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US4537862A
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Lead-free and cadmium-free glass frit compositions for glazing, enameling and decorating
Assignee: Libbey Glass Inc
•
Filing: 1984-04-27
•
Granted: 1985-08-27
•
Expires: 2004-04-27
Abstract
Abstract Glass frit compositions are shown that are lead-free, cadmium-free, and zinc-free, the compositions having improved chemical resistance, especially acid resistance (acetic acid) of a loss of generally less than about 1.9% by weight. The compositions contain B 2 O 3 , SiO 2 , ZrO 2 and rare earth oxides, the weight ratio of ZrO 2 to rare earth oxides being critical and being about 1/1 to 1.4/1.
Inventors
- 👤 Josef Francel
- 👤 Uriah Horn
- 👤 Daniel R. Stewart
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 21:34
CPC Classifications
C; C03; C03C; C03C8/00; C03C8/02; C03C8/10; C03C8/12; C03C3/00; C03C3/04; C03C3/062; C03C3/064; C03C3/068; C03C8/06
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
159 words
A glass frit composition having a fiber softening point of at least about 535° C., the composition being free of lead, cadmium, and zinc, the composition consisting essentially of the following components in approximate weight percents: ______________________________________
Component %
______________________________________
SiO.sub.2 25-32
B.sub.2 O.sub.3 25-32
ZrO.sub.2 10-18
Rare earth oxide 10-18
Li.sub.2 O 0-9
Na.sub.2 O 0-9
K.sub.2 O 0-5
SrO 0-6
F 0-3
CaO 0-3
SnO.sub.2 0-2
WO.sub.3 0-10
______________________________________ in which the ratio of ZrO 2 to rare earth oxide is about 1:1 to 1.4:1, the amount of ZrO 2 +rare earth oxide is about 20 to 33 and the amount of Li 2 O, K 2 O and Na 2 O is about 1 to 10, the composition having an alkali resistance of less than about 1% (5% sodium pyrophosphate at 60° C. for 8 hours) and an acid resistance of less than about 1.9% (4% by weight acetic acid for 24 hours at room temperature).
Claim 2
Dependent Claim
159 words
A glass frit composition having a fiber softening point of at least about 535° C., the composition being free of lead, cadmium, and zinc, the composition consisting essentially of the following components in approximate weight percents: ______________________________________
Component %
______________________________________
SiO.sub.2 25-32
B.sub.2 O.sub.3 25-32
ZrO.sub.2 10-18
Rare earth oxide 10-18
Li.sub.2 O 0-9
Na.sub.2 O 0-9
K.sub.2 O 0-5
SrO 0-6
F 0-3
CaO 0-3
SnO.sub.2 0-2
WO.sub.3 0-10
______________________________________ in which the ratio of ZrO 2 to rare earth oxide is about 1:1 to 1.4:1, the amount of ZrO 2 +rare earth oxide is about 20 to 33 and the amount of Li 2 O, K 2 O and Na 2 O is about 1 to 10, the composition having an alkali resistance of less than about 1% (5% sodium pyrophosphate at 60° C. for 8 hours) and an acid resistance of less than about 1.9% (4% by weight acetic acid for 24 hours at room temperature).
Claim 3
Dependent Claim
20 words
A composition as defined in claim 1 in which the rare earth oxide is a mixture of rare earth oxides.
Claim 4
Dependent Claim
25 words
A composition as defined in claim 1 in which the rare earth oxide is a mixture of La 2 O 3 and CeO 2 .
Claim 5
Dependent Claim
46 words
A composition as defined in claim 1 in which the rare earth oxide is a mixture of rare earth oxides of from about 5 to 40 parts by weight of La 2 O 3 and about 20 to 60 parts by weight of CeO 2 .
Claim 6
Dependent Claim
39 words
A composition as defined in claim 1 in which the rare earth oxide is a mixture of rare earth oxides of La 2 O 3 , CeO 2 , Nd 2 O 3 and Pr 2 O 3 .
Claim 7
Dependent Claim
45 words
A composition as defined in claim 1 in which the rare earth oxide is a mixture of rare earth oxides of La 2 O 3 , CeO 2 , Nd 2 O 3 and Pr 2 O 3 from bastnasite as a raw batch material.
Claim 8
Dependent Claim
37 words
A composition as defined in claim 1 in which the ratio of ZrO 2 to rare earth oxide is about 1.1/1 to 1.3/1, and the amount of ZrO 2 +rare earth oxide is about 30 to 33.
Claim 9
Dependent Claim
33 words
A composition as defined in claim 1 in which the composition has excellent physical and chemical properties, the coefficient of thermal expansion (0° to 300° C.×10 -7 /°C.) being about 71 to 78.
Claim 10
Dependent Claim
34 words
A composition as defined in claim 1 in which the composition is as follows: ______________________________________
Component
%
______________________________________
SiO.sub.2
27
B.sub.2 O.sub.3
29
ZrO.sub.2
18
Li.sub.2 O
7
SrO 4
La.sub.2 O.sub.3
15.
______________________________________
Claim 11
Dependent Claim
35 words
A composition as defined in claim 1 in which the composition is as follows: ______________________________________
Component
%
______________________________________
SiO.sub.2
28
B.sub.2 O.sub.3
30
ZrO.sub.2
18
LiO.sub.2
6
SrO 3
La.sub.2 O.sub.3
15
F 2.
______________________________________
Claim 12
Dependent Claim
36 words
A composition as defined in claim 1 in which the composition is as follows: ______________________________________
Component
%
______________________________________
SiO.sub.2
30
B.sub.2 O.sub.3
30
ZrO.sub.2
16
Li.sub.2 O
7
La.sub.2 O.sub.3
15
F 2
CaO 2.
______________________________________
Claim 13
Dependent Claim
34 words
A composition as defined in claim 1 in which the composition is as follows: ______________________________________
Component
%
______________________________________
SiO.sub.2
27
B.sub.2 O.sub.3
29
ZrO.sub.2
18
Li.sub.2 O
9
SrO 2
La.sub.2 O.sub.3
15.
______________________________________
Claim 14
Dependent Claim
36 words
A composition as defined in claim 1 in which the composition is as follows: ______________________________________
Component
%
______________________________________
SiO.sub.2
30
B.sub.2 O.sub.3
30
ZrO.sub.2
10
Li.sub.2 O
9
La.sub.2 O.sub.3
10
SnO.sub.2
3
WO.sub.3
8.
______________________________________
Claim 15
Dependent Claim
34 words
A composition as defined in claim 1 in which the composition is as follows: ______________________________________
Component
%
______________________________________
SiO.sub.2
27
B.sub.2 O.sub.3
29
ZrO.sub.2
18
Li.sub.2 O
8
SrO 5
La.sub.2 O.sub.3
13.
______________________________________
Claim 16
Dependent Claim
101 words
A glass frit composition having a fiber softening point of at least about 535° C., the composition being free of lead, cadmium, and zinc, the composition consisting essentially of the following components in parts by weight: ______________________________________
Components [Percent] Parts by Weight
______________________________________
SiO.sub.2 30
B.sub.2 O.sub.3 30
ZrO.sub.2 16
Na.sub.2 O 9
Rare earth oxide (bastnasite)
15
F 2
______________________________________ the composition having an alkali resistance of less than about 1% (5% sodium pyrophosphate at 60° C. for 8 hours) and an acid resistance of less than about 1.9% (4% by weight acetic acid for 24 hours at room temperature).
Claim 17
Dependent Claim
101 words
A glass frit composition having a fiber softening point of at least about 535° C., the composition being free of lead, cadmium, and zinc, the composition consisting essentially of the following components in parts by weight: ______________________________________
Components [Percent] Parts by Weight
______________________________________
SiO.sub.2 30
B.sub.2 O.sub.3 30
ZrO.sub.2 16
Na.sub.2 O 9
Rare earth oxide (bastnasite)
15
F 2
______________________________________ the composition having an alkali resistance of less than about 1% (5% sodium pyrophosphate at 60° C. for 8 hours) and an acid resistance of less than about 1.9% (4% by weight acetic acid for 24 hours at room temperature).
Claim 18
Dependent Claim
101 words
A glass frit composition having a fiber softening point of at least about 535° C., the composition being free of lead, cadmium, and zinc, the composition consisting essentially of the following components in parts by weight: ______________________________________
Components [Percent] Parts by Weight
______________________________________
SiO.sub.2 30
B.sub.2 O.sub.3 32
ZrO.sub.2 16
Na.sub.2 O 9
Rare earth oxide (bastnasite)
15
F 4
______________________________________ the composition having an alkali resistance of less than about 1% (5% sodium pyrophosphate at 60° C. for 8 hours) and an acid resistance of less than about 1.9% (4% by weight acetic acid for 24 hours at room temperature).
Claim 19
Dependent Claim
101 words
A glass frit composition having a fiber softening point of at least about 535° C., the composition being free of lead, cadmium, and zinc, the composition consisting essentially of the following components in parts by weight: ______________________________________
Components [Percent] Parts by Weight
______________________________________
SiO.sub.2 30
B.sub.2 O.sub.3 32
ZrO.sub.2 16
Na.sub.2 O 9
Rare earth oxide (bastnasite)
15
F 4
______________________________________ the composition having an alkali resistance of less than about 1% (5% sodium pyrophosphate at 60° C. for 8 hours) and an acid resistance of less than about 1.9% (4% by weight acetic acid for 24 hours at room temperature).
Claim 20
Dependent Claim
101 words
A glass frit composition having a fiber softening point of at least about 535° C., the composition being free of lead, cadmium, and zinc, the composition consisting essentially of the following components in parts by weight: ______________________________________
Components [Percent] Parts by Weight
______________________________________
SiO.sub.2 30
B.sub.2 O.sub.3 32
ZrO.sub.2 16
Na.sub.2 O 9
Rare earth oxide (bastnasite)
15
F 2
______________________________________ the composition having an alkali resistance of less than about 1% (5% sodium pyrophosphate at 60° C. for 8 hours) and an acid resistance of less than about 1.9% (4% by weight acetic acid for 24 hours at room temperature).
Claim 21
Dependent Claim
101 words
A glass frit composition having a fiber softening point of at least about 535° C., the composition being free of lead, cadmium, and zinc, the composition consisting essentially of the following components in parts by weight: ______________________________________
Components [Percent] Parts by Weight
______________________________________
SiO.sub.2 30
B.sub.2 O.sub.3 32
ZrO.sub.2 16
Na.sub.2 O 9
Rare earth oxide (bastnasite)
15
F 2
______________________________________ the composition having an alkali resistance of less than about 1% (5% sodium pyrophosphate at 60° C. for 8 hours) and an acid resistance of less than about 1.9% (4% by weight acetic acid for 24 hours at room temperature).
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-08-26 | 1989-02-25 | 1989-08-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-08-26 | 1993-02-25 | 1993-08-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-08-26 | 1997-02-25 | 1997-08-27 | $7700.00 | Window Closed / Lapsed |