CN106458712A - 发光玻璃组合物 - Google Patents
发光玻璃组合物 Download PDFInfo
- Publication number
- CN106458712A CN106458712A CN201580033080.3A CN201580033080A CN106458712A CN 106458712 A CN106458712 A CN 106458712A CN 201580033080 A CN201580033080 A CN 201580033080A CN 106458712 A CN106458712 A CN 106458712A
- Authority
- CN
- China
- Prior art keywords
- weight
- glass
- facet
- jewel
- vitreous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C17/00—Gems or the like
- A44C17/001—Faceting gems
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C17/00—Gems or the like
- A44C17/007—Special types of gems
- A44C17/008—Glass stones
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
- C03C3/108—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0028—Compositions for glass with special properties for crystal glass, e.g. lead-free crystal glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7742—Antimonates; Arsenates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/778—Borates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7782—Antimonates; Arsenates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/77924—Aluminosilicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7797—Borates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7798—Antimonates; Arsenates
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/645—Specially adapted constructive features of fluorimeters
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/87—Investigating jewels
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Abstract
本发明涉及基于发光玻璃组合物的刻面宝石,该发光玻璃组合物含有特定的稀土金属氧化物,因此使得刻面宝石可被识别;还涉及用于识别宝石的方法。
Description
技术领域
本发明涉及基于发光玻璃组合物的刻面宝石,该发光玻璃组合物含有特定的稀土金属氧化物,因此能够识别所述刻面宝石;还涉及用于识别宝石的方法。
背景技术
由无铅和含铅玻璃和合成宝石制成的合成宝石通常以完全不同的品质制造。在许多国家,宝石受制于所谓的产品合规性准则,该准则限制了可能有害成分的含量。
在宝石行业,自2005年以来,在世界市场上出现了巨大的价格压力,竞争激烈。品牌产品经常被复制或者以虚假的原产地声明交易。由于交易的石头的繁多种类,原件和复制品之间的快速区分是非常困难的。商标假冒造成的损失非常巨大。此外,宝石复制品通常不符合相同的质量标准和合规性规定;根据不同的国家,有害成分可能导致巨大的责任问题。
目前,通常在相应的专业实验室中检查合成宝石的真实性。为此目的,确定宝石玻璃的化学成分,并分析和比较其磨削几何形状/光泽。这种测试相对昂贵和耗时,并且不能被用于市场上的快速分析。
用于识别合成宝石的已知方法是用激光雕刻标记。由于其高成本和技术限制,这种方法仅能在非常有限的程度上被用于玻璃的合成宝石。
为了保护奢侈品免遭商标伪造,存在着许多产品认证的解决方案,例如多级安全贴纸,全息图,安全油墨,RFID(射频识别)系统等。然而,这些方法不适用于宝石,因为它们会不利地影响宝石的光学外观。
从WO 2011/141461 A1(Uni Berlin)已知,发光标记物的组合可以被应用于或引入到制品中。这些发光标记物保持化学键,不能被熔化到玻璃中。相反,作为发光标记的组分的原始化学化合物在熔化之后溶解在玻璃网络中。根据该专利的陶瓷颗粒的原始发光消失,因此在成品中不再能够被检测到。
US 2005 0253113(Schott)专利说明书公开了含有多于2mol%的稀土金属的特定氧化物的发光磷玻璃。EP 0 466 932 A1(Furukawa)公开了掺杂有稀土元素的石英玻璃。
US 7,256,398公开了含有0.5至3mol%的选自稀土的掺杂剂的玻璃珠。然而,玻璃中这种相对高浓度的掺杂剂是不合要求的,因为已知稀土会改变玻璃的颜色。此外,以上述浓度添加的掺杂剂会导致玻璃混合物原料成本的显著增加,使得这种组合物不再能以经济有效的方式被用于合成宝石。
可以使用常见的分析方法(例如RFA)相对简单地检测一位数百分比(1%对应于10,000mg/kg)浓度的掺杂剂。然而,它们导致玻璃的着色,因此不适合作为这种浓度的掺杂剂。
本发明的目的是提供具有发光性的刻面玻璃宝石,由于其掺杂剂的低含量,一方面它们不会引起玻璃的颜色变化,另一方面它们在发射光谱中具有清晰可识别的频带。掺杂剂作为“真伪的标志物”,使得便携式分析装置进行鉴定成为可能。
发明内容
令人惊奇的是,已经发现,根据权利要求1所述的刻面玻璃宝石可以实现本发明的目的。在这些组合物中稀土金属钪、镧、铈、镨、钐、铕、钇、铽、镝、钬、铥、镱和镥等的氧化物的浓度为每千克玻璃组合物中含2~2000mg(对应于按重量计0.0002-0.2%,基于1千克玻璃组合物),并且提供足够强的荧光辐射,使得在这样低的浓度下也能够鉴定(参见图1至4)。玻璃组合物的优选实施方案中,每千克玻璃组合物包含约5至约1000mg的稀土金属的特定氧化物;特别优选约5至约700mg,特别是约5至约500mg,更优选约5至约300mg的浓度。
当用光激发时,特别是在可见光范围内,根据权利要求所述的刻面玻璃宝石显示用于标记物和晶体玻璃基体的特征荧光信号,该信号可以用相应的装置读出。优选地,本发明的刻面玻璃宝石包含所述稀土金属中的至少两种,更优选至少三种的不同的氧化物。这使得荧光发射光谱能够被用作用于鉴定玻璃组合物的“指纹”。此外,在玻璃制造过程中,改变各批次中的稀土金属的氧化物的浓度比并且整合峰的强度不仅能够进行真实性检查,而且还能够分配批次,即生产日期的确定。
由于宝石的刻面所导致的特定反射性质,即使在珠宝中包含相对较小的宝石,也可以通过小型化的高性能光谱仪识别非常低含量的标记元素。这种效果的原因在于光束在刻面宝石中通常的多次反射,这导致较长的行进路径或较高的激发概率。在这样低的浓度下,对下面的玻璃组合物,特别是其掺杂剂的定量分析是不可能的,或者只有在非常高的成本下才是可能的。获得刻面(例如,通过研磨和抛光或坯料压制)的方法对于本领域技术人员是充分已知的。
本发明基于权利要求的掺杂玻璃组合物的刻面宝石是可获得的,例如获得自施华洛世奇,商品名为A 5328 MM2.5Cry,A 5000 MM10 Cry,A 6041 MM18 Cry。
此外,特别是当刻面宝石被镜面化(“贴箔”)时,荧光信号的出口优选朝向观察者方向。因此,根据本发明,特别优选被部分镜面化的刻面玻璃宝石。“部分镜面化”是指至少一个刻面或面被镜面化。例如,水钻中,亭部的面被镜面化。镜面化和镜面化的方法对于本领域技术人员是充分已知的(见下文)。根据本发明的刻面和镜面化的宝石是可获得的,例如获得自施华洛世奇,商品名为A 1100 PPO Cry F(F代表贴箔;银镜),A 1088 SS39Cry F,A 2058 SS6 Cry F,A 2088 SS34 Cry F,A 2078 SS6 Cry A HF(A表示替代银镜),A 2078SS6 Cry M HF(M表示铝镜)。
通过以不同的浓度比混合不同的标记元素,可以实现上所述方式标记的晶体玻璃产品的某种内部编码。因此,在实施例2(表1)中,氧化铽的比例选择为按重量计0.015%,氧化镝的比例选择为按重量计0.006%。
与未研磨的玻璃片相比,由于玻璃宝石的刻面化和因此增加的反射,可以使用极低浓度的掺杂剂(见上文),甚至低至5至300mg/kg的范围内。
具体实施方式
激发和检测
用便携式光学分析装置进行标记的检测,该装置用选定波长范围内的电磁辐射激发刻面宝石。荧光发射辐射以及可选地其衰减行为随后以波长选择性的方式读出并通过合适的算法进行分析,以识别宝石的真实性。这样的分析装置由例如瑞士认证研究和开发公司(Swiss Authentication Research and Development AG)制备和销售。波长选择性评价,使得能够在混合的稀土金属氧化物其各自特征波长处,对荧光信号进行定量比较。根据本发明,优选使用由玻璃制成的刻面宝石,其在电磁辐射激发时,呈现出在300至3000nm范围内,优选在300至1100nm范围内的荧光。
本发明还涉及一种用于识别由玻璃制成的刻面宝石的方法,包括以下步骤:
(a)提供根据本发明的由玻璃制成的刻面宝石;
(b)用电磁辐射激发它;
(c)检测所产生的荧光;以及
(d)可选地将所述信号与给定模式进行比较。
优选地,激发以波长选择性方式进行,更优选在300至780nm的波长下进行。在优选实施例中,该方法用于识别由玻璃制成的刻面宝石的生产批次。
玻璃组合物
对于制备刻面宝石的玻璃的组分,本发明原则上是不限制的。“玻璃”是指形成无定形固体的冷冻的过冷液体。根据本发明,可以使用掺杂的氧化物玻璃和硫属化物玻璃,金属玻璃或非金属玻璃。氧氮化物玻璃也可以是适合的。玻璃可以是单组分(例如石英玻璃)或双组分(例如碱金属硼酸盐玻璃)或多组分(钠钙玻璃)玻璃。
根据本发明的刻面宝石的掺杂玻璃组合物可以通过熔融,溶胶-凝胶法或通过冲击波制备。所述方法是本领域技术人员已知的。本发明优选无机玻璃,特别是氧化玻璃。这些包括硅酸盐玻璃、硼酸盐玻璃或磷酸盐玻璃,特别优选无铅玻璃。对于刻面宝石的制备,优选硅酸盐玻璃。硅酸盐玻璃的共同之处在于它们的网络主要由二氧化硅(SiO2)形成。通过加入另外的氧化物,例如氧化铝或各种碱金属氧化物,形成铝硅酸盐或碱金属硅酸盐玻璃。对于分级,关键的是在数量上,哪种氧化物是硅酸盐基础玻璃中第二丰富的。没有其它组分,即纯SiO2的硅酸盐玻璃被称为二氧化硅或石英玻璃。如果五氧化二磷或三氧化硼是玻璃的主要网络形成剂,则它们分别被称为磷酸盐或硼酸盐玻璃,其性质也可以通过添加另外的氧化物来调节。所述玻璃主要由氧化物组成,这就是为什么它们通常被称为氧化玻璃。
在优选实施方案中,除了稀土金属钪、镧、铈、镨、钐、铕、钇、铽、镝、钬、铥、镱和镥等的氧化物外,掺杂的玻璃组合物根据权利要求所述的量还包含以下组分:
(a)按重量计约35至约85%的SiO2;
(b)按重量计0至约20%的K2O;
(c)按重量计0至约20%的Na2O;
(d)按重量计0至约5%的Li2O;
(e)按重量计0至约13%的ZnO;
(f)按重量计0至约11%的CaO;
(g)按重量计0至约7%的MgO;
(h)按重量计0至约10%的BaO;
(i)按重量计0至约4%的Al2O3;
(j)按重量计0至约5%的ZrO2;
(k)按重量计0至约6%的B2O3;
(1)按重量计0至约3%的F;
(m)按重量计0至约2.5%的Cl。
优选地,掺杂的玻璃组合物包含:
(a)按重量计约45至约75%的SiO2;
(b)按重量计0至约10%的K2O;
(c)按重量计约5至约20%的Na2O;
(d)按重量计约0.5至约5%的Li2O;
(e)按重量计约3至约13%的ZnO;
(f)按重量计约2至约11%的CaO;
(g)按重量计0至约7%的MgO;
(h)按重量计0至约10%的BaO;
(i)按重量计约0.5至约4%的Al2O3;
(j)按重量计约0.5至约4%的ZrO2;
(k)按重量计约1至约6%的B2O3;
(1)按重量计0至约3%的F;
(m)按重量计0至约2.5%的Cl。
根据本发明特别优选的是包含以下物质的玻璃组合物:
(a)按重量计约48至约65%的SiO2;
(b)按重量计约1至约5%的K2O;
(c)按重量计约10至约17%的Na2O;
(d)按重量计约0.5至约3%的Li2O;
(e)按重量计约7至约13%的ZnO;
(f)按重量计约4至约11%的CaO;
(g)按重量计0至约3%的MgO;
(h)按重量计0至约1%的BaO;
(i)按重量计约0.5至约4%的Al2O3;
(j)按重量计约0.5至4%的ZrO2;
(k)按重量计约3至约6%的B2O3;
(1)按重量计0至约3%的F;
(m)按重量计0至约2.5%的Cl。
在基于硼硅酸盐玻璃的另一个优选实施方案中,掺杂的玻璃组合物除了权利要求所述的掺杂剂之外,还包含处于根据权利要求所述的浓度的以下组分:
(a)按重量计约30至约95%的B2O3;
(b)按重量计0至约20%的K2O;
(c)按重量计0至约25%的Na2O;
(d)按重量计0至约5%的Li2O;
(e)按重量计0至约13%的ZnO;
(f)按重量计0至约11%的CaO;
(g)按重量计0至约7%的MgO;
(h)按重量计0至约10%的BaO;
(i)按重量计0至约4%的Al2O3;
(j)按重量计0至约5%的ZrO2;
(k)按重量计0至约3%的F;
(1)按重量计0至约2.5%的Cl。
在基于磷酸盐玻璃的另一个优选实施方案中,掺杂的玻璃组合物除了权利要求所述的掺杂剂之外,还包含根据权利要求的浓度的以下组分:
(a)按重量计约30至约95%的P2O5;
(b)按重量计0至约30%的K2O;
(c)按重量计0至约30%的Na2O;
(d)按重量计0至约10%的Li2O;
(e)按重量计0至约20%的ZnO;
(f)按重量计0至约20%的CaO;
(g)按重量计0至约15%的MgO;
(h)按重量计0至约30%的BaO;
(i)按重量计0至约15%的Al2O3;
(j)按重量计0至约15%的SiO2;
(k)按重量计0至约15%的B2O3;
(1)按重量计0至约20%的BaO。
所有上述的量应理解为按重量计总共为100%。
玻璃涂层(贴箔或镜面化)
涂层通常包含一层金属和/或金属化合物,例如金属氧化物、金属氮化物、金属氟化物、金属碳化物或这些化合物以任何顺序的任意组合,其通过一种常用的涂敷方法施加到刻面宝石上。此外,可以涂覆不同金属或金属化合物的连续层。所述方法和涂层对本领域技术人员为充分已知。
镜面化方法尤其包括根据现有技术的PVD(物理气相沉积),CVD(化学气相沉积),涂漆方法和湿化学方法。
荧光光谱的测量的一般原理
合适的测量装置由Horiba Jobin Yvon GmbH公司出售。在这种测量装置中,由不同波长范围的一个或多个光源发射的辐射被光谱分解并通过光学元件和孔隙的布置来选择。限制类型的辐射光谱由光束整形元件会聚,并被引导到待测物体上。如果由于上述对样品物体的照射而发生发射,则其发射到围绕待测物体的样品室中。通过在检测器上游的光学装置(检测器装置),发射的辐射再次被光谱分解,并几何的定向朝向检测器。这可以通过反射镜系统,在与激发辐射成直角以及在相对于激发辐射的法线很小的角度下进行。检测器装置基本上由光敏传感器的阵列组成。通过光谱分解的辐射在检测器元件阵列上的上述几何调整,波长范围可以分配给各个传感器。读出系统包含可编程电子单元,其使得接收的信号能够被处理以及数字化评估。因此,可以数字化地处理及存储所获得的测量信号。
便携式探测器的测量原理
合适的装置由Swiss Authentication Research and Development AG公司(见上文)出售。由一个或多个光源发射的辐射,通过光束整形元件的布置被引导到待测物体上。如果由于上述样品物体的照射而发生发射,则其通过光学元件的布置被收集并被引导到光栅上。以这种方式光谱分解的辐射被投影到检测器阵列上,使得波长范围被分配给各个传感器。读出系统包含可编程电子单元,其使得接收的信号能够被处理以及数字化评估。因此,可以数字化地处理及存储所获得的测量信号。
表1的玻璃组合物制成的刻面宝石(尺寸为40mm×12mm×12mm的立方体),除了各玻璃基质(玻璃荧光)典型的发射外,都显示出允许明确鉴别的荧光光谱(参见图1-4),其在不同玻璃中显示出不同范围。在下文中,通过实施例描述了根据本发明的实施例1、2和3的光谱。应当注意,在图中还示出了在测量装置的样品室中散射的激发辐射,其作为散射激发辐射的第一和第二阶可见。例如实施例1,可以在471nm(一阶)和942nm(二阶)看到激发。因此,在这些波长处的峰值是测量伪像,可以被忽略。
荧光发射的模拟
为了比较非刻面玻璃和刻面玻璃的荧光发射,并检查刻面玻璃石的镜面化效果,通过Radiant Zemax公司的光线跟踪软件Zemax(装置,参见图5)进行荧光发射的模拟。
模拟三种不同的荧光发射:
(i)对于4mm半径的玻璃珠和存在于程序中的Schott-N-BK7@玻璃的参数;与光源的距离2.2mm;
(ii)对于来自施华洛世奇公司,直径为8.3mm,总长度为5.8mm的1028SS39水钻和存在于程序中的玻璃的参数为;与光源的距离2.2mm;水钻的台面垂直于光的传播方向;
(iii)对于对应于b)的水钻,其亭部刻面被模拟为被镜面化的(即,假定亭面刻面是完全反射的)。
在模拟中,假定光源完全准直,总功率为1瓦,半径为1mm,发射波长为450nm。在模拟中,光源被定位成使得光束入射到物体上的方向垂直于进入点的切平面(在珠子的情况下),或垂直于台平面并且穿过台的外接圆(在水钻的情况下)。
通过参数“自由路径”,定义了入射光束在被吸收并以荧光辐射(650nm)的形式发射之前将穿透到玻璃对象中多远。这对应于玻璃组合物中不同浓度的掺杂剂的模拟。自由路径越短,掺杂剂的浓度越高;自由路径越长,掺杂剂的浓度越低。
在模拟中,30mm×30mm的矩形区域被用作荧光发射的检测器,并被放置在距离光源-5mm处(即在光源后面5mm;参见图5),垂直于光源的光束轴并且仅记录发射的辐射(650nm)。
照射在相应玻璃物体a)至c)上的光束经受Snell折射和反射。源自光源的波长450nm的辐射在不同程度上被玻璃体当为波长为650nm的荧光辐射来发射。
撞击在用于三种不同几何形状的检测器上的光功率被进行比较。模拟(图6)清楚地示出在球面几何(a)的情况下发生最少的荧光发射。1028水钻SS39的荧光发射在自由路径的整个范围内高出两倍以上;这对当于与非刻面玻璃体相比,荧光增加大于100%。涂敷/镜面化水钻显示荧光发射的进一步增加,尽管不太显著。
附图说明
图1:在尺寸为40mm×12mm×12mm的长方体上测量的根据实施例1的具有200ppmSm2O 3添加剂(在471nm激发)的无铅晶体玻璃的荧光发射;
图2:在尺寸为40mm×12mm×12mm的立方体上测量的根据实施例2的具有60ppmDy2O3和150ppm Tb2O3添加剂(在453nm激发)的高铅晶体玻璃的荧光发射;
图3:在尺寸为40mm×12mm×12mm的长方体上测量的根据实施例3的具有5ppmEu2O3添加剂(在465nm激发)的钠钙玻璃的荧光发射;
图4(对照例):在尺寸为40mm×12mm×12mm的立方体上测量的没有添加掺杂剂的钠钙玻璃(在465nm激发)的荧光发射;
图5:使用以下图例的模拟设置的示意图:
·#1光源,波长为450nm的准直光束;
·#2水钻的几何形状;
·#3 650nm处的荧光发射;
·#4探测器;
图6:几何形状和自由路径的函数的荧光发射的模拟。
实施例
实施例1-15
下表1表示用于制造刻面宝石的不同玻璃的氧化物组成。所有量均以重量百分比表示。实施例涉及以下玻璃:
实施例1:根据专利CZ302723的无铅晶体玻璃(参见图1);实施例2:市售高铅晶体玻璃(参见图2);实施例3:市售的钠钙玻璃(参见图3);实施例4:标准光学玻璃N-BK7@;实施例5:市售硼硅酸盐玻璃;实施例6~15:市售的着色玻璃。
所有玻璃都含有掺杂剂,所述掺杂剂的量如本发明所述。
表一 具有掺杂剂的玻璃组合物(第1部分)
实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
SiO2 | 59.11 | 55.25 | 72.69 | 70.30 | 80.24 | 72.28 | 70.30 |
PbO | 31.90 | ||||||
K2O | 3.49 | 8.80 | 7.70 | 0.20 | 4.00 | 5.90 | |
Na2O | 11.40 | 2.30 | 13.20 | 10.24 | 4.60 | 15.00 | 10.60 |
B2O3 | 3.07 | 0.30 | 10.00 | 12.60 | |||
Li2O | 2.15 | ||||||
CaO | 7.19 | 9.29 | 0.20 | 2.90 | 6.70 | ||
MgO | 3.80 | ||||||
ZnO | 7.71 | 1.00 | 1.10 | ||||
Al2O3 | 0.43 | 0.70 | 2.30 | 0.10 | 1.60 | ||
TiO2 | 2.08 | 0.20 | 4.00 | ||||
As2O3 | |||||||
Sb2O3 | 0.47 | 0.43 | 0.32 | 0.26 | 0.12 | 0.50 | |
BaO | 0.90 | 1.50 | |||||
ZrO2 | 2.08 | ||||||
P2O5 | 0.70 | ||||||
Gd2O3 | 0.10 | ||||||
Nd2O3 | 1.30 | ||||||
SnO2 | 1.90 | ||||||
Sm2O3 | 0.0200 | - | 0.0300 | ||||
Eu2O3 | 0.0005 | 0.0050 | |||||
Ho2O3 | - | 0.1700 | 0.0500 | ||||
Tb4O7 | 0.0150 | 0.0300 | 0.0300 | ||||
Dy2O3 | 0.0060 | 0.0100 | |||||
Sc2O3 | 0.0400 | ||||||
CeO | 0.0400 | ||||||
Yb2O3 | 0.0300 | ||||||
Lu2O3 | 0.0300 |
表一 具有掺杂剂的玻璃组合物(第2部分)
实施例 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
SiO2 | 73.00 | 69.10 | 65.29 | 64.94 | 65.73 | 70.57 | 71.93 | 73.80 |
PbO | 0.90 | |||||||
K2O | 7.50 | 11.00 | 4.70 | 2.20 | 2.60 | 0.70 | ||
Na2O | 12.00 | 8.00 | 8.40 | 20.80 | 19.30 | 17.20 | 15.20 | 10.90 |
B2O3 | 2.00 | 3.80 | 4.10 | 2.40 | 1.00 | |||
CaO | 2.80 | 7.00 | 6.40 | 4.80 | 4.20 | 3.30 | 5.30 | 7.00 |
MgO | 2.70 | 0.20 | 0.10 | 0.20 | 0.10 | 0.20 | ||
ZnO | 3.00 | 1.70 | 0.70 | |||||
Al2O3 | 2.00 | 1.00 | 0.10 | 0.20 | 2.70 | 1.70 | 4.90 | 6.80 |
As2O3 | 0.70 | |||||||
Sb2O3 | 0.30 | 0.30 | 0.30 | 0.18 | ||||
BaO | 0.30 | 0.50 | 11.00 | |||||
SrO | 0.10 | |||||||
P2O5 | 3.80 | |||||||
F | 1.30 | 0.50 | ||||||
Er2O3 | 1.80 | |||||||
Sm2O3 | 0.0100 | 0.0300 | ||||||
Eu2O3 | 0.0300 | 0.0200 | 0.0250 | 0.0200 | ||||
Ho2O3 | 0.0200 | 0.0125 | 0.0100 | |||||
Tb4O7 | 0.0300 | |||||||
Dy2O3 | 0.0300 | 0.0300 | 0.0200 | 0.0300 | ||||
Sc2O3 | 0.0200 | 0.0500 | 0.0100 | |||||
Y2O3 | 0.0200 | 0.0100 | 0.0100 | |||||
La2O3 | 0.0400 | 0.0150 | ||||||
CeO | 0.0125 | |||||||
Pr6O11 | 0.0300 | 0.0200 | ||||||
Tm2O3 | 0.0200 | 0.0300 | 0.0200 | |||||
Yb2O3 | 0.0300 | 0.0300 | 0.0250 | 0.0300 | ||||
Lu2O3 | 0.0300 |
Claims (11)
1.一种刻面玻璃宝石,该宝石含有至少一种掺杂剂,所述掺杂剂选自稀土金属氧化物组成的组,所述稀土金属氧化物中的稀土金属包括钪、镧、铈、镨、钐、铕、钇、铽、镝、钬、铥、镱和镥,其特征在于,每千克所述玻璃组合物中所述稀土金属氧化物的总量为2-2000mg。
2.根据权利要求1所述的刻面玻璃宝石,其特征在于,每千克所述玻璃组合物中所述稀土金属氧化物的总量为5-700mg。
3.根据权利要求1和/或2所述的刻面玻璃宝石,其特征在于,所述玻璃是无机玻璃,优选为氧化玻璃。
4.根据权利要求3所述的刻面玻璃宝石,其特征在于,所述氧化玻璃选自硅酸盐玻璃、硼酸盐玻璃和磷酸盐玻璃。
5.根据前述权利要求1至4中至少一项所述的刻面玻璃宝石,其特征在于,使用至少两种,优选至少三种所述稀土金属氧化物的混合物。
6.根据前述权利要求1至5中至少一项所述的刻面玻璃宝石,其特征在于,所述刻面宝石在电磁辐射激发时,表现出在300至3000nm范围内,优选在300至1100nm范围内的荧光辐射。
7.根据前述权利要求中至少一项所述的刻面玻璃宝石,其特征在于,所述玻璃包括以下组分:
(a)按重量计35~85%的SiO2;
(b)按重量计0~20%的K2O;
(c)按重量计0~20%的Na2O;
(d)按重量计0~5%的Li2O;
(e)按重量计0~13%的ZnO;
(f)按重量计0~11%的CaO;
(g)按重量计0~7%的MgO;
(h)按重量计0~10%的BaO;
(i)按重量计0~4%的Al2O3;
(j)按重量计0~2%的ZrO2;
(k)按重量计0~6%的B2O3;
(1)按重量计0~3%的F;
(m)按重量计0~2.5%的Cl;
上述的量按重量计共达100%。
8.根据前述权利要求中至少一项所述的刻面玻璃宝石,其特征在于,所述玻璃包括以下组分:
(a)按重量计30~95%的B2O3;
(b)按重量计0~20%的K2O;
(c)按重量计0~25%的Na2O;
(d)按重量计0~5%的Li2O;
(e)按重量计0~13%的ZnO;
(f)按重量计0~11%的CaO;
(g)按重量计0~7%的MgO;
(h)按重量计0~10%的BaO;
(i)按重量计0~4%的Al2O3;
(j)按重量计0~5%的ZrO2;
(k)按重量计0~3%的F;
(1)按重量计0~2.5%的Cl;
上述的按重量计共达100%。
9.根据前述权利要求中至少一项所述的刻面玻璃宝石,其特征在于,所述玻璃包括以下组分:
(a)按重量计30~95%的P2O5;
(b)按重量计0~30%的K2O;
(c)按重量计0~30%的Na2O;
(d)按重量计0~10%的Li2O;
(e)按重量计0~20%的ZnO;
(f)按重量计0~20%的CaO;
(g)按重量计0~15%的MgO;
(h)按重量计0~30%的BaO;
(i)按重量计0~15%的Al2O3;
(j)按重量计0~15%的SiO2;
(k)按重量计0~15%的B2O3;
(1)按重量计0~20%的BaO;
上述的量按重量计共达100%。
10.根据前述权利要求中至少一项所述的刻面玻璃宝石,其特征在于,所述刻面玻璃宝石是部分镜面化的。
11.一种用于识别根据前述权利要求中至少一项所述的由玻璃制成的刻面宝石的方法,包括以下步骤:
(a)提供根据权利要求1至11中至少一项所述的由玻璃制成的刻面宝石;
(b)用电磁辐射激发它;
(c)检测所产生的荧光;以及
(d)可选地将信号与给定模式进行比较。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14182551.3A EP2990390A1 (de) | 2014-08-27 | 2014-08-27 | Lumineszierende Glaszusammensetzung |
EP14182551.3 | 2014-08-27 | ||
PCT/EP2015/069382 WO2016030340A1 (de) | 2014-08-27 | 2015-08-24 | Lumineszierende glaszusammensetzung |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106458712A true CN106458712A (zh) | 2017-02-22 |
CN106458712B CN106458712B (zh) | 2022-03-18 |
Family
ID=51398583
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201580033080.3A Active CN106458712B (zh) | 2014-08-27 | 2015-08-24 | 发光玻璃组合物 |
Country Status (5)
Country | Link |
---|---|
US (1) | US10414686B2 (zh) |
EP (2) | EP2990390A1 (zh) |
CN (1) | CN106458712B (zh) |
RU (1) | RU2717594C2 (zh) |
WO (1) | WO2016030340A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108793733A (zh) * | 2018-06-20 | 2018-11-13 | 昆明理工大学 | 一种高熔点led用荧光玻璃及放电等离子体烧结制备方法 |
CN113387565A (zh) * | 2020-03-13 | 2021-09-14 | 包头稀土研究院 | 荧光玻璃及其制备方法和用途 |
CN113651531A (zh) * | 2021-09-22 | 2021-11-16 | 烟台希尔德材料科技有限公司 | 一种第二相玻璃增强的荧光体化合物及其制备方法和组合物 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106630603A (zh) * | 2016-12-27 | 2017-05-10 | 钦州市中玻玻璃有限责任公司 | 一种发光玻璃 |
US11713268B2 (en) * | 2019-05-30 | 2023-08-01 | Owens-Brockway Glass Container Inc. | Period-coded containers with a traceable material composition |
GB2590932B (en) * | 2020-01-07 | 2024-02-07 | De Beers Uk Ltd | Determination of a gemstone's composition |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1105343A (zh) * | 1993-11-03 | 1995-07-19 | 化学技术大学 | 折射率高于1.52的无铅晶体玻璃 |
US5516227A (en) * | 1994-07-07 | 1996-05-14 | Iit Research Institute | Spherodized fluorescent beads for improved roadway pavement marker visibility |
RU2207991C2 (ru) * | 2001-06-04 | 2003-07-10 | Кочанова Александра Васильевна | Декоративное стекло |
RU2212380C2 (ru) * | 2001-06-04 | 2003-09-20 | Кочанова Александра Васильевна | Авантюриновое стекло |
US20040262547A1 (en) * | 2003-06-26 | 2004-12-30 | Ncr Corporation | Security labelling |
CN1754851A (zh) * | 2004-09-29 | 2006-04-05 | Hoya株式会社 | 磷酸盐光学玻璃、精密压制成形用预制件及其制造方法、光学元件及其制造方法 |
CN101269910A (zh) * | 2006-03-20 | 2008-09-24 | 肖特股份有限公司 | 具有短陶瓷化时间的锂-铝硅酸盐玻璃 |
CN101843394A (zh) * | 2009-03-27 | 2010-09-29 | 施华洛世奇公司 | 具有镜面反光的正面的宝石 |
US20110189412A1 (en) * | 2008-06-25 | 2011-08-04 | Olivier Renard | Vitreous Material with Visual Effects and Its Applications |
CN102858703A (zh) * | 2010-04-28 | 2013-01-02 | D.施华洛世奇两合公司 | 着红色玻璃及其制备方法 |
CN103936281A (zh) * | 2014-01-26 | 2014-07-23 | 齐鲁工业大学 | 一种稀土掺杂发光玻璃及其制备方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3855144A (en) * | 1963-04-16 | 1974-12-17 | Owens Illinois Inc | Luminescent device, process, composition, and article |
US5262365A (en) | 1990-02-05 | 1993-11-16 | The Furukawa Electric Co., Ltd. | Quartz glass doped with rare earth element and production thereof |
RU2093617C1 (ru) | 1996-09-26 | 1997-10-20 | Олег Валерьевич Бакунов | Монокристаллический ювелирный материал |
US6705114B2 (en) * | 2002-05-29 | 2004-03-16 | D. Swarovski & Co. | Decorative stone made of glass |
US7758774B2 (en) * | 2002-11-29 | 2010-07-20 | Japan Science And Technology Agency | Luminescent glass |
EP1433750A1 (en) | 2002-12-26 | 2004-06-30 | Nec Tokin Corporation | Ornamental material performing particular light emission or particular color emission |
DE10311820A1 (de) | 2003-03-13 | 2004-09-30 | Schott Glas | Halbleiterlichtquelle |
US7256398B2 (en) | 2003-06-26 | 2007-08-14 | Prime Technology Llc | Security markers for determining composition of a medium |
AT414310B (de) | 2004-03-19 | 2007-01-15 | Swarovski & Co | Blei- und bariumfreies kristallglas |
DE102004026432A1 (de) * | 2004-05-29 | 2005-12-22 | Schott Ag | Glaszusammensetzungen als antimikrobieller Zusatz für Dentalmaterialien und deren Verwendung |
EP1674431B1 (fr) | 2004-12-24 | 2017-09-20 | Baccarat | Volume de cristal présentant un effet visuel décoratif de nature dichroïque |
RU2421710C2 (ru) | 2009-09-17 | 2011-06-20 | Общество с ограниченной ответственностью "Алмазинтех-консультации и инжиниринг" | Способ идентификации необработанных алмазов, бриллиантов и других драгоценных камней |
DE102010028801A1 (de) | 2010-05-10 | 2011-11-10 | Freie Universität Berlin | Thermisch leitfähige Zusammensetzung umfassend thermisch leitfähige Kohlenstoffnanoröhren und eine kontinuierliche Metallphase |
RU2426488C1 (ru) * | 2010-05-20 | 2011-08-20 | Авакян Карен Хоренович | Синтетический материал для ювелирной промышленности и способ его получения |
CZ302723B6 (cs) | 2010-07-26 | 2011-09-21 | Preciosa, A.S. | Krištálové sklo s indexem lomu vyšším než 1,53 bez obsahu sloucenin olova, barya a arzénu |
-
2014
- 2014-08-27 EP EP14182551.3A patent/EP2990390A1/de not_active Withdrawn
-
2015
- 2015-08-24 WO PCT/EP2015/069382 patent/WO2016030340A1/de active Application Filing
- 2015-08-24 EP EP15760114.7A patent/EP3186206B1/de active Active
- 2015-08-24 CN CN201580033080.3A patent/CN106458712B/zh active Active
- 2015-08-24 US US15/318,534 patent/US10414686B2/en active Active
- 2015-08-24 RU RU2016149800A patent/RU2717594C2/ru active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1105343A (zh) * | 1993-11-03 | 1995-07-19 | 化学技术大学 | 折射率高于1.52的无铅晶体玻璃 |
US5516227A (en) * | 1994-07-07 | 1996-05-14 | Iit Research Institute | Spherodized fluorescent beads for improved roadway pavement marker visibility |
RU2207991C2 (ru) * | 2001-06-04 | 2003-07-10 | Кочанова Александра Васильевна | Декоративное стекло |
RU2212380C2 (ru) * | 2001-06-04 | 2003-09-20 | Кочанова Александра Васильевна | Авантюриновое стекло |
US20040262547A1 (en) * | 2003-06-26 | 2004-12-30 | Ncr Corporation | Security labelling |
CN1754851A (zh) * | 2004-09-29 | 2006-04-05 | Hoya株式会社 | 磷酸盐光学玻璃、精密压制成形用预制件及其制造方法、光学元件及其制造方法 |
CN101269910A (zh) * | 2006-03-20 | 2008-09-24 | 肖特股份有限公司 | 具有短陶瓷化时间的锂-铝硅酸盐玻璃 |
US20110189412A1 (en) * | 2008-06-25 | 2011-08-04 | Olivier Renard | Vitreous Material with Visual Effects and Its Applications |
CN101843394A (zh) * | 2009-03-27 | 2010-09-29 | 施华洛世奇公司 | 具有镜面反光的正面的宝石 |
CN102858703A (zh) * | 2010-04-28 | 2013-01-02 | D.施华洛世奇两合公司 | 着红色玻璃及其制备方法 |
CN103936281A (zh) * | 2014-01-26 | 2014-07-23 | 齐鲁工业大学 | 一种稀土掺杂发光玻璃及其制备方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108793733A (zh) * | 2018-06-20 | 2018-11-13 | 昆明理工大学 | 一种高熔点led用荧光玻璃及放电等离子体烧结制备方法 |
CN113387565A (zh) * | 2020-03-13 | 2021-09-14 | 包头稀土研究院 | 荧光玻璃及其制备方法和用途 |
CN113387565B (zh) * | 2020-03-13 | 2022-04-05 | 包头稀土研究院 | 荧光玻璃及其制备方法和用途 |
CN113651531A (zh) * | 2021-09-22 | 2021-11-16 | 烟台希尔德材料科技有限公司 | 一种第二相玻璃增强的荧光体化合物及其制备方法和组合物 |
CN113651531B (zh) * | 2021-09-22 | 2022-11-22 | 烟台希尔德材料科技有限公司 | 一种第二相玻璃增强的荧光体化合物及其制备方法和组合物 |
Also Published As
Publication number | Publication date |
---|---|
RU2016149800A3 (zh) | 2019-02-22 |
EP2990390A1 (de) | 2016-03-02 |
US20170166474A1 (en) | 2017-06-15 |
EP3186206A1 (de) | 2017-07-05 |
US10414686B2 (en) | 2019-09-17 |
RU2717594C2 (ru) | 2020-03-24 |
RU2016149800A (ru) | 2018-09-27 |
EP3186206B1 (de) | 2023-07-19 |
WO2016030340A1 (de) | 2016-03-03 |
EP3186206C0 (de) | 2023-07-19 |
CN106458712B (zh) | 2022-03-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106458712A (zh) | 发光玻璃组合物 | |
Jochum et al. | The preparation and preliminary characterisation of eight geological MPI‐DING reference glasses for in‐situ microanalysis | |
Orellana et al. | Applications of laser-ablation-inductively-coupled plasma-mass spectrometry in chemical analysis of forensic evidence | |
CN1914126B (zh) | 在cvd金刚石中引入标记的方法 | |
Liang et al. | Luminescence properties of Tb3+–Sm3+ codoped glasses for white light emitting diodes | |
Abduriyim et al. | Applications of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to gemology | |
JP2003524839A (ja) | 物品の認証 | |
US9224082B2 (en) | Combination of luminescent substances | |
CN107316075A (zh) | 珠宝身份追溯物证一体多维绑定防伪方法及套件 | |
Marzouk et al. | Gamma irradiation effect on structural and spectral properties of CeO 2, Nd 2 O 3, Gd 2 O 3 or Dy 2 O 3–doped strontium borate glass | |
US20050143249A1 (en) | Security labels which are difficult to counterfeit | |
EP1963446B1 (en) | Secure tag | |
Efenji et al. | Description and dosimetric features of lithium borate glass doped with transition metals for thermoluminesce, a re-evaluation | |
US7521670B2 (en) | Standard for referencing luminescence signals | |
Hickman et al. | The selection of the best elemental variables for the classification of glass samples | |
Dussubieux et al. | Chemical composition of 16th-to 18th-century glass beads excavated in Paris | |
Caucia et al. | New physical, geochemical and gemological data of opals from Acari Mine (Arequipa Department, Peru) | |
US20070290170A1 (en) | Method of increasing fluorescence intensity of oxide glass | |
CN1892217A (zh) | 用于从矿场到市场的钻石和其它宝石的检验、标识和评级过程 | |
Bulus et al. | Structural and luminescence characterization of lithium-borosulfophosphate glasses containing dysprosium ions | |
EP1630549A1 (en) | Method for gemstone tracing | |
Nandyala et al. | Time resolved emission spectra and electron paramagnetic resonance studies of Gd3+ doped calcium phosphate glasses | |
CN110407463A (zh) | 一种超宽带近红外发光碲团簇掺杂玻璃及制备方法 | |
Sun et al. | G&G Gem News International. | |
Officer | Alternative strategies for security labelling/encoding of paper and plastic products. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |