CN1046689C - 用于高质量玻璃的可玻璃化组合物 - Google Patents
用于高质量玻璃的可玻璃化组合物 Download PDFInfo
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- 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
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S501/00—Compositions: ceramic
- Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
- Y10S501/901—Optical glass, e.g. silent on refractive index and/or ABBE number having R.I. at least 1.8
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S501/00—Compositions: ceramic
- Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
- Y10S501/903—Optical glass, e.g. silent on refractive index and/or ABBE number having refractive index less than 1.8 and ABBE number less than 70
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Abstract
该玻璃具有下列重量百分比范围的化学组成:氧化硅50-58,钾0-13,钠0-9,氧化锂0-4,氧化钙0-3,氧化镁0-4,硼酐0-2,氧化锌16-30,氧化钡0-12,氧化钛0-6,氧化锆0-5,氧化钇0-5,氧化铝0-3,氧化锡0-5,氧化镧0-9,氧化钕0-9,氧化铋0-12,氧化锗0-5。
Description
技术领域
本发明涉及具有铅晶质玻璃的特性但没有铅存在的玻璃组合物。领域状况
铅晶质玻璃作为具有特殊亮度、折射率、比重和响度的玻璃而为人们所熟知。
按照EEC标准69/493(在26/11/73的意大利法827中采用,附件b,栏e和f,行2),对于称为铅晶质玻璃的玻璃,它必须是含有至少24%铅的玻璃,其比重大于2.90克/立方厘米,折射率大于1.545。这些特性是通过铅含量来保证的,它还使玻璃具有良好的操作性、响度和光泽。
由于铅潜在的毒性,它已经被禁止用于某些生产过程而且这种限制在不远的将来有可能被扩大,因此人们需要发明一种新的具有与水晶相同的特性。
为此,人们对获得不含铅但具有上述水晶的物理特性的玻璃的其它途径进行了研究。为了达到此目的,可以用元素如钡、锌、钙、锶、铋、钛和其它无毒且能增加比重和折射率的元素的混合物来代替铅。但是除了这些性能以外,这些元素中许多元素的价钱较高并且会影响玻璃的操作性能或颜色,因而它们不适用于工业运用。
为此,研究者们努力确定最合适的组合物,以获得具有适用于手工和工业操作特性的无铅“晶质”玻璃,例如像在Compagnie des Cristalleriesde Baccarat申请的国际专利申请WO93/16964中所说的玻璃,其组成在下表中给出。
该组合物的特征在于用锌、锶和钙的混合物代替铅,相应的玻璃具有令人满意的比重和折射率,但它难以操作,其原因在于它具有较高的熔化点和软化点和不适合连续熔化的析晶温度。
氧化物 | 重量% |
SiO2 | 53-58 |
Li2O | 0-0.3 |
Na2O | 4.5-7.5 |
K2O | 6-10 |
SrO | 0-12 |
BaO | |
ZnO | 16-21 |
SrO+CaO+ZnO | 26.5-31 |
Al2O3 | 0-1.5 |
Sb2O3 | 0.5-1.5 |
TiO2 | 0-2 |
CaO | 0-9 |
SnO2 | 0-2.5 |
B2O3 | 0-1.2 |
La2O3 | 0-3 |
另一种无铅晶质玻璃是在Toyo Glass Co.Ltd.申请的欧洲专利申请0594422中所说的具有下表所示的组成的玻璃。根据该发明,铅被钡、锌、钛和硼的混合物代替并且该玻璃在合适的成本下具有令人满意的物理参数值,特别是比重和折射率。
氧化物 | 重量% |
SiO2 | 50.0-60.0 |
CaO | 1.0-5.0 |
BaO | 10.0-15.0 |
Na2O | 3.0-10.0 |
K2O | 5.0-13.0 |
Li2O | 0-1.0 |
TiO2 | 5.0-8.0 |
ZnO | 5.0-10.0 |
ZrO2 | 0-2.0 |
B2O3 | 1.0-2.0 |
Sb2O3 | 0.3-0.8 |
但是,具有该表中所说的化学组成的玻璃由于其钛含量较高它难以脱色及用工操作。本发明的内容
为了克服已知的无铅玻璃的缺陷,根据本发明,它设计了具有下表组成的用于可玻璃化混合物的组合物:
表1
SiO2 | 50-58 | TiO2 | 0-6 |
K2O | 0-13 | ZrO | 0-5 |
Na2O | 0-9 | Y2O3 | 0-5 |
Li2O | 0-4 | Al2O3 | 0-3 |
CaO | 0-3 | SnO2 | 0-5 |
MgO | 0-4 | La2O3 | 0-9 |
B2O3 | 0-2 | Nb2O5 | 0-9 |
ZnO | 16-30 | Bi2O3 | 0-12 |
BaO | 0-12 | GeO2 | 0-5 |
在该组合物中,铅被主要含有锌、钡、镧、钕和铋的混合物代替,从而使所说元素氧化物的总量为26%-33%。除氧化锌以外的这些氧化物的总量必须为7%-14%,并且还可以加入锆、钇和钛,这些氧化物的总量低于6%,从而进一步改善该玻璃的化学稳定性和折射率。
其它用来限定形成本发明的玻璃的氧化物混合物的特征为:-SiO2和Al2O3的总重量含量为52%-58%,以确保足够的化学稳定性;-钾、钠和锂氧化物总重量含量为12%-18%,以改善操作性和熔化性;-钾碱(K2O)和钠碱(Na2O)的摩尔比为0.9-2,以确保重金属离子的低转移;-作为澄清剂和脱色剂的砷、锑、镍、钴、锰、铒、钕、硒、铈氧化物的总量低于2%;-氧化铝和钙及镁的氧化物的存在总量低于4%,以增加耐水解性;-锡和锗的存在总量不超过5%,以达到所需的比重和折射率。
在上述范围内的可能的组成的框架内下列内容具有特别的意义:A)具有在下表2中所示的组成的玻璃:
表2
SiO2 | 53-57 | ZnO | 16-22 |
K2O | 7-12 | BaO | 7-12 |
Na2O | 3-6 | B2O3 | 0-1 |
Li2O | 0-2 | ZnO+BaO | 26-30 |
K2O+Na2O+Li2O | 12-17 | ZrO2 | 0-3 |
MgO | 0-2 | TiO2+ZrO2 | 0-6 |
TiO2 | 0-6 | Sb2O3 | 0-1 |
这些对应于在合理的成本下具有等于或大于上述EEC标准的比重和折射率并具有良好化学稳定性的玻璃,例如可以用作铅晶质玻璃替代物的下列玻璃(表2/1):
表2/1
1 | 2 | 3 | 4 | |
SiO2 | 53.5-54.5 | 55.5-56.5 | 54.5-55.5 | 53.5-54.5 |
K2O | 7.5-8.5 | 8-9 | 7.5-85 | 10-11 |
Na2O | 4.5-5.5 | 4-5 | 4.5-5.5 | 5-6 |
ZnO | 18-19 | 16.5-17.5 | 15.5-16.5 | 18.5-19.5 |
BaO | 9.5-10.5 | 10.5-11.5 | 10.5-11.5 | 9.5-10.5 |
Sb2O3 | 0.22-0.27 | 0.73-0.77 | 0.73-0.77 | 0.73-0.77 |
TiO2 | 3.5-4.5 | 1.5-2.5 | 3.5-4.5 | - |
更进一步地说,下表(表2/2)给出了具有按表2/1限定的范围的玻璃的组成及某些参数的测定值:
表2/2
1 | 2 | 3 | 4 | |
SiO2 | 54 | 56.25 | 55 | 54.15 |
K2O | 7.84 | 8.50 | 7.84 | 10.8 |
Na2O | 5.16 | 4.5 | 5.16 | 5.5 |
ZnO | 18.5 | 17 | 16 | 18.8 |
BaO | 10 | 11 | 11 | 10 |
Sb2O3 | 0.25 | 0.75 | 0.75 | 0.75 |
TiO2 | 4.25 | 2 | 4.25 | - |
K2O+Na2O+Li2O | 13 | 13.0 | 13 | 16.3 |
ZnO+BaO | 28.5 | 28 | 27 | 28.8 |
D.I.N.12111 | 0.12 | 0.14 | 0.13 | 0.30 |
d | 2.9575 | 2.9316 | 2.9441 | 2.938 |
nd | 1.5720 | 1.5570 | 1.5695 | 1.5510 |
α | 91.9 | 90.5 | 89 | 103.0 |
Abben° | 50.5 | 55.3 | 53.5 | 53 |
Tg | 563 | 569 | 567 | 523 |
Mg | 635 | 626 | 632 | 600 |
在该表及下表中,对各种玻璃给出了数值,其中“DIN 12111”是根据该标准测定的化学稳定性;“d”是按照ASTM标准C729-25测定的比重,单位为公斤/立方厘米;“α”是根据UNI标准7460在0-300℃范围内测定的热膨胀系数,单位为℃-1×10-6;“Tg”是玻璃转化温度,单位为℃;“Mg”为软化温度,单位为℃;“Abbe数”是表达式(nD-1)/(nF-nC)的值;Abbe值是光学分散率,该值越低对应越高的分散。B)与前面一种玻璃相比具有较少钡并具有更好质量的玻璃-具有相同或更好的物理参数,例如响度和分散性-但成本较高,它具有下列限定范围的组成(表3):
表3
下表(表3/1)表示根据该限定范围的两个组成范围:
SiO2 | 53-57 | TiO2 | 0-6 |
K2O | 7-12 | Bi2O3 | 1-12 |
Na2O | 3-6 | Bi2O3+ZnO+Bao | 26-30 |
Li2O | 0-1 | Bi2O3+BaO | 7-14 |
K2O+Na2O+Li2O | 12-17 | B2O3 | 0-1 |
Al2O3 | 0-1 | ZrO2 | 0-2 |
SiO2+Al2O3 | 53-57 | Y2O3 | 0-1 |
ZnO | 16-22 | TiO2+Y2O3+ZrO2 | 0-6 |
BaO | 0-13 | Sb2O3 | 0-1 |
表3/1
5 | 6 | |
SiO2 | 54.5-55.5 | 54.5-55.5 |
K2O | 10.5-11.5 | 10.5-11.5 |
Na2O | 5-6 | 5-6 |
ZnO | 18.5-19.5 | 18.5-19.5 |
BaO | 5.5-6.5 | - |
Bi2O3 | 2.5-3.5 | 8.5-9.5 |
Sb2O3 | 0.73-0.77 | 0.73-0.77 |
更进一步地说,下表(表3/2)给出了具有按表3/1限定的范围的两种玻璃的组成及某些参数的测定值:
表3/2
5 | 6 | |
SiO2 | 55.15 | 55.15 |
K2O | 10.8 | 10.8 |
Na2O | 5.5 | 5.5 |
ZnO | 18.8 | 18.8 |
BaO | 6 | - |
Bi2O3 | 3 | 9 |
Sb2O3 | 0.75 | 0.75 |
K2O+Na2O+Li2O | 16.3 | 16.3 |
ZnO+BaO+Bi2O3+Nb2O5 | 27.8 | 27.8 |
BaO+Bi2O3+Nb2O5 | 9 | 9 |
SiO2+Al2O3 | 55.15 | 55.15 |
D.I.N.12111 | 0.24 | 0.26 |
d | 2.911 | 2.939 |
nd | 1.5495 | 1.5570 |
α | 98.0 | 97.7 |
Abben° | 55 | 52.5 |
Tg | 528 | 529 |
Mg | 617 | 609 |
由上述两个实施例可以看出仅仅用铋替代钡就可以使光分散性增加。
已经进行的试验表明利用适当的氧化物组合,可以达到可以与铅晶质玻璃相比的参数值,根据不同的情况,它们利益于下列特性:产品的廉价,可操作性,颜色和光分散性。更进一步地说,上述组成范围可以产生具有改进的光学质量、高比重和较高的化学稳定性的玻璃,而不采用可能有毒的或污染的成分;上述特定的小范围限定了从工业制造和/市场观点看特别令人感兴趣的组成。
给出这些实施例的目的仅仅在于证实本发明的实用性,本发明在不脱离其所限定的范围情况下还可以有所变化。
Claims (5)
1.一种比重大于2.9克/立方厘米、折射率大于1.545的无铅玻璃,其特征在于它具有下表所述范围的氧化物重量百分比:
SiO2
50-58
TiO2
0-6
K2O
0-13
La2O3
0-9
Na2O
0-9
Nb2O5
0-9
Li2O
0-4
Bi2O3
0-12
K2O+Na2O+Li2O
12-18
Bi2O3+ZnO+BaO+La2O3+Nb2O5
26-33
GaO
0-3
Bi2O3+BaO+La2O3+Nb2O5
7-14
MgO
0-4
GeO2
0-5
Al2O3
0-3
B2O3
0-2
Al2O3+MgO+CaO
0-4
ZrO2
0-5
SiO2+Al2O3
52-58
Y2O3
0-5
ZnO
16-30
SnO2
0-5
BaO
0-12
TiO2+Y2O3+ZrO2
0-6
其它次要成分,如Ni、Mn、Nd、Er、Co、Sb、As、Se和Ce的总和低于2%重量且K2O和Na2O之间摩尔比为0.9-2。
2.权利要求1的玻璃,其特征在于它具有下列重量百分比化学组成:
SiO2
53-57
ZnO
16-22
K2O
7-12
BaO
7-13
Na2O
3-6
B2O3
0-1
Li2O
0-2
ZnO+BaO
26-30
K2O+Na2O+Li2O
12-17
ZrO2
0-3
MgO
0-2
TiO2+ZrO2
0-6
TiO2
0-6
Sb2O3
0-1
3.权利要求2的玻璃,其特征在于它具有下列化学组成:
1
2
3
4
SiO2
53.5-54.5
55.5-56.5
54.5-55.5
53.5-54.5
K2O
7.5-8.5
8-9
7.5-85
10-11
Na2O
4.5-5.5
4-5
4.5-5.5
5-6
ZnO
18-19
16.5-17.5
15.5-16.5
18.5-19.5
BaO
9.5-10.5
10.5-11.5
10.5-11.5
9.5-10.5
Sb2O3
0.22-0.27
0.73-0.77
0.73-0.77
0.73-0.77
TiO2
3.5-4.5
1.5-2.5
3.5-4.5
-
4.权利要求1的玻璃,其特征在于其重量百分比化学组成在下列范围内:
SiO2
53-57
TiO2
0-6
K2O
7-12
Bi2O3
1-13
Na2O
3-6
Bi2O3+ZnO+Bao
26-30
Li2O
0-1
Bi2O3+BaO
7-14
K2O+Na2O+Li2O
12-17
B2O3
0-1
Al2O3
0-1
ZrO2
0-2
SiO2+Al2O3
53-57
Y2O3
0-1
ZnO
16-22
TiO2+Y2O3+ZrO2
0-6
BaO
0-13
Sb2O3
0-1
5.权利要求4的玻璃,其特征在于它具有下列化学组成:
SiO2
54.5-55.5
54.5-55.5
K2O
10.5-11.5
10.5-11.5
Na2O
5-6
5-6
ZnO
18.5-19.5
18.5-19.5
BaO
5.5-6.5
-
Bi2O3
2.5-3.5
8.5-9.5
Sb2O3
0.73-0.77
0.73-0.77
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ITFI94A000223 | 1994-12-13 | ||
IT94FI000223A IT1268814B1 (it) | 1994-12-13 | 1994-12-13 | Miscela vetrificabile per vetri di qualita' |
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CN1296941C (zh) * | 2003-06-11 | 2007-01-24 | 日本特殊陶业株式会社 | 介电材料及其制造方法 |
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JP2881573B2 (ja) * | 1996-06-07 | 1999-04-12 | 東洋ガラス株式会社 | 鉛を含まないクリスタルなガラス組成物の製造方法 |
US20040185039A1 (en) * | 2002-08-30 | 2004-09-23 | Heinz Kohler | Therapeutic applications of noncovalent dimerizing antibodies |
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1994
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1995
- 1995-11-28 IL IL11618095A patent/IL116180A/xx not_active IP Right Cessation
- 1995-12-11 AT AT95940408T patent/ATE202328T1/de not_active IP Right Cessation
- 1995-12-11 KR KR1019970703982A patent/KR100262262B1/ko not_active IP Right Cessation
- 1995-12-11 SI SI9520147A patent/SI9520147A/sl not_active IP Right Cessation
- 1995-12-11 DK DK95940408T patent/DK0797550T3/da active
- 1995-12-11 CN CN95196772A patent/CN1046689C/zh not_active Expired - Fee Related
- 1995-12-11 EP EP95940408A patent/EP0797550B1/en not_active Expired - Lifetime
- 1995-12-11 ES ES95940408T patent/ES2160181T3/es not_active Expired - Lifetime
- 1995-12-11 CZ CZ19971816A patent/CZ289336B6/cs not_active IP Right Cessation
- 1995-12-11 RU RU97111785/03A patent/RU2137725C1/ru not_active IP Right Cessation
- 1995-12-11 HU HU9800676A patent/HUT77862A/hu unknown
- 1995-12-11 BR BR9509993A patent/BR9509993A/pt not_active IP Right Cessation
- 1995-12-11 PT PT95940408T patent/PT797550E/pt unknown
- 1995-12-11 SK SK747-97A patent/SK74797A3/sk unknown
- 1995-12-11 DE DE69521440T patent/DE69521440T2/de not_active Expired - Fee Related
- 1995-12-11 WO PCT/IT1995/000215 patent/WO1996018586A1/en active IP Right Grant
- 1995-12-11 AU AU41870/96A patent/AU4187096A/en not_active Abandoned
- 1995-12-11 JP JP8518561A patent/JPH10510793A/ja active Pending
- 1995-12-11 TR TR95/01556A patent/TR199501556A2/xx unknown
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1999
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Also Published As
Publication number | Publication date |
---|---|
SI9520147A (sl) | 1998-02-28 |
MX9704206A (es) | 1997-09-30 |
PT797550E (pt) | 2001-10-31 |
TR199501556A2 (tr) | 1996-07-21 |
IT1268814B1 (it) | 1997-03-06 |
EP0797550B1 (en) | 2001-06-20 |
EP0797550A1 (en) | 1997-10-01 |
HUT77862A (hu) | 1998-08-28 |
RU2137725C1 (ru) | 1999-09-20 |
BR9509993A (pt) | 1997-12-30 |
DK0797550T3 (da) | 2001-09-03 |
US6235667B1 (en) | 2001-05-22 |
CN1169707A (zh) | 1998-01-07 |
DE69521440D1 (de) | 2001-07-26 |
AU4187096A (en) | 1996-07-03 |
DE69521440T2 (de) | 2001-10-25 |
KR100262262B1 (ko) | 2000-07-15 |
AR000318A1 (es) | 1997-06-18 |
GR3036121T3 (en) | 2001-09-28 |
ITFI940223A1 (it) | 1996-06-13 |
IL116180A0 (en) | 1996-01-31 |
CZ181697A3 (en) | 1997-11-12 |
IL116180A (en) | 2000-01-31 |
ITFI940223A0 (it) | 1994-12-13 |
CZ289336B6 (cs) | 2002-01-16 |
SK74797A3 (en) | 1998-03-04 |
ATE202328T1 (de) | 2001-07-15 |
WO1996018586A1 (en) | 1996-06-20 |
ES2160181T3 (es) | 2001-11-01 |
JPH10510793A (ja) | 1998-10-20 |
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