  57
 1000MgO  46  33
 133MgO  44  35
 参考  45  19
表IV中表示为参考的样品由矾土构成，无添加剂或掺杂物。
附图说明
图1示出由本发明矾土制成的放电管电灯的实例。
具体实施方式
具有由本发明矾土制成的放电管电灯的实例参照附图来描述。此附图给出有本发明透明陶瓷陶瓷壁2的放电管1的灯10。该灯装有部分剖开的外泡11。该灯的放电管配备电极60、70，它们通过本领域中所知的穿透构造6、7与电流导线13、14连接。此电流导线以通常方式与灯座12的电接头连接。在第一个实例中，放电管由制备的稀浆粉浆浇铸制成，按照上述的方法，有2000ppm La2O3。将这样形成的含镧成型坯体在1350℃的烧结温度烧结2个小时，然后在1250℃的温度给它以HIP处理24个小时。
在第二个实例中，放电管由制备的稀浆粉浆浇铸制成，按照上述的方法，有300ppm MgO。将这样形成的含镁成型坯体在1220℃的烧结温度烧结2个小时，然后在1150℃的温度给它以HI P处理24个小时。
这样所形成的放电管每个有平均晶粒大小为0.5至0.7μm的陶瓷壁。在两个放电管实例中，其陶瓷壁材料显示了至少60％的RIT值。

Claims (9)

1.含有添加剂的多晶矾土组件，其特征在于该矾土平均晶粒大小≤2μm，而在对样品厚度0.8mm、并用单波长λ光越过最大0.5°孔径角所测量的实际轴向透光度RIT≥30％情况下，相对密度高于99.95％，以及在于该添加剂包括至少一种Mg、Y和La的氧化物。
2.权利要求1的多晶矾土组件，其特征在于该添加剂以至少10ppm的量存在。
3.权利要求1或2的多晶矾土组件，其特征在于该添加剂为至少50ppm及最多1000ppm Y2O3。
4.权利要求1或2的多晶矾土组件，其特征在于该添加剂为至少100ppm及最多5000ppm La2O3。
5.权利要求1或2的多晶矾土组件，其特征在于该添加剂为至少100ppm及最多1000ppm MgO。
6.放电灯，其特征在于该灯装备有具有权利要求1的陶瓷制的壁的放电管。
7.权利要求6的灯，其特征在于该放电管有含金属卤化物的可电离填料。
8.形成前述权利要求的任一项的多晶矾土组件的方法，其特征在于该方法包括的步骤为：
-制备具有平均晶粒大小≤0.2μm的刚玉粉末稀浆，
-加入选自含有元素Mg、Y和La以及Mg、Y和La的氧化物中的一种或多种的前体的掺杂物，
-在模中浇铸该稀浆，
-干燥并烧结这样形成的模制体，以及
-在至少1150℃的温度进行HIP处理至少2个小时。
9.权利要求8的方法，其中再加入掺杂物后，将所制得的稀浆在模中粉浆浇铸。
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