Lead-free optical glasses

Details Lead-free optical glasses Lead-free optical glasses

2002-07-09

2004-04-06

Sample, David (Department: 1755)

Compositions: ceramic

Ceramic compositions

Glass compositions, compositions containing glass other than...

C501S057000, C501S903000

Reexamination Certificate

active

06716781

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to lead-free optical glasses with indices of refraction n
d
between 1.49 and 1.55 and with Abbé{acute over ( )} numbers &ngr;
d
between 47 and 59.
2. Description of the Related Art
Since the glass components PbO and As
2
O
3
have entered public discussion as being environmental pollutants, the manufacturers of optical instruments demand PbO-free and preferably also As
2
O
3
-free glasses having appropriate optical properties.
Simple replacement of the lead oxide by one or more ingredients is generally not a successful way of reproducing the desired optical and glass performance properties affected by PhO. Instead, new developments or substantial modifications to the glass composition are necessary.
Lead-free optical glasses having optical values in the above range and similar compositions are already known. However these glasses have various disadvantages.
DE 196 09 735 A1 describes crown flint glasses which have a high SiO
2
content and therefore are relatively difficult to melt and have high melting temperatures.
U.S. Pat. No. 3,940,278 describes a glass for optical glass fibers. Although its rather low SiO
2
content and rather high Al
2
O
3
content are a way to achieve the desired flow behavior at high temperatures and, chemical resistance, it is necessary to use very large amounts of Na
2
O and BaO in the glass. Because of these high levels of Na
2
O and BaO, these glasses become very susceptible to crystallization.
EP 0 645 349 A1 describes an optical glass consisting of the system SiO
2
—Nb
2
O
5
—R
2
O—F and further optional components. Because of its Nb
2
O
5
level of up to 15% by weight, the glass is very susceptible to crystallization.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a lead-free optical glass having a refractive index n
d
between 1.49 and 1.55 and an Abbé number &ngr;
d
between 47 and 59, which is inexpensive to produce, has good melting and processing properties and sufficient crystallization stability.
According to the invention the lead-free optical glass has an index of refraction (n
d
) between 1.49 and 1.55 and an Abbé{acute over ( )} number (&ngr;
d
) between 47 and 59, and comprises (in percent by weight on an oxide basis):
SiO
2
 60 to 70
Al
2
O
3
0.3 to 5
Na
2
O
 16 to 25
TiO
2
  0 to 9
ZrO
2
  0 to 7
Nb
2
O
5
  0 to <0.5
Ta
2
O
5
  0 to 7
F
  0 to 3
and optionally at least one fining agent in an amount sufficient for fining.
The glasses contain the glass-forming oxides SiO
2
(60-70 percent by weight) and Al
2
O
3
(0.3 to 5 percent by weight), SiO
2
being the main glass former. Preference is given to a minimum SiO
2
content of >60 percent by weight. If the above-mentioned maximum Al
2
O
3
content were exceeded, the devitrification tendency and the melting temperature would increase excessively. Preference is given to a maximum Al
2
O
3
content of <5% by weight. On the other hand, omission of this second glass former would lead to a reduction in chemical resistance. In total, the high glass former level of at least 60.3%, by weight and up to 75% by weight results in a relatively high viscosity.
This is counteracted by the high level of Na
2
O (16-25 percent by weight) which acts as fluxing agent for improving the meltability. In addition, the glass formers, in this ratio to the fluxing agent Na
2
O, have a beneficial influence on the glass “length” so that these glasses are easy to process. At even higher levels, in particular in the presence of TiO
2
and ZrO
2
, the crystallization tendency would be increased excessively. For the same reason, Li
2
O is completely omitted.
The glasses can contain both TiO
2
(up to 9 percent by weight) and ZrO
2
(up to 7 percent by weight). These two components improve the chemical resistance, but do not reduce the meltability as much as Al
2
O
3
. At higher levels, the crystallization stability would be substantially reduced, as with Al
2
O
3
. In addition, higher TiO
2
levels, together with the iron ion impurities in the glass, promote yellow discoloration of the glasses by formation of ilmenite.
The crystallization tendency is counteracted by the addition of both components, because in this case the potential pure crystal structure is disturbed, and therefore it is possible to incorporate higher total levels of both components than of a single component. In this way, it is also possible to counteract ilmenite formation and thus discoloration of the glasses. For these reasons, compositions, which contain both ingredients, are preferred in terms of crystallization stability.
Both components are also used in order to achieve the desired refractive index and dispersion range. Both components make it possible to establish a high refractive index at the same time as a low Abbé number. Here, it is likewise preferred to use both components in order to facilitate establishing a specific optical status by variation.
For this reason, the glasses according to the invention can additionally contain up to 7% by weight of Ta
2
O
5
and/or up to <0.5% by weight of Nb
2
O
5
. Higher levels of Nb
2
O
5
would increase the crystallization tendency of the glasses. In particularly preferred embodiments, the glasses are free from Nb
2
O
5
. At the above-mentioned levels, these components allow the optical status to be varied in particularly wide ranges with the same base glass composition. These components are in particular used in order to achieve medium Abbé numbers at particularly high refractive indices. Furthermore it is possible to achieve X-ray opacity in the glasses by using Ta
2
O
5
, just as by using TiO
2
or ZrO
2
, at higher levels within the claimed range. The glasses preferably contain at least two percent by weight of a sum total of TiO
2
+ZrO
2
+Ta
2
O
5
. It is thus already possible to obtain X-ray-opaque glass bodies from these glasses. In order to achieve adequate X-ray opacity, even at low thickness of the glass bodies, the glasses should contain a total of at least 4.5 percent by weight of these components. A further increase of their content would, in certain combinations of the three components determining the optical status, lead to n
d
and v
d
deviations from the desired values and to an unnecessary increase in batch price owing to the unneccesarily high Ta
2
O
5
levels. Furthermore, adequate potential X-ray opacity is already achieved with the claimed amounts.
It is therefore preferred that the sum total of TiO
2
, ZrO
2
and Ta
2
O
5
is no more than 15 percent by weight. Glasses having a TiO
2
+ZrO
2
+Ta
2
O
5
content of between 2 and 15 percent by weight have refractive indices n
d
between 1.50 and 1.55 and Abbé numbers &ngr;
d
between 47 and 57.
For precise adjustment and thus to counterbalance the components adjusting the low Abbé numbers at the same time as high refractive indices, the glasses can contain up to 3 percent by weight of F. In addition, low amounts of F increase transmission by suppressing ilmenite formation (complex formation with Fe
III
) and can have an additional fining effect, so that these glasses have significantly fewer bubble defects than comparable glasses containing no F.
In order to improve the glass quality, one or more fining agents known per se can be added to the batch in conventional amounts in order to refine the glass. The glass then has a particularly good internal quality with respect to freedom from bubbles and streaks.
If the fining agent used is not As
2
O
3
, but instead, for example, Sb
2
O
3
, which is possible without losses regarding the glass quality, the glasses, which are lead-free according to the invention, are in addition free from arsenic, except for trace arsenic oxide impurities. The Sb
2
O
3
content is preferably between 0.1 and 0.5 percent by weight.
Within the above-mentioned composition range, there are various groups of particularly preferred composition ranges.
On the one hand, in particularly prefe

Affiliated with

Also associated with

Rating

Lead-free optical glasses does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Lead-free optical glasses, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Lead-free optical glasses will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3215128