WO2010142256A2 - High-lead content glass - Google Patents

High-lead content glass Download PDF

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Publication number
WO2010142256A2
WO2010142256A2 PCT/CZ2010/000068 CZ2010000068W WO2010142256A2 WO 2010142256 A2 WO2010142256 A2 WO 2010142256A2 CZ 2010000068 W CZ2010000068 W CZ 2010000068W WO 2010142256 A2 WO2010142256 A2 WO 2010142256A2
Authority
WO
WIPO (PCT)
Prior art keywords
glass
oxide
lead content
lead
less
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.)
Ceased
Application number
PCT/CZ2010/000068
Other languages
French (fr)
Other versions
WO2010142256A3 (en
Inventor
Jan KOŘENOVSKÝ
Květa SÁZANOVÁ
Jiři Vavřena
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Preciosa AS
Original Assignee
Preciosa AS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Preciosa AS filed Critical Preciosa AS
Priority to CN2010800354557A priority Critical patent/CN102803169A/en
Priority to US13/377,631 priority patent/US20120129680A1/en
Priority to RU2011152468/03A priority patent/RU2560045C2/en
Priority to EP10744657A priority patent/EP2454208A2/en
Publication of WO2010142256A2 publication Critical patent/WO2010142256A2/en
Publication of WO2010142256A3 publication Critical patent/WO2010142256A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C17/00—Gems or the like
    • 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

Definitions

  • the invention relates to a crystal glass with a high content of lead.
  • the crystal glass is advantageously used in a jewellery production.
  • compositions containing lead monoxide > 30 % wt. (category 1, Directive No.69/493).
  • high-lead content glass the typical composition of which is 48 to 55% of SiO 2 , 3 ⁇ 1o '33% PbO, 10 to 15% K 2 O + Na 2 O, completed with stabilizing oxides Al 2 ⁇ 3 , ZnO, BaO, B 2 ⁇ 3 , and that show the following properties:
  • At room temperature glass may be considered a solid substance and the ratio between the acting force and deformation on tension or pressure strain is given by the Hook law.
  • Young's moduluses are influenced by the chemical composition, temperature, crystallization, cooling of the semi-finished product, etc. (Fanderlik). Young's moduluses are connected with the solidity of bonds and closeness of arrangement of particles in the glass network.
  • the solidity of glass is increased by oxides that increase chemical resistance (VoIf). Higher E values mean that glass is ' less deformed by the effect of external forces.
  • the invention relates to high-lead content crystal glass that shows with advantage refraction index > 1.58 at 589.3 nm and high light transmission, further, increased mechanical solidity and chemical resistance. According to this invention the improvement of high-lead content crystal optic
  • boron trioxide influences the Young's modulus E within a very wide extent. If alkalis prevail over boron trioxide and the ratio of ion radiuses is larger than 2, the influence (factor)' of B 2 O 3 achieves also in minority quantity the maximum increase of the Young's modulus E. Boron oxide as the minority component does not influence chemical resistance, but increases the lustre of the products. It is caused by the orientation of the bonds cation - oxygen (coordination number 3) for boron atoms.
  • Zinc oxide then improves the hardness of glass in comparison with the elements of triad Ca - Sr - Ba. In comparison with those elements it is characterized also by larger solidity of bond to oxygen. Zinc oxide improves glass chemical resistance to the effects of water. However, with acid and alkali leaches calcium oxide is more efficient. Detail description of the embodiments
  • Nominal luminosity (dimensionlessj > 93 > 93
  • Example number 1 represents electrically molten glass with the share of 50% wt. of cullets themselves.
  • the glass according to example 1 is usable for the production of utility objects, including chandelier trimmings and semi-finished products or for the production of minor glass jewellery moulded pieces by one-stage technology.
  • Example number 2 represents molten glass molten at gas glass-making unit with the share of 40% wt. of cullets themselves.
  • the glass according to this example is intended for the production of rods or glass jewellery semi-finished products by one- and two-stage technologies.
  • the invention is especially suitable for the production of glass for making decorative and glass jewellery objects. Of course, it is also possible to use it anywhere else where it will be suitable thanks to its 'properties. '

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

High-lead content crystal glass shows with advantage the refraction index higher than 1.58, high light transmission, increased mechanical solidity and chemical resistance is suitable, especially, for the production and refinement of glass jewellery products, decorative and utility objects, including chandelier trimmings and semi-finished products. This glass contains, presented in % wt., 48 to 53 % of silica SiO2, 30 to 33 % of lead monoxide PbO, 10 to 13 % of the sum of potassium oxide and sodium oxide K2O + Na2O, 1 to 3 % of calcium oxide CaO, 0.5 to 1 % of zinc oxide ZnO, 0.5 to 1 % of boron trioxide B2O3, less than 0.3 % of barium monoxide BaO, less than 0.3% of aluminium oxide AI2O3, 0.2 to 0.5 % of antimony trioxide Sb2O3, 0.007 to 0.01 % of oxides of iron.

Description

High-Lead Content Glass
Field of the invention
The invention relates to a crystal glass with a high content of lead. The crystal glass is advantageously used in a jewellery production.
Background of the invention
The properties of crystal glass that is used in the field of utility and glass jewellery production respect the European directive on convergence of legal regulations of the member states relating to crystal glass No. 69/493 of December 15, 1969. Directive No. 69/493/EEC provides for the requirements for the properties of crystal glass depending on composition, density, refraction index and surface hardness.
Used for the products requiring marked optic-aesthetic properties, as a rule, are compositions containing lead monoxide > 30 % wt. (category 1, Directive No.69/493).
At present, used most frequently' is high-lead content glass the typical composition of which is 48 to 55% of SiO2, 3θ1o '33% PbO, 10 to 15% K2O + Na2O, completed with stabilizing oxides Al2θ3, ZnO, BaO, B2θ3, and that show the following properties:
Figure imgf000002_0001
Used in the manufacture of utility and glass jewellery objects and in their use the refined crystal products are subject to mechanical and chemical strain (Gotz). By the influence of mechanical forces the edges and surface of the products might be damaged (scratched). Acting in parallel with this factor are physical - chemical influences of the environment in which the products appear (Rana).
At room temperature glass may be considered a solid substance and the ratio between the acting force and deformation on tension or pressure strain is given by the Hook law.
Young's moduluses are influenced by the chemical composition, temperature, crystallization, cooling of the semi-finished product, etc. (Fanderlik). Young's moduluses are connected with the solidity of bonds and closeness of arrangement of particles in the glass network.
The solidity of glass is increased by oxides that increase chemical resistance (VoIf). Higher E values mean that glass is'less deformed by the effect of external forces.
Summary of the invention
The invention relates to high-lead content crystal glass that shows with advantage refraction index > 1.58 at 589.3 nm and high light transmission, further, increased mechanical solidity and chemical resistance. According to this invention the improvement of high-lead content crystal optic
* ^ ,- aesthetic and utility properties is achieved by glass composition containing oxides in
% wt.:
50 to 53% of silica SiO2
30 to 33% of lead monoxide PbO . 10 to 13% sum of potassium oxide,and sodium oxide K2O + Na2O
1 to 3 % of calcium oxide CaO
0.5 to 1 % of zinc oxide ZnO
0.5 to 1 % of boron trioxide B2O3 less than 0.3% of barium monoxide BaO less than 0.3% of aluminium oxide AI2O3
0.2 to 0.5% of antimony trioxide Sb2O3
0.006 to 0.01% of oxides of iron. In the proposed high-lead content glass the depressive influence of barium monoxide is suppressed and, on the contrary, the positive influence of calcium oxide on Young's modulus E is strengthened.
Mechanical properties of the glass depend on the solidity of bond cation - oxygen and on the deformability of ions. With divalent elements the ion potential decreases in the line Ca - Sr - Pb - Ba. Deformability of lead ions changes the order of elements into the new line Ca - Sr - Ba - Pb.
Deformability of lead ions causes that lead containing glass is softer by 20% than barium glass. With increasing content of PbO the E values decrease.
For glass containing around 30% of PbO of common composition the Young's modulus E < 60 000 MPa. By using the proposed composition according to this invention E value will increase minimum to 70 000 MPa. The advantage of the presence of calcium oxide in lead containing glass according to the invention is that in parallel chemical resistance increases both to water and to acids and alkalis.
According to this invention boron trioxide influences the Young's modulus E within a very wide extent. If alkalis prevail over boron trioxide and the ratio of ion radiuses is larger than 2, the influence (factor)' of B2O3 achieves also in minority quantity the maximum increase of the Young's modulus E. Boron oxide as the minority component does not influence chemical resistance, but increases the lustre of the products. It is caused by the orientation of the bonds cation - oxygen (coordination number 3) for boron atoms.
Zinc oxide then improves the hardness of glass in comparison with the elements of triad Ca - Sr - Ba. In comparison with those elements it is characterized also by larger solidity of bond to oxygen. Zinc oxide improves glass chemical resistance to the effects of water. However, with acid and alkali leaches calcium oxide is more efficient. Detail description of the embodiments
The examples of types of the invention and properties of glass are presented in the following tables.
Example No. 1 2
Glass components content of oxides in % wt.
Silica SiO2 51.36 51.22
Lead monoxide PbO 32.00 31.90
Zinc oxide ZnO 0.71 0.71
Calcium oxide CaO 1.96 1.96
Potassium oxide K2O 6.58 6.56
Sodium oxide Na2O 6.31 6.18
Boron trioxide B2θ3 0.77 1.16
Aluminium oxide AI2O3 0.1 0.1
Antimony trioxide Sb2O3 0.21 0.21
Neodymium oxide Nd2O3 0.002 0.002
Erbium oxide Er2O3 0.02 0.02
Properties of glass according to example types:
Figure imgf000005_0001
TG ex) 465.35 464.25
Tm (X) 532.25 523.50
T ,av (°C) 1232 1237 α 10"6 (K ~1) 10.4109 9.4568
Refraction index at 589.3 nm 1.5804 * 1.5803*
Nominal luminosity (dimensionlessj > 93 > 93
Abbe's number 60.21 * 60.34*
Class of water resistance 3. 3. Density (g/cm ) 3.202 (3.180*) (3.176*)
Grinding hardness (mm 3Zs) 2.648 2.504
Polishability (mm3/s) 0.0558 0.0518
* - calculated values
Example number 1 represents electrically molten glass with the share of 50% wt. of cullets themselves. The glass according to example 1 is usable for the production of utility objects, including chandelier trimmings and semi-finished products or for the production of minor glass jewellery moulded pieces by one-stage technology.
Example number 2 represents molten glass molten at gas glass-making unit with the share of 40% wt. of cullets themselves. The glass according to this example is intended for the production of rods or glass jewellery semi-finished products by one- and two-stage technologies.
Industrial applicability
The invention is especially suitable for the production of glass for making decorative and glass jewellery objects. Of course, it is also possible to use it anywhere else where it will be suitable thanks to its 'properties. '

Claims

Claims
1/ High-lead content glass characterized in that it contains % wt:
50 to 53% of SiO2 30 to 33% of PbO "
10 to 13% of sum of K2O + Na2O 1 to 3% of CaO 0.5 to 1% Of ZnO 0.5 to 1% Of B2O3 less than 0.3% of BaO less than 0.3% Of AI2O3 0.2 to 0.5% of Sb2O3 0.07 to 0.01 % of oxides of iron
2/ High-lead content glass according to claim 1 characterized in that the weight ratio of oxide BaO and oxide CaO is 1 :3 to 1 :10.
3/ High-lead content glass according to claim 1 characterized in that the sum of
% wt. of oxides B2O3 and ZnO is < 2%.
4/ High-lead content glass according to claim 1 characterized in that the Young's modulus E achieves minimum 70.000 Mpa.
5/ High-lead content glass according to claim 1 characterized in that the content of potassium oxide is higher than the content of sodium oxide.
PCT/CZ2010/000068 2009-06-10 2010-06-09 High-lead content glass Ceased WO2010142256A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN2010800354557A CN102803169A (en) 2009-06-10 2010-06-09 High-lead content glass
US13/377,631 US20120129680A1 (en) 2009-06-10 2010-06-09 High-lead content glass
RU2011152468/03A RU2560045C2 (en) 2009-06-10 2010-06-09 Glass with high lead content
EP10744657A EP2454208A2 (en) 2009-06-10 2010-06-09 High-lead content crystal glass

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZPV2009-373 2009-06-10
CZ20090373A CZ2009373A3 (en) 2009-06-10 2009-06-10 High-lead glass

Publications (2)

Publication Number Publication Date
WO2010142256A2 true WO2010142256A2 (en) 2010-12-16
WO2010142256A3 WO2010142256A3 (en) 2011-04-14

Family

ID=42932073

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PCT/CZ2010/000068 Ceased WO2010142256A2 (en) 2009-06-10 2010-06-09 High-lead content glass

Country Status (7)

Country Link
US (1) US20120129680A1 (en)
EP (1) EP2454208A2 (en)
KR (1) KR20120048557A (en)
CN (1) CN102803169A (en)
CZ (1) CZ2009373A3 (en)
RU (1) RU2560045C2 (en)
WO (1) WO2010142256A2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3339262A1 (en) 2016-12-23 2018-06-27 PRECIOSA, a.s. Material for the production of fashion jewellery and jewellery stones with high refractive index and high thermal resistance
WO2020169130A1 (en) 2019-02-18 2020-08-27 Preciosa, A.S. Glass ceramic material of a spinel type for the production of fashion jewellery and jewellery stones

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103241946B (en) * 2013-05-21 2015-02-11 大连卡莎慕玻璃艺术有限公司 Lead-free crystal glass and preparation method thereof

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870531A (en) * 1971-07-28 1975-03-11 Jenaer Glaswerk Schott & Gen Optical flint glass with relatively low refractive indices and high dispersion
SE361874B (en) * 1972-07-06 1973-11-19 Glasforskningsinstitutet
DE3404363A1 (en) * 1984-02-08 1985-08-14 Schott Glaswerke, 6500 Mainz HIGH PBO-CONTAINING GLASSES IN THE SIO SYSTEM (DOWN ARROW) 2 (DOWN ARROW) PBO-M (DOWN ARROW) 2 (DOWN ARROW) O WITH INCREASED CHEMICAL RESISTANCE
SU1528748A1 (en) * 1987-11-02 1989-12-15 Гусевский Филиал Государственного Научно-Исследовательского Института Стекла Crystal glass
JPH04188781A (en) * 1990-11-22 1992-07-07 Asahi Glass Co Ltd Acoustooptical q-switch element
US6251811B1 (en) * 1998-07-10 2001-06-26 Asahi Glass Company Ltd. Funnel glass for a cathode ray tube
US7196027B2 (en) * 2000-06-05 2007-03-27 Kabushiki Kaisha Ohara Optical glass suffering little change in refractive index by radiation of light
DE10203226A1 (en) * 2002-01-28 2003-09-04 Schott Glas Optical glass
DE10207732B4 (en) * 2002-02-22 2008-07-24 Schott Ag Glass with significantly improved stability against radiation damage, a process for its preparation and its use
CN1213956C (en) * 2003-03-12 2005-08-10 成都光明光电信息材料有限公司 Violet optical glass
RU2312078C1 (en) * 2006-06-14 2007-12-10 Юлия Алексеевна Щепочкина Crystal glass
DE102009027109B4 (en) * 2009-06-23 2012-02-16 Schott Ag Leaded space glass, its manufacture and use
DE102009027110B4 (en) * 2009-06-23 2012-02-16 Schott Ag Leaded space glass, its manufacture and use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3339262A1 (en) 2016-12-23 2018-06-27 PRECIOSA, a.s. Material for the production of fashion jewellery and jewellery stones with high refractive index and high thermal resistance
RU2758310C2 (en) * 2016-12-23 2021-10-28 ПРЕСИОСА, а.с. Material for manufacturing jewelry and jewelry gems with high refractive index and high temperature resistance
WO2020169130A1 (en) 2019-02-18 2020-08-27 Preciosa, A.S. Glass ceramic material of a spinel type for the production of fashion jewellery and jewellery stones
US11987519B2 (en) 2019-02-18 2024-05-21 Preciosa, A.S. Glass ceramic material of a spinel type for the production of fashion jewellery and jewellery stones

Also Published As

Publication number Publication date
US20120129680A1 (en) 2012-05-24
RU2011152468A (en) 2013-06-27
WO2010142256A3 (en) 2011-04-14
KR20120048557A (en) 2012-05-15
CZ302100B6 (en) 2010-10-13
CZ2009373A3 (en) 2010-10-13
EP2454208A2 (en) 2012-05-23
CN102803169A (en) 2012-11-28
RU2560045C2 (en) 2015-08-20

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