CN101107206B - 荧光陶瓷及其制备方法 - Google Patents
荧光陶瓷及其制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 10
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 10
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
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- 238000007731 hot pressing Methods 0.000 claims abstract description 8
- 239000000049 pigment Substances 0.000 claims abstract description 6
- 239000002019 doping agent Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及用M掺杂的具有通式Gd2O2S的荧光陶瓷,其中M代表至少一种选自Ce、Pr、Eu、Tb、Yb、Dy、Sm和/或Ho的元素,其中所述荧光陶瓷在其体积内包括单相;本发明还涉及采用单轴热压制备荧光陶瓷的方法;用于检测电离辐射的检测器和所述检测器用于检测电离辐射的用途。所述采用单轴热压制造荧光陶瓷材料的方法包括下列步骤:a)选择用M掺杂的Gd2O2S颜料粉末,且M代表至少一种选自Eu、Tb、Yb、Dy、Sm、Ho、Ce和/或Pr的元素,其中所述用于热压的粉末的晶粒大小为1μm,且所述热压在1000℃-1400℃温度下进行;和/或在100MPa-300Mpa压力下进行;在700℃-1200℃下空气退火0.5小时至30小时。
Description
本发明涉及用M掺杂的具有通式Gd2O2S的荧光陶瓷,其中M代表选自Ce、Pr、Eu、Tb、Yb、Dy、Sm和/或Ho的至少一种元素。
本发明还涉及使用单轴热压方法制造荧光陶瓷的方法。
本发明还另外涉及用于检测电离辐射的检测器。
本发明还另外涉及所述用于检测电离辐射的检测器的用途。
用于检测高能辐射的荧光元件含有能吸收辐照并将其转化为可见光的磷光体。由此产生的光发射是电子器件要求的并借助于光敏系统(例如光电二极管或者光电倍增器)来评价。这些荧光元件可以由单晶材料(例如经掺杂的碱金属卤化物)进行制备。非单晶材料可以用作粉末化的磷光体或者以由由其制造的陶瓷元件形式采用。
已知方法(参见例如US 5518659)的缺陷在于所述具有10nm-100nm晶粒大小的粉末在空气中存储时是化学不稳定的,导致粉末的表面氧化。该表面氧化不可避免地导致在所得陶瓷体积中出现不理想的第二相。第二相不利地导致在陶瓷体积内的散射并由此降低了光输出。必须注意到,甚至在空气中短时间处理原材料(例如称量原材料和装载压模)时也会发生表面氧化。为了将含氧硫酸盐还原成硫氧化物,在US 5518659中建议在热压过程中使用还原气氛,在炉空间中气压不超过0.1MPa(大致为大气压)。然而,由于在多晶砖孔隙中存在大气反压,压实受到限制。因此,这些孔隙不能被完全封闭以致不能形成最佳微结构。
本发明的目标在于提供制备具有更进一步改善的光输出和余辉性质的闪烁陶瓷的方法。
根据本发明,上述目标可以通过采用单轴热压来制备荧光陶瓷材料的方法而实现,其中所述发明方法包括下面步骤:
a)选择用M掺杂的Gd2O2S颜料粉末,且M代表至少一种选自Eu、Tb、Yb、Dy、Sm、Ho、Ce和/或Pr的元素,其中所述用于热压的粉末的晶粒大小为1μm-20μm,且所述热压在以下条件下进行:
1000-1400℃的温度;和/或
100MPa-300Mpa的压力;
b)在700℃-1200℃下空气退火0.5小时至30小时。
Gd2O2S颜料粉末可以含有0.1ppm-1000ppm(重量份数)的M。
已经发现在空气中化学稳定的相对粗颗粒粉末可以被成功地压制成具有改善的特性的荧光晶体。
这样,根据本发明,可能优选的是在下面条件下进行压制模式:
1000-1400℃,优选1100-1300℃,更优选1150-1250℃的温度;和/或
100MPa至300MPa,优选180MPa至280MPa和更优选200MPa至250MPa的压力。优选地,在根据本发明的单轴压制步骤期间真空为小于或等于100Pa且大于或等于0.01Pa。
根据本发明,真空可以调节为≥0.01Pa并≤50Pa,优选为≥0.01Pa并≤10Pa,和最优选真空被调节为≥0.01Pa并<1Pa。
在真空下单轴热压步骤之后,所述荧光陶瓷可以通过在700℃-1200℃,优选800℃-1100℃,更优选900℃-1000℃下空气退火进一步处理;其中所述空气退火处理的时间为0.5小时至30小时,优选1小时至20小时,更优选2小时至10小时和最优选2小时至4小时。
本发明的另一优点在于具有1μm-20μm的平均晶粒大小的Gd2O2S材料通常可以由荧光陶瓷的制造商作为原材料购买而无需被破碎为低于100nm的更小微粒。在一个实施方案中,优选的是根据本发明所用的Gd2O2S颜料粉末具有2μm-10μm和更优选4μm-6μm的平均晶粒大小。此外,因为本发明方法不需要特殊的粉末生产工艺,由常规可得的粉末就可以成功地用于生产发光陶瓷。
下列陶瓷参数已经通过本发明的方法实现:
-在500ms时1×10-6~8×10-5的余辉;和/或
-在513nm波长下测得,0-50%,优选10%-50%,更优选20-50%的总透明度。
本发明的陶瓷可以有利地用于制备发出x射线的陶瓷,其用作制造医学计算机X线断层照相术(CT)中的原材料。
已经发现有利的是引入真空退火步骤,以再进一步提高所得陶瓷的光学性能。在该步骤期间,在陶瓷中进行了进一步晶粒生长,这由于孔隙率的降低而进一步改进了透明度。除此之外,由于晶粒生长,在硫氧化物的晶格中掺杂原子的额外扩散使得进一步改善了陶瓷的闪烁性质。
因此,根据本发明方法的一个实施方案,在步骤a)和步骤b)之间可以实施额外的步骤c),其中步骤c)包括在真空下在1000℃-1400℃温度下使荧光陶瓷退火0.5小时至30小时。
优选地,所述退火温度被选择为1100℃-1300℃,更优选为1200-1250℃。
用于真空退火的时间优选设定为1小时至20小时,更优选为2小时至10小时,并最优选为3小时至5小时。
在根据本发明的方法的又一个实施方案中,对于步骤a)使晶粒大小为1μm-20μm的未经掺杂的Gd2O2S粉末与包括含Pr、Ce、Eu、Tb、Yb、Dy、Sm和/或Ho的稀土离子的至少一种元素的组合物相混合。
这一技术措施还进一步简化了陶瓷制备工艺,这是因为可以使用宽广范围的可用材料。例如,在选择Pr或者Ce作为掺杂剂的情况下,引入Pr或者Ce离子可以使用相应盐的含水溶液进行:PrCl3、PrBr3、PrI3、Pr(NO3)3、Pr2(SO4)3、CeCl3、CeBr3、CeI3、Ce(NO3)3、Ce2(SO4)3等等。备选地,引入掺杂剂离子可以在Gd2O2S和含有掺杂剂(例如氧化物如Pr6O11、Pr2O3、Ce2O3、CeO2)的不溶组合物的机械混合期间进行。
另一备选是,Gd2O2S粉末可以与掺杂剂的水不溶性盐(例如PrF3、Pr2S3、Pr2O2S、Pr2(CO3)3、Pr2(C2O4)3、CeF3、Ce2O2S、Ce2(CO3)3、Ce2(C2O4)3等等)机械混合。
这种掺杂剂引入的原理可以用于引入离子(例如Tb、Eu和其它稀土元素)。另外,非稀土离子的其它元素离子也可以相应引入。优选地,在热压前共混合适合的烧结助剂。各种烧结助剂是本领域所公知的。
本发明还涉及用M掺杂的由化学式Gd2O2S代表的陶瓷,其中M代表至少一种选自Pr、Ce、Eu、Tb、Yb、Dy、Sm和/或Ho的元素,其中所述发光陶瓷在其体积内含有单相。
由于本发明的技术措施,也即在所得陶瓷的体积中不存在外来相,其透明度值增加。
此外,还已经发现,相对于在市场上可获得的陶瓷荧光材料,本发明的荧光陶瓷可以具有显著增加的相对光产率或者光输出。这种差别特别在陶瓷厚度等于或者大于1.5mm时可以看出。所述光输出可以比相同厚度的钨酸镉晶体的光输出高2.3倍。
经掺杂的Gd2O2S颜料粉末可以具有按照BET为≥0.01m2/g且≤1m2/g,优选≥0.05m2/g且≤0.5m2/g和更优选≥0.1m2/g且≤0.2m2/g的比表面积。
Gd2O2S可以用至少一种选自Ce、Pr、Eu、Tb、Yb、Dy、Sm和/或Ho的元素掺杂。优选地,Gd2O2S粉末仅用一种选自Ce、Pr、Eu、Tb、Yb、Dy、Sm和Ho的元素掺杂。最优选的是使用元素Ce或Pr。
以重量份数计在Gd2O2S粉末中Ce的含量为0.1ppm-100ppm、优选5ppm-50ppm,并更优选10ppm-25ppm和/或在Gd2O2S粉末中Pr的含量可以为100ppm-1000ppm,优选300ppm-800ppm和更优选500ppm-800ppm。
已经发现,本发明的Gd2O2S荧光陶瓷在500ms时可以具有1×10-6-8×10-5的显著降低的余辉。本发明的荧光陶瓷优选在500ms时可以具有1.0×10-6-6×10-5的余辉,优选在500ms时具有1.0×10-6-5×10-5的余辉,更优选在500ms时具有1.0×10-6-3.0×10-5的余辉。
根据本发明的荧光陶瓷优选在制造期间经受单轴热压。在单轴热压步骤中,所述多晶砖块被优选地压实为接近理论密度的密度值,prel>99.7%ptheor。由于高密度,本发明的荧光陶瓷可以提供在光学范围内的良好透明度。因此,优选地,本发明的荧光陶瓷具有≥99.0%、优选≥99.5%和更优选≥99.7%并≤100%的密度。
此外,令人惊奇地发现,本发明的荧光陶瓷具有0.74-1.00、优选0.80-1.00和更优选地0.84-1.00的显著增加的相对光产率或者光输出。
根据本发明的荧光陶瓷的微晶尺寸优选大于用M掺杂的Gd2O2S晶粒的起始粉末的晶粒尺寸。优选地,≥50%、优选≥70%和更优选≥90%的M掺杂的Gd2O2S的荧光陶瓷微晶应当具有1-300μm、优选10-100μm的微晶尺寸。
根据本发明的荧光陶瓷可以在001平面具有一种纹理,该平面对应于在晶格中取向基本上垂直于在单轴压制过程期间所施加的压力方向的平面。
因此,根据本发明的一个实施方案,本发明的荧光陶瓷在其体积内含有单相,至少70%的所述荧光陶瓷的用M掺杂的微晶的晶粒大小为10μm-100μm,和所述陶瓷在至少一个晶面中具有织构。
这样,对于制造根据本发明的荧光陶瓷材料,通常有两种备选方案。备选方案I包括步骤a)和b),而备选方案II包括步骤a)、b)和c),其中步骤c)在步骤a)和步骤b)之间进行。
本发明通过本发明的实施例1-12的具体实施方案进行进一步阐述。
实施例1-12
将具有表I中给出的晶粒大小的表I的实施例1-12的起始原材料在约0.1-1Pa真空下经受单轴热压。压制温度在表I中给出且在实施例1-5、7-10和12中压力为200MPa,在实施例6和11中为250MPa,继之以空气退火,对比实施例1除外。
实施例1-12的数据即相对光产率和在500ms时以10-6为单位的余辉在下面表I中给出。
表I
实施例13-21
使具有6-9μm的晶粒大小的表II的实施例13-12的起始原材料在约0.1-1Pa真空下经受单轴热压。压制温度在表II中给出且在实施例13和14中压力为250MPa,在实施例15-21中为200MPa。实施例13、15、18和20在表II中给定的条件下经空气退火处理。实施例14、16、17、19和21在1Pa真空下退火处理,然后在表II中给定的条件下空气退火处理。
实施例13-21的数据即相对光产率和在500ms时以10-6为单位的余辉在下面表II中给出。
表II
在1200℃-1300℃下真空退火过程中,在陶瓷中发生晶粒生长和其中残余孔隙率发生降低,这导致陶瓷透明度的增加。在513nm自然发射波长下的总透过率相对于热处理之前的样品的透过率增加了约5%-15%。相对于仅用空气热处理的陶瓷,本发明的在真空下然后在空气中退火陶瓷由于它们的高透明度而在发光时具有更高的光输出。总透光率的测量使用采用60mm直径的积分球的Hitachi 330分光计实施。
在空气中退火导致在陶瓷中光输出显著增加约3倍和余辉显著降低约10倍。在真空压制和真空退火后,Gd2O2S微晶结构相对于氧和硫的化学计量受到干扰,导致在所述陶瓷中的有害电子阱浓度增加。在空气中退火后陶瓷x射线发光特性的显著增加由陶瓷的微晶结构的化学计量确定,以获得在本发明的荧光陶瓷的最佳性能。光输出和余辉借助National Instruments ADC的Hamamatsu PMT测量,其中光电倍增器通过铅屏蔽而屏蔽了直接辐射。余辉在120kV/100mA,80cmFDD(18-20mGy/s),2s脉冲的条件下测量,其中所有余辉值以静态信号ppm给出。信号值(光输出)在用硅胶粘附到光电二极管上的4×4mm2像素上测得。
根据本发明的荧光陶瓷可以例如用于:
-用于检测电离辐射,特别是x射线、γ射线和电子束的闪烁或者荧光元件;和/或
-在医学领域中使用的设备或装置,特别是计算机X线断层照相术(CT)。
特别优选的是,根据本发明的至少一种荧光陶瓷可以用于适用于医学成像的检测器或者设备。
然而,所述荧光陶瓷可以用于任何医学领域中已知的检测器。这些检测器是例如X射线检测器、CT检测器、电子射野影像检测器(Electronic Portal Imaging detector)等等。
Claims (8)
1.一种采用单轴热压制备荧光陶瓷材料的方法,所述方法包括下列步骤:
a)选择用M掺杂的Gd2O2S颜料粉末,且M代表至少一种选自Yb、Dy、Sm、Ho、Ce和/或Pr的元素,其中所述用于热压的粉末的晶粒大小为1μm-20μm,且所述热压在真空下在以下条件下进行1000-1400℃的温度;和/或
100MPa-300MPa的压力;
b)在700℃-1200℃下空气退火0.5小时至30小时。
2.权利要求1的方法,其中在步骤a)和步骤b)之间实施了额外步骤c),其中步骤c)包括在1000℃-1400℃温度下在真空中使荧光陶瓷退火0.5小时-30小时。
3.权利要求1或2的方法,其中在步骤a)中晶粒大小为1μm-20μm的未经掺杂的Gd2O2S粉末与包括含Pr、Ce、Yb、Dy、Sm和/或Ho的稀土离子的至少一种元素的组合物相混合。
4.由权利要求1-3任一项的方法制备的用于将电离辐射转化为光的荧光陶瓷,其中所述荧光陶瓷在其体积内含有单相,至少70%的所述荧光陶瓷的用M掺杂的微晶的晶粒大小为10μm-100μm,和所述陶瓷在至少一个晶面中具有织构。
5.权利要求4的荧光陶瓷,其中所述掺杂剂是0.1ppm-100ppm重量分数的Ce;和/或所述掺杂剂是100ppm-1000ppm重量分数的Pr。
6.设计用于检测电离辐射的检测器,所述检测器含有根据权利要求4的荧光陶瓷。
7.权利要求6的检测器,其中所述掺杂剂是0.1ppm-100ppm重量分数的Ce;和/或所述掺杂剂是100ppm-1000ppm重量分数的Pr。
8.权利要求6的检测器在适用于医学成像的设备中的用途。
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EP1753705B1 (en) | 2011-03-02 |
WO2005110943A1 (en) | 2005-11-24 |
EP1753705A1 (en) | 2007-02-21 |
RU2006146017A (ru) | 2008-07-27 |
JP2008501611A (ja) | 2008-01-24 |
DE602005026652D1 (de) | 2011-04-14 |
RU2004114975A (ru) | 2005-10-27 |
RU2350579C2 (ru) | 2009-03-27 |
ATE500208T1 (de) | 2011-03-15 |
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