U.S. patent application number 13/684632 was filed with the patent office on 2013-05-30 for colored alkali aluminosilicate glass articles.
The applicant listed for this patent is John Christopher Mauro, Marcel Potuzak. Invention is credited to John Christopher Mauro, Marcel Potuzak.
Application Number | 20130136909 13/684632 |
Document ID | / |
Family ID | 47428997 |
Filed Date | 2013-05-30 |
United States Patent
Application |
20130136909 |
Kind Code |
A1 |
Mauro; John Christopher ; et
al. |
May 30, 2013 |
COLORED ALKALI ALUMINOSILICATE GLASS ARTICLES
Abstract
A glass article including at least about 40 mol % SiO.sub.2 and,
optionally, a colorant imparting a preselected color is disclosed.
In general, the glass includes, in mol %, from about 40-70
SiO.sub.2, 0-25 Al.sub.2O.sub.3, 0-10 B.sub.2O.sub.3; 5-35
Na.sub.2O, 0-2.5 K.sub.2O, 0-8.5 MgO, 0-2 ZnO, 0-10% P.sub.2O.sub.5
and 0-1.5 CaO. As a result of ion exchange, the glass includes a
compressive stress (.sigma..sub.s) at at least one surface and,
optionally, a color. In one method, communicating a colored glass
with an ion exchange bath imparts .sigma..sub.s while in another;
communicating imparts .sigma..sub.s and a preselected color. In the
former, a colorant is part of the glass batch while in the latter;
it is part of the bath. In each, the colorant includes one or more
metal containing dopants formulated to impart to a preselected
color. Examples of one or more metal containing dopants include one
or more transition and/or rare earth metals.
Inventors: |
Mauro; John Christopher;
(Corning, NY) ; Potuzak; Marcel; (Corning,
NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mauro; John Christopher
Potuzak; Marcel |
Corning
Corning |
NY
NY |
US
US |
|
|
Family ID: |
47428997 |
Appl. No.: |
13/684632 |
Filed: |
November 26, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61565196 |
Nov 30, 2011 |
|
|
|
Current U.S.
Class: |
428/220 ;
428/410; 65/30.14 |
Current CPC
Class: |
Y10T 428/315 20150115;
C03C 21/002 20130101; C03C 3/11 20130101; C03C 3/087 20130101; C03C
4/02 20130101 |
Class at
Publication: |
428/220 ;
428/410; 65/30.14 |
International
Class: |
C03C 4/02 20060101
C03C004/02; C03C 21/00 20060101 C03C021/00 |
Claims
1. A colored glass formulated to be ion exchangeable comprising: a.
one or more metal containing dopants formulated to impart a
preselected color; b. following an ion exchange treatment (IOX) up
to about 64 hours: i. having at least one surface under a
compressive stress (.sigma..sub.s) comprising at least about 500
MPa; ii. the at least one surface under the compressive stress
(.sigma..sub.s) exhibiting a depth of layer (DOL) comprising at
least about 15 .mu.m; and iii. a color difference (.DELTA.E) in the
CIELAB color coordinates space of the preselected color of the
colored glass after IOX treatment and before IOX treatment
determined from specular transmittance measurements using a
spectrophotometer comprising: 7. up to about 8.2 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant A; or 8. up to about 9.1 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant F02; or 9. up to about 8.4 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant D65; or 10. up to about 5.2 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant A; or 11. up to about 6.3 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant F02; or 12. up to about 6.5 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant D65; and c. SiO.sub.2 comprising at least
about 40 mol %.
2. The colored glass of claim 1, further comprising
Al.sub.2O.sub.3; at least one alkali metal oxide of the form
R.sub.2O, wherein R comprises one or more of Li, Na, K, Rb, and Cs;
and one or more of B.sub.2O.sub.3, K.sub.2O, MgO, ZnO, and
P.sub.2O.sub.5.
3. The colored glass of claim 1, wherein: c. SiO.sub.2 comprises
from about 40 mol % to about 70 mol %; d. Al.sub.2O.sub.3 comprises
from about 0 mol % to about 25 mol %; e. B.sub.2O.sub.3 comprises
from 0 mol % to about 10 mol %; f. Na.sub.2O comprises from about 5
mol % to about 35 mol %; g. K.sub.2O comprises from 0 mol % to
about 2.5 mol %; h. MgO comprises from 0 mol % to about 8.5 mol %;
i. ZnO comprises from 0 mol % to about 2 mol %; j. P.sub.2O.sub.5
comprises from about 0 to about 10%; k. CaO comprises from 0 mol %
to about 1.5 mol %; l. Li.sub.2O comprises from 0 mol % to about 20
mol %; m. Rb.sub.2O comprises from 0 mol % to about 20 mol %; and
n. Cs.sub.2O comprises from 0 mol % to about 20 mol %.
4. The colored glass of claim 1, wherein one or more metal
containing dopants formulated to impart a preselected color
comprises one or more of transition metals, one or more of rare
earth metals, or one or more of transition metals and one or more
of rare earth metals.
5. The colored glass of claim 4, wherein one or more metal
containing dopants sources comprises one or more of one or more of
Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Ce, Pr, Nd, Sm, Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yb, and Lu.
6. The colored glass of claim 1, wherein one or more metal
containing dopants formulated to impart a preselected color
comprises one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, and V.
7. The colored glass of claim 2, wherein a sum of the mol % of
R.sub.2O+Al.sub.2O.sub.3+MgO+ZnO comprises at least about 25 mol
%.
8. The colored glass of claim 1, wherein the ion exchange treatment
(IOX) is at between about 350.degree. C. and 500.degree. C. for
between about 1 hours and 64 hours.
9. The colored glass of claim 1, wherein: iii. the color difference
(.DELTA.E) in the CIELAB color coordinate space of the preselected
color of the colored glass after IOX treatment and before IOX
treatment determined from specular transmittance measurements using
a spectrophotometer comprises: 7. up to about 3.5 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant A; or 8. up to about 3.6 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant F02; or 9. up to about 3.3 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant D65; or 10. up to about 5.2 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant A; or 11. up to about 6.3 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant F02; or 12. up to about 6.5 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant D65; and
10. The colored glass of claim 1, wherein the colored glass
comprises a glass article comprising a thickness of up to about 1
mm.
11. The colored glass of claim 1, further comprising at least one
fining agent comprising one or more of F, Cl, Br, I,
As.sub.2O.sub.3, Sb.sub.2O.sub.3, CeO.sub.2, SnO.sub.2, and
combinations thereof.
12. A method of making a glass article having at least one surface
under a compressive stress (.sigma..sub.s), the at least one
surface under the compressive stress (.sigma..sub.s) exhibiting a
depth of layer (DOL), and a preselected colored at least one
surface, the method comprising communicating at least one surface
of an aluminosilicate glass article comprising SiO.sub.2 comprising
at least about 40 mol % and a bath comprising one or more metal
containing dopant sources and formulated to impart the preselected
color to the aluminosilicate glass article by an ion exchange
treatment of the aluminosilicate glass article at a temperature
between about 350.degree. C. and about 500.degree. C. for a
sufficient time up to about 64 hours to impart the compressive
stress (.sigma..sub.s), the depth of layer (DOL), and the
preselected color at least one surface of the aluminosilicate
glass.
13. The method of claim 12, wherein the compressive stress
(.sigma..sub.s) comprising at least about 500 MPa and the at least
one surface under the compressive stress (.sigma..sub.s) exhibits a
depth of layer (DOL) comprising at least about 15 .mu.m.
14. The method of claim 12, wherein the aluminosilicate glass
comprises: a. SiO.sub.2 comprises from about 40 mol % to about 70
mol %; b. Al.sub.2O.sub.3 comprises from about 0 mol % to about 25
mol %; c. B.sub.2O.sub.3 comprises from 0 mol % to about 10 mol %;
d. Na.sub.2O comprises from about 5 mol % to about 35 mol %; e.
K.sub.2O comprises from 0 mol % to about 2.5 mol %; f. MgO
comprises from 0 mol % to about 8.5 mol %; g. ZnO comprises from 0
mol % to about 2 mol %; h. P.sub.2O.sub.5 comprises from about 0 to
about 10%; i. CaO comprises from 0 mol % to about 1.5 mol %; j.
Li.sub.2O comprises from 0 mol % to about 20 mol %; k. Rb.sub.2O
comprises from 0 mol % to about 20 mol %; and l. Cs.sub.2O
comprises from 0 mol % to about 20 mol %.
15. The method of claim 12, wherein the bath comprises a
composition comprising (1) one or more salts comprising a
strengthening ion source, optionally: (a) when the aluminosilicate
glass comprises a lithium aluminosilicate glass the one or more
strengthening ion sources comprise one or more ions of sodium
(Na.sup.+), potassium (K.sup.+), rubidium (Rb.sup.+), and/or cesium
(Cs.sup.+) exchangeable for lithium (Li.sup.+) ions; or (b) when
the aluminosilicate glass comprises a sodium aluminosilicate glass
the one or more strengthening ion sources comprise one or more ions
of potassium (K.sup.+), rubidium (Rb.sup.+), and/or cesium
(Cs.sup.+) exchangeable for sodium (Na.sup.+) ions; or (c) when the
aluminosilicate glass comprises a potassium aluminosilicate glass
the one or more strengthening ion sources comprise one or more ions
of rubidium (Rb.sup.+), and/or cesium (Cs.sup.+) exchangeable for
potassium (K.sup.+); (2) the one or more metal containing dopant
sources, and (3) a melting temperature less than or equal to the
ion exchange treatment temperature.
16. The method of claim 12, wherein the one or more metal
containing dopants sources comprises one or more of transition
metals, one or more of rare earth metals, or one or more of
transition metals and one or more of rare earth metals.
17. The method of claim 16, wherein the one or more metal
containing dopants sources comprises one or more of one or more of
Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Ce, Pr, Nd, Sm, Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yb, and Lu.
18. The method of claim 12, wherein the one or more metal
containing dopants sources comprises one or more of one or more of
Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, and V.
19. The method of claim 12, wherein the one or more salts comprises
a formulation comprising one or more of a halide, cyanide,
carbonate, chromate, a nitrogen oxide radical, manganate,
molybdate, chlorate, sulfide, sulfite, sulfate, vanadyl, vanadate,
tungstate, and combinations of two or more of the proceeding.
20. The method of claim 19, wherein the one or more salts comprises
a formulation comprising one or more of a metal halide, carbonate,
chromate, a nitrate, manganate, sulfide, sulfite, sulfate, vanadyl,
vanadate, and combinations of two or more of the proceeding.
21. A method of making a colorfast, ion exchangeable glass
comprising: a. forming a glass composition comprising: i. SiO.sub.2
comprising at least about 40 mol %; ii. Al.sub.2O.sub.3; and iii.
one or more metal containing dopants in amounts formulated to
impart a preselected color, wherein following an ion exchange
treatment (10.times.) up to about 64 hours, the ion exchanged glass
article comprises 1. at least one surface under a compressive
stress (.sigma..sub.s) comprising at least about 500 MPa; 2. the at
least one surface under the compressive stress (.sigma..sub.s)
exhibiting a depth of layer (DOL) comprising at least about 15
.mu.m; and 3. a color difference
(.DELTA.E=[{.DELTA.L*}.sup.2+{.DELTA.*}.sup.2+{.DELTA.b*}.sup.2].sup.0.5)
in the CIELAB color space coordinates of the preselected color of
the colored glass after IOX treatment and before IOX treatment
determined from specular transmittance measurements using a
spectrophotometer comprising: a. up to about 8.2 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant A; or b. up to about 9.1 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant F02; or c. up to about 8.4 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant D65; or d. up to about 5.2 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant A; or e. up to about 6.3 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant F02; or f. up to about 6.5 when measurement
results obtained between about 360 nm-750 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant D65.
22. The method of making the colorfast, ion exchangeable glass of
claim 21, wherein the glass composition further comprising at least
one alkali metal oxide of the form R.sub.2O, wherein R comprises
one or more of Li, Na, K, Rb, and Cs; and one or more of
B.sub.2O.sub.3, K.sub.2O, MgO, ZnO, and P.sub.2O.sub.5.
23. The method of making the colorfast, ion exchangeable glass of
claim 21, wherein: i. SiO.sub.2 comprises from about 40 mol % to
about 70 mol %; ii. Al.sub.2O.sub.3 comprises from about 0 mol % to
about 25 mol %; iii. B.sub.2O.sub.3 comprises from 0 mol % to about
10 mol %; iv. Na.sub.2O comprises from about 5 mol % to about 35
mol %; v. K.sub.2O comprises from 0 mol % to about 2.5 mol %; vi.
MgO comprises from 0 mol % to about 8.5 mol %; vii. ZnO comprises
from 0 mol % to about 2 mol %; viii. P.sub.2O.sub.5 comprises from
about 0 to about 10%; ix. CaO comprises from 0 mol % to about 1.5
mol %; x. Li.sub.2O comprises from 0 mol % to about 20 mol %; xi.
Rb.sub.2O comprises from 0 mol % to about 20 mol %; and xii.
Cs.sub.2O comprises from 0 mol % to about 20 mol %.
24. The method of making the colorfast, ion exchangeable glass of
claim 21, wherein the one or more metal containing dopants
formulated to impart a preselected color comprises one or more of
transition metals, one or more of rare earth metals, or one or more
of transition metals and one or more of rare earth metals.
25. The method of making the colorfast, ion exchangeable glass of
claim 24, wherein the one or more metal containing dopants sources
comprises one or more of one or more of Au, Ag, Cu, Ni, Co, Fe, Mn,
Cr, V, Ti, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and
Lu.
26. The method of making the colorfast, ion exchangeable glass of
claim 21, wherein the one or more metal containing dopants
formulated to impart a preselected color comprises one or more of
Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, and V.
27. The method of making the colorfast, ion exchangeable glass of
claim 22, wherein a sum of the mol % of
R.sub.2O+Al.sub.2O.sub.3+MgO+ZnO comprises at least about 25 mol %.
Description
[0001] This application claims the benefit of priority under 35
U.S.C. .sctn.119 of U.S. Provisional Application Ser. No.
61/565,196 filed on Nov. 30, 2011 the content of which is relied
upon and incorporated herein by reference in its entirety.
BACKGROUND
[0002] 1. Field
[0003] Aspects of embodiments and/or embodiments of this disclosure
generally relate to the field of glass materials technology and
more specifically to the field of alkali aluminosilicate glass
materials technology. Also, aspects of embodiments and/or
embodiments of this disclosure are directed to one or more of: an
ion exchangeable colored glass composition that substantially
maintains its original color following an ion exchange treatment;
an ion exchangeable, colorable glass composition to which a
preselected color can be imparted by an ion exchange treatment; an
ion exchanged (IOX) colored glass composition; an article or
machine or equipment of or including an IOX colored glass
composition; and one or more processes for making an IOX colored
glass composition.
[0004] 2. Technical Background
[0005] Glass articles are commonly utilized in a variety of
consumer and commercial applications such as electronic
applications, automotive applications, and even architectural
applications. For example, consumer electronic devices, such as
mobile phones, computer monitors, GPS devices, televisions and the
like, commonly incorporate glass substrates as part of a display.
In some of these devices, the glass substrate is also utilized to
enable touch functionality, such as when the displays are touch
screens. As many of these devices are portable, it can be desirable
that the glass articles incorporated in such devices be
sufficiently robust to tolerate impact and/or damage, such as
scratches and the like, during both use and transport.
[0006] Corning GORILLA.RTM. glass, a clear alkali aluminosilicate
glass, has been a successful product due to its ability to achieve
high strength and damage resistance. To date, this alkali
aluminosilicate glass has been primarily used for applications that
require transmission of visible light. However, new potential
applications relating to product color(s) and/or aesthetics as not
addressed by clear alkali aluminosilicate glasses.
[0007] The problem(s) of attaining product color(s) and/or
aesthetics are solved by one or more ion exchangeable colored glass
compositions that substantially maintain their original color
following an ion exchange treatment (IOX); one or more ion
exchangeable, colorable glass compositions to which one or more
preselected colors can be imparted by an ion exchange treatment
(IOX); one or more ion exchanged (IOX) colored glass compositions;
and one or more processes for making one or more IOX colored glass
compositions. Such one or more ion exchangeable colored glass
compositions and/or one or more ion exchangeable, colorable glass
compositions can combine the ion exchangeability characteristics of
GORILLA.RTM. glass with the depth and breadth colors found in
stained art glass. In aspects, such one or more ion exchangeable
colored glass compositions exhibit colorfastness following an ion
exchange treatment (IOX). Also, such one or more IOX colored glass
compositions combine the high strength and damage resistance of
GORILLA.RTM. glass with the depth and breadth colors found in
stained art glass. To that end, the forgoing one or more glass
compositions might be utilized and/or incorporated, for example, in
personal electronic devices as an underside or backplates and/or
household appliances as protective shells/casings.
[0008] Additionally, the problem(s) of attaining product color(s)
and/or aesthetics on an industrial scale are solved by the forgoing
one or more glass compositions being compatible with large-scale
sheet glass manufacturing methods, such as down-draw processes and
slot-draw processes that are commonly used today in the manufacture
thin glass substrates, for example, for incorporation into
electronic devices.
SUMMARY
[0009] Some aspects of embodiments and/or embodiments of this
disclosure relate to one or more ion exchangeable colored glass
compositions that substantially maintain their original color
following an ion exchange treatment (IOX); one or more ion
exchangeable, colorable glass compositions to which one or more
preselected colors can be imparted by an ion exchange treatment
(IOX); one or more IOX colored glass compositions; and one or more
processes for making one or more IOX colored glass
compositions.
[0010] As to some aspects relating to compositions, such one or
more ion exchangeable colored glass compositions and/or such one or
more ion exchangeable, colorable glass compositions and/or such one
or more IOX colored glass compositions included at least about 40
mol % SiO.sub.2. As to other aspects, such one or more ion
exchangeable colored glass compositions and/or such one or more IOX
colored glass compositions include one or more metal containing
dopants formulated to impart a preselected color (e.g., any one or
more of any of preselected hue {e.g., shades of red, orange,
yellow, green, blue, and violet}, preselected saturation,
preselected brightness, and/or preselected gloss).
[0011] As to other aspects, such one or more ion exchangeable
colored glass compositions and/or such one or more ion
exchangeable, colorable glass compositions are formulated so that,
following an ion exchange treatment (IOX), for example, up to about
64 hours, the IOX colored glass has at least one surface under a
compressive stress (.sigma..sub.s) of at least about 500 MPa and a
depth of layer (DOL) of at least about 15 .mu.m.
[0012] As to aspects relating to one or more ion exchangeable
colored glass compositions, such compositions are formulated so
that, following an ion exchange treatment (IOX) up to about 64
hours, the color substantially retains its original hue without
fading or running (e.g., is substantially color fast). In aspects
relating to substantial color retention, a color difference in the
CIELAB color space coordinates of a preselected color of such one
or more ion exchangeable glass compositions after an IOX treatment
and before the IOX treatment may be characterized by
.DELTA.E=[{.DELTA.L*}.sup.2+{.DELTA.a*}.sup.2+{.DELTA.b*}.sup.2].sup.0-
.5 determined from specular transmittance measurements using a
spectrophotometer.
[0013] Returning to aspects relating to compositions, such one or
more ion exchangeable colored glass compositions and/or such one or
more ion exchangeable, colorable glass compositions and/or such one
or more IOX colored glass compositions also might include SiO.sub.2
from about 40 mol % to about 70 mol %; Al.sub.2O.sub.3 comprises
from about 0 mol % to about 25 mol %; B.sub.2O.sub.3 comprises from
0 mol % to about 10 mol %; Na.sub.2O comprises from about 5 mol %
to about 35 mol %; K.sub.2O comprises from 0 mol % to about 2.5 mol
%; MgO comprises from 0 mol % to about 8.5 mol %; ZnO comprises
from 0 mol % to about 2 mol %; P.sub.2O.sub.5 comprises from about
0 to about 10%; CaO comprises from 0 mol % to about 1.5 mol %;
Rb.sub.2O comprises from 0 mol % to about 20 mol %; and Cs.sub.2O
comprises from 0 mol % to about 20 mol %. It will be appreciated
that one of more sub-ranges of any one or more of the preceding are
contemplated.
[0014] Other aspects of embodiments and/or embodiments of this
disclosure relate to a method of making a colored glass article
having at least one surface under a compressive stress
(.sigma..sub.s) and a depth of layer (DOL) and a preselected
colored. Such method can include communicating at least one surface
of an aluminosilicate glass article, which has SiO.sub.2 at least
about 40 mol %, and a bath including one or more metal containing
dopant sources and in amounts formulated to impart a preselected
color to the aluminosilicate glass article by an ion exchange
treatment of the aluminosilicate glass article at a temperature,
for example, between about 350.degree. C. and about 500.degree. C.
for a sufficient time up to about 64 hours to impart the
compressive stress (.varies..sub.s), the depth of layer (DOL), and
the preselected color at the at least one surface of the
aluminosilicate glass. It will be appreciated, that in some other
aspects, the compressive stress (.sigma..sub.s) might be at least
about 500 MPa while the depth of layer (DOL) might at least about
15 .mu.m. In aspects, a bath is formulated using one or more salts
including one or more strengthening ion sources, such as, for
example, a potassium source; the one or more metal containing
dopant sources; and a melting temperature less than or equal to the
ion exchange treatment temperature. In other aspects, the one or
more salts might be a formulation of one or more of a metal halide,
cyanide, carbonate, chromate, a nitrogen oxide radical, manganate,
molybdate, chlorate, sulfide, sulfite, sulfate, vanadyl, vanadate,
tungstate, and combinations of two or more of the proceeding,
alternatively, a formulation of one or more of a metal halide,
carbonate, chromate, a nitrate, manganate, sulfide, sulfite,
sulfate, vanadyl, vanadate, and combinations of two or more of the
proceeding.
[0015] In any aspects relating to one or more ion exchangeable
colored glass compositions that substantially maintain their
original color following an IOX; one or more ion exchangeable,
colorable glass compositions to which one or more preselected
colors can be imparted by an IOX; one or more IOX colored glass
compositions; and/or one or more processes for making one or more
IOX colored glass compositions, an ion exchange treatment (IOX)
might be performed at between about 350.degree. C. and 500.degree.
C. and/or between about 1 hour and 64 hours.
[0016] Also in any aspects relating to such one or more ion
exchangeable colored glass compositions and/or such one or more ion
exchangeable, colorable glass compositions and/or such one or more
IOX colored glass compositions, a glass article having a thickness
of up to about 1 mm or more might be made using such
compositions.
[0017] In any aspects relating to one or more ion exchangeable
colored glass compositions that substantially maintain their
original color following an IOX; one or more ion exchangeable,
colorable glass compositions to which one or more preselected
colors can be imparted by an IOX; one or more IOX colored glass
compositions; and/or one or more processes for making one or more
IOX colored glass compositions, a colorant might include one or
more metal containing dopants in amounts formulated to impart a
preselected color (e.g., any one or more of any of preselected hue
{e.g., shades of red, orange, yellow, green, blue, and violet},
preselected saturation, preselected brightness, and/or preselected
gloss) to the glass. Such one or more metal containing dopants
include, in some aspects, one or more of transition metals, one or
more of rare earth metals, or one or more of transition metals and
one or more of rare earth metals; in other aspects, one or more of
one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; in still other
aspects, one or more metal containing dopants formulated to impart
a preselected color comprises one or more of Au, Ag, Cu, Ni, Co,
Fe, Mn, Cr, and V.
[0018] Yet other aspects of embodiments and/or embodiments of this
disclosure relate to one or more methods of making one or more
colorfast, ion exchangeable glass compositions as disclosed and
described herein. In some aspect, the one or more methods impart
the one or more glass articles with a layer under a compressive
stress (.sigma..sub.s) and a depth of layer (DOL), the layer
extending from a surface of the glass article toward the depth of
layer. The one or more methods can involve subjecting at one
surface of an alkali aluminosilicate glass article to an ion
exchanging bath at a temperature of up to about 500.degree. C. for
up to about 64 hours, optionally, up to about 16 hours, for a
sufficient time to form the layer. In further aspects, the bath can
comprise at least at least a colorant including one or more metal
containing dopants formulated to impart a preselected color as
disclosed and described herein.
[0019] Numerous other aspects of embodiments, embodiments,
features, and advantages of this disclosure will appear from the
following description and the accompanying drawings. In the
description and/or the accompanying drawings, reference is made to
exemplary aspects of embodiments and/or embodiments of this
disclosure which can be applied individually or combined in any way
with each other. Such aspects of embodiments and/or embodiments do
not represent the full scope of this disclosure. Reference should
therefore be made to the claims herein for interpreting the full
scope of this disclosure. In the interest of brevity and
conciseness, any ranges of values set forth in this specification
contemplate all values within the range and are to be construed as
support for claims reciting any sub-ranges having endpoints which
are real number values within the specified range in question. By
way of a hypothetical illustrative example, a recitation in this
disclosure of a range of from about 1 to 5 shall be considered to
support claims to any of the following ranges: 1-5; 1-4; 1-3; 1-2;
2-5; 2-4; 2-3; 3-5; 3-4; and 4-5. Also in the interest of brevity
and conciseness, it is to be understood that such terms as "is,"
"are," "includes," "having," "comprises," and the like are words of
convenience and are not to be construed as limiting terms and yet
may encompass the terms "comprises," "consists essentially of,"
"consists of," and the like as is appropriate.
[0020] These and other aspects, advantages, and salient features of
this disclosure will become apparent from the following
description, the accompanying drawings, and the appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The drawings referenced herein form a part of the
specification. Features shown in the drawings are meant to be
illustrative of some, but not all, embodiments of this disclosure,
unless otherwise explicitly indicated, and implications to the
contrary are otherwise not to be made. Although like reference
numerals correspond to similar, though not necessarily identical,
components and/or features in the drawings, for the sake of
brevity, reference numerals or features having a previously
described function may not necessarily be described in connection
with other drawings in which such components and/or features
appear.
[0022] FIG. 1 shows a matrix of photographs (which have been
converted from color to black-gray-white) illustrating a retention
of original hue without fading or running (e.g., colorfastness) of
ion exchangeable colored glass compositions and IOX colored glass
compositions made according to aspects of embodiments and/or
embodiments of this disclosure;
[0023] FIG. 2 shows the compressive stress (.sigma..sub.s) as a
function of ion exchange treatment (IOX) time (t [h]) at
410.degree. C. for substrates of IOX colored glass compositions
(i.e., Samples 1-18) according to aspects of embodiments and/or
embodiments of this disclosure;
[0024] FIG. 3 shows the depth of layer (DOL) as a function of IOX
time (t [h]) at 410.degree. C. for the substrates of IOX colored
glass compositions (i.e., Samples 1-18) of FIG. 2 according to
aspects of embodiments and/or embodiments of this disclosure;
[0025] FIG. 4 shows the transmittance [%] as a function of
wavelength, .lamda. [nm], for the substrates of IOX colored glass
compositions (i.e., Samples 1-6) made by an IOX at 410.degree. C.
for 2 [h] according to aspects of embodiments and/or embodiments of
this disclosure;
[0026] FIG. 5 shows the transmittance [%] as a function of
wavelength, .lamda. [nm], for substrates of ion exchangeable Glass
A colored using a iron (Fe) dopant and corresponding IOX colored
glass compositions IOX at 450.degree. C. for 2 [h], 410.degree. C.
for 32 [h], and 410.degree. C. for 64 [h] (i.e., Samples 19, 25,
& 31, respectively) of FIG. 1 according to aspects of
embodiments and/or embodiments of this disclosure;
[0027] FIG. 6 shows the transmittance [%] as a function of
wavelength, .lamda. [nm], for substrates of ion exchangeable Glass
B colored using a vanadium (V) dopant and corresponding IOX colored
glass compositions IOX at 450.degree. C. for 2 [h], 410.degree. C.
for 32 [h], and 410.degree. C. for 64 [h] (i.e., Samples 20, 26,
& 32, respectively) of FIG. 1 according to aspects of
embodiments and/or embodiments of this disclosure;
[0028] FIG. 7 shows the transmittance [%] as a function of
wavelength, .lamda. [nm], for substrates of ion exchangeable Glass
C colored using a chromium (Cr) dopant and corresponding IOX
colored glass compositions IOX at 450.degree. C. for 2 [h],
410.degree. C. for 32 [h], and 410.degree. C. for 64 [h] (i.e.,
Samples 21, 27, & 33, respectively) of FIG. 1 according to
aspects of embodiments and/or embodiments of this disclosure;
[0029] FIG. 8 shows the transmittance [%] as a function of
wavelength, .lamda. [nm], for substrates of ion exchangeable Glass
D colored using a cobalt (Co) dopant and corresponding IOX colored
glass compositions IOX at 450.degree. C. for 2 [h], 410.degree. C.
for 32 [h], and 410.degree. C. for 64 [h] (i.e., Samples 22, 28,
& 34, respectively) of FIG. 1 according to aspects of
embodiments and/or embodiments of this disclosure;
[0030] FIG. 9 shows the transmittance [%] as a function of
wavelength, .lamda. [nm], for substrates of ion exchangeable Glass
E colored using a copper (Co) dopant and corresponding IOX colored
glass compositions IOX at 450.degree. C. for 2 [h], 410.degree. C.
for 32 [h], and 410.degree. C. for 64 [h] (i.e., Samples 23, 29,
& 35, respectively) of FIG. 1 according to aspects of
embodiments and/or embodiments of this disclosure;
[0031] FIG. 10 shows the transmittance [%] as a function of
wavelength, .lamda. [nm], for substrates of ion exchangeable Glass
F colored using a gold (Au) dopant and corresponding IOX colored
glass compositions IOX at 450.degree. C. for 2 [h], 410.degree. C.
for 32 [h], and 410.degree. C. for 64 [h] (i.e., Samples 24, 30,
& 36, respectively) of FIG. 1 according to aspects of
embodiments and/or embodiments of this disclosure;
[0032] FIG. 11 shows the internal absorbance [%] for a 1 mm path
length as a function of wavelength, .lamda. [nm], for substrates of
10.times. glass compositions (i.e., Samples 37-61 made using ion
exchangeable clear Glass G) colored using a silver (Ag) dopant by
IOX at 410.degree. C. for 8 [h] using a 5 wt % AgNO.sub.3-95 wt %
KNO.sub.3 bath according to aspects of embodiments and/or
embodiments of this disclosure; and
[0033] FIG. 12 shows a detail of the internal absorbance [%] for a
1 mm path length as a function of wavelength, .lamda. [nm], of FIG.
11 for substrates of 10.times. glass compositions (i.e., Samples
37-61 made using ion exchangeable clear Glass G) colored using a
silver (Ag) dopant by IOX at 410.degree. C. for 8 [h] using a 5 wt
% AgNO.sub.3-95 wt % KNO.sub.3 bath according to aspects of
embodiments and/or embodiments of this disclosure
DETAILED DESCRIPTION
[0034] In the following description of exemplary aspects of
embodiments and/or embodiments of this disclosure, reference is
made to the accompanying drawings that form a part hereof, and in
which are shown by way of illustration specific aspects of
embodiments and/or embodiments in which this disclosure may be
practiced. While these aspects of embodiments and/or embodiments
are described in sufficient detail to enable those skilled in the
art to practice this disclosure, it will nevertheless be understood
that no limitation of the scope of this disclosure is thereby
intended. Alterations and further modifications of the features
illustrated herein, and additional applications of the principles
illustrated herein, which would occur to one skilled in the
relevant art and having possession of this disclosure, are to be
considered within the scope of this disclosure. Specifically, other
aspects of embodiments and/or embodiments may be utilized, logical
changes (e.g., without limitation, any one or more of chemical,
compositional {e.g., without limitation, any one or more of
chemicals, materials, . . . and the like}, electrical,
electrochemical, electromechanical, electro-optical, mechanical,
optical, physical, physiochemical, . . . and the like) and other
changes may be made without departing from the spirit or scope of
this disclosure. Accordingly, the following description is not to
be taken in a limiting sense and the scope of aspects of
embodiments and/or embodiments of this disclosure are defined by
the appended claims. It is also understood that terms such as
"top," "bottom," "outward," "inward," . . . and the like are words
of convenience and are not to be construed as limiting terms. Also,
unless otherwise specified herein, a range of values includes both
the upper and lower limits of the range. For example, a range of
about 1-10 mol % includes the values of 1 mol % and 10 mol %.
[0035] As noted, various aspects of embodiments and/or embodiments
of this disclosure relate to an article and/or machine or equipment
formed from and/or including one or more IOX colored glass
compositions of this disclosure. As one example, an ion
exchangeable, colored glass compositions; ion exchangeable,
colorable glass compositions; and/or IOX colored glass compositions
might be used in a variety of electronic devices or portable
computing devices, which might be configured for wireless
communication, such as, computers and computer accessories, such
as, "mice", keyboards, monitors (e.g., liquid crystal display
(LCD), which might be any of cold cathode fluorescent lights
(CCFLs-backlit LCD), light emitting diode (LED-backlit LCD) . . .
etc, plasma display panel (PDP) . . . and the like), game
controllers, tablets, thumb drives, external drives, whiteboards .
. . etc.; personal digital assistants (PDAs); portable navigation
device (PNDs); portable inventory devices (PIDs); entertainment
devices and/or centers, devices and/or center accessories such as,
tuners, media players (e.g., record, cassette, disc, solid-state .
. . etc.), cable and/or satellite receivers, keyboards, monitors
(e.g., liquid crystal display (LCD), which might be any of cold
cathode fluorescent lights (CCFLs-backlit LCD), light emitting
diode (LED-backlit LCD) . . . etc, plasma display panel (PDP) . . .
and the like), game controllers . . . etc.; electronic reader
devices or e-readers; mobile or smart phones . . . etc. As
alternative examples, an ion exchangeable, colored glass
compositions; ion exchangeable, colorable glass compositions;
and/or IOX colored glass compositions might be used in automotive,
appliances, and even architectural applications. To that end, it is
desirable that such ion exchangeable, colored glass compositions
and ion exchangeable, colorable glass compositions are formulated
to have a sufficiently low softening point and a sufficiently low
coefficient of thermal expansion so as to be compatible with to
shaping into complex shapes.
[0036] As to some aspects relating to compositions, such one or
more ion exchangeable colored glass compositions and/or such one or
more ion exchangeable, colorable glass compositions and/or such one
or more IOX colored glass compositions included at least about 40
mol % SiO.sub.2. As to other aspects, such one or more ion
exchangeable colored glass compositions and/or such one or more IOX
colored glass compositions include one or more metal containing
dopants formulated to impart a preselected color (e.g., any one or
more of any of preselected hue {e.g., shades of red, orange,
yellow, green, blue, and violet}, preselected saturation,
preselected brightness, and/or preselected gloss).
[0037] As to aspects relating to one or more ion exchangeable
colored glass compositions, such compositions are formulated so
that, following an ion exchange treatment (IOX) up to about 64
hours, the color substantially retains its original hue without
fading or running (e.g., is substantially color fast). In aspects
relating to substantial color retention, a color difference
(.DELTA.E=[{.DELTA.L*}.sup.2+{.DELTA.a*}.sup.2+{.DELTA.b*}.sup.2].sup.0.5-
) in the CIELAB color space coordinates of a preselected color of
such one or more ion exchangeable glass compositions after an IOX
treatment and before the IOX treatment determined from specular
transmittance measurements using a spectrophotometer include:
[0038] 1. up to about 8.2 when measurement results obtained between
about 200 nm-2500 nm are presented in CIELAB color space
coordinates for an observer angle of 10.degree. and a CIE
illuminant A; or [0039] 2. up to about 9.1 when measurement results
obtained between about 200 nm-2500 nm are presented in CIELAB color
space coordinates for an observer angle of 10.degree. and a CIE
illuminant F02; or [0040] 3. up to about 8.4 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant D65; or [0041] 4. up to about 5.2 when
measurement results obtained between about 360 nm-750 nm are
presented in CIELAB color space coordinates for an observer angle
of 10.degree. and a CIE illuminant A; or [0042] 5. up to about 6.3
when measurement results obtained between about 360 nm-750 nm are
presented in CIELAB color space coordinates for an observer angle
of 10.degree. and a CIE illuminant F02; or [0043] 6. up to about
6.5 when measurement results obtained between about 360 nm-750 nm
are presented in CIELAB color space coordinates for an observer
angle of 10.degree. and a CIE illuminant D65;
[0044] alternatively, a color difference
(.DELTA.E=[{.DELTA.L*}.sup.2+{.DELTA.a*}.sup.2+{.DELTA.b*}.sup.2].sup.0.5-
) in the CIELAB color space coordinates of a preselected color of
such one or more ion exchangeable glass compositions after an IOX
treatment and before the IOX treatment determined from specular
transmittance measurements using a spectrophotometer include:
[0045] 1. up to about 3.5 when measurement results obtained between
about 200 nm-2500 nm are presented in CIELAB color space
coordinates for an observer angle of 10.degree. and a CIE
illuminant A; or [0046] 2. up to about 3.6 when measurement results
obtained between about 200 nm-2500 nm are presented in CIELAB color
space coordinates for an observer angle of 10.degree. and a CIE
illuminant F02; or [0047] 3. up to about 3.3 when measurement
results obtained between about 200 nm-2500 nm are presented in
CIELAB color space coordinates for an observer angle of 10.degree.
and a CIE illuminant D65; or [0048] 4. up to about 5.2 when
measurement results obtained between about 360 nm-750 nm are
presented in CIELAB color space coordinates for an observer angle
of 10.degree. and a CIE illuminant A; or [0049] 5. up to about 6.3
when measurement results obtained between about 360 nm-750 nm are
presented in CIELAB color space coordinates for an observer angle
of 10.degree. and a CIE illuminant F02; or [0050] 6. up to about
6.5 when measurement results obtained between about 360 nm-750 nm
are presented in CIELAB color space coordinates for an observer
angle of 10.degree. and a CIE illuminant D65.
[0051] Returning to aspects relating to compositions, such one or
more ion exchangeable colored glass compositions and/or such one or
more ion exchangeable, colorable glass compositions and/or such one
or more IOX colored glass compositions might include
Al.sub.2O.sub.3; at least one alkali metal oxide of the form
R.sub.2O, wherein R comprises one or more of Li, Na, K, Rb, and Cs;
and one or more of B.sub.2O.sub.3, K.sub.2O, MgO, ZnO, and
P.sub.2O.sub.5. In some other aspects, such one or more ion
exchangeable colored glass compositions and/or such one or more ion
exchangeable, colorable glass compositions and/or such one or more
IOX colored glass compositions also might include SiO.sub.2 from
about 40 mol % to about 70 mol %; Al.sub.2O.sub.3 comprises from
about 0 mol % to about 25 mol %; B.sub.2O.sub.3 comprises from 0
mol % to about 10 mol %; Na.sub.2O comprises from about 5 mol % to
about 35 mol %; K.sub.2O comprises from 0 mol % to about 2.5 mol %;
MgO comprises from 0 mol % to about 8.5 mol %; ZnO comprises from 0
mol % to about 2 mol %; P.sub.2O.sub.5 comprises from about 0 to
about 10%; CaO comprises from 0 mol % to about 1.5 mol %; Rb.sub.2O
comprises from 0 mol % to about 20 mol %; and Cs.sub.2O comprises
from 0 mol % to about 20 mol %. It will be appreciated that one of
more sub-ranges of any one or more of the preceding are
contemplated. In further aspects, in such one or more ion
exchangeable colored glass compositions and/or such one or more ion
exchangeable, colorable glass compositions and/or such one or more
IOX colored glass compositions a sum of the mol % of
R.sub.2O+Al.sub.2O.sub.3+MgO+ZnO might be at least about 25 mol %.
In still further aspects, such one or more ion exchangeable colored
glass compositions and/or such one or more ion exchangeable,
colorable glass compositions and/or such one or more IOX colored
glass compositions might include at least one fining agent of one
or more of F, Cl, Br, I, As.sub.2O.sub.3, Sb.sub.2O.sub.3,
CeO.sub.2, SnO.sub.2, and combinations thereof.
[0052] In any aspects relating to one or more ion exchangeable
colored glass compositions that substantially maintain their
original color following an IOX; one or more ion exchangeable,
colorable glass compositions to which one or more preselected
colors (e.g., any one or more of any of preselected hue {e.g.,
shades of red, orange, yellow, green, blue, and violet},
preselected saturation, preselected brightness, and/or preselected
gloss) can be imparted by an IOX; one or more IOX colored glass
compositions; and/or one or more processes for making one or more
IOX colored glass compositions. a colorant might include one or
more metal containing dopants in amounts formulated to impart a
preselected color (e.g., any one or more of preselected hue {e.g.,
shades of red, orange, yellow, green, blue, and violet},
preselected saturation, preselected brightness, and/or preselected
gloss) to the glass. Such one or more metal containing dopants
include, in some aspects, one or more of transition metals, one or
more of rare earth metals, or one or more of transition metals and
one or more of rare earth metals; in other aspects, one or more of
one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; in still other
aspects, one or more metal containing dopants formulated to impart
a preselected color comprises one or more of Au, Ag, Cu, Ni, Co,
Fe, Mn, Cr, and V.
[0053] Other aspects of embodiments and/or embodiments of this
disclosure relate to a method of making a colored glass article
having at least one surface under a compressive stress
(.sigma..sub.s) and a depth of layer (DOL) and a preselected
colored. Such method can include communicating at least one surface
of an aluminosilicate glass article, which has SiO.sub.2 at least
about 40 mol %, and a bath including one or more metal containing
dopant sources and in amounts formulated to impart a preselected
color to the aluminosilicate glass article by an ion exchange
treatment of the aluminosilicate glass article at a temperature,
for example, between about 350.degree. C. and about 500.degree. C.
for a sufficient time up to about 64 hours to impart the
compressive stress (.sigma..sub.s), the depth of layer (DOL), and
the preselected color at the at least one surface of the
aluminosilicate glass. It will be appreciated, that in some other
aspects, the compressive stress (.sigma..sub.s) might be at least
about 500 MPa while the depth of layer (DOL) might at least about
15 .mu.m. In aspects, a bath is formulated using one or more salts
including one or more strengthening ion sources, such for example,
a potassium source; the one or more metal containing dopant
sources; and a melting temperature less than or equal to the ion
exchange treatment temperature. In other aspects, the one or more
metal containing dopants sources comprises one or more of one or
more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti, La, Ce, Pr, Nd, Sm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, alternately, one or more of
one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, and V. In still
other aspects, the one or more salts might be a formulation of one
or more of a metal halide, cyanide, carbonate, chromate, a nitrogen
oxide radical, manganate, molybdate, chlorate, sulfide, sulfite,
sulfate, vanadyl, vanadate, tungstate, and combinations of two or
more of the proceeding, alternatively, a formulation of one or more
of a metal halide, carbonate, chromate, a nitrate, manganate,
sulfide, sulfite, sulfate, vanadyl, vanadate, and combinations of
two or more of the proceeding.
[0054] Yet other aspects of embodiments and/or embodiments of this
disclosure relate to one or more methods of making one or more
colorfast, ion exchangeable glass compositions as disclosed and
described herein. In some aspect, the one or more methods impart
the one or more glass articles with a layer under a compressive
stress (.sigma..sub.s) and a depth of layer (DOL), the layer
extending from a surface of the glass article toward the depth of
layer. The one or more methods can involve subjecting at one
surface of an alkali aluminosilicate glass article to an ion
exchanging bath at a temperature of up to about 500.degree. C. for
up to about 64 hours, optionally, up to about 16 hours, for a
sufficient time to form the layer. In further aspects, the bath can
comprise at least at least a colorant including one or more metal
containing dopants formulated to impart a preselected color as
disclosed and described herein.
[0055] As to other aspects, such one or more ion exchangeable
colored glass compositions and/or such one or more ion
exchangeable, colorable glass compositions are formulated so that,
following an ion exchange treatment (IOX), for example, up to about
64 hours, the IOX colored glass has at least one surface under a
compressive stress (.sigma..sub.s) of at least about 500 MPa and a
depth of layer (DOL) of at least about 15 .mu.m.
[0056] In any aspects relating to the one or more glass
compositions described herein (e.g., one or more ion exchangeable
colored glass compositions that substantially maintain their
original color following an IOX; one or more ion exchangeable,
colorable glass compositions to which one or more preselected
colors can be imparted by an IOX; and one or more IOX colored glass
compositions) and/or one or more processes for making one or more
IOX colored glass compositions, an ion exchange treatment (IOX)
might be performed at between about 350.degree. C. and 500.degree.
C. and/or between about 1 hour and 64 hours.
[0057] Also in any aspects relating to the one or more glass
compositions described herein, a glass article having a thickness
of up to about 1 mm or more might be made using such
compositions.
[0058] In any aspects relating to the one or more ion exchangeable
colored glass compositions that substantially maintain their
original color following an IOX, a colorant formulated to impart a
preselected color (e.g., any one or more of any of preselected hue
{e.g., shades of red, orange, yellow, green, blue, and violet},
preselected saturation, preselected brightness, and/or preselected
gloss) to a glass article is added to a glass composition. A
colorant can include one or more metal containing dopants in
amounts formulated to impart such preselected color. In some
aspects, such one or more metal containing dopants can include one
or more transition metals, one or more rare earth metals, or one or
more transition metals and one or more rare earth metals. In some
other aspects, such one or more metal containing dopants can
include one or more of one or more of Au, Ag, Cu, Ni, Co, Fe, Mn,
Cr, V, Ti, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and
Lu; while in still other aspects, such one or more metal containing
dopants can include one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr,
and V. It will be appreciated that metal containing dopants might
be in the form of an element (e.g., Au, Ag . . . etc.) and/or a
compound (e.g., CuO, V.sub.2O.sub.5, Cr.sub.2O.sub.3,
CO.sub.3O.sub.4, Fe.sub.2O.sub.3 . . . etc.). Also, such metal
containing dopants are added in amounts formulated to impart a
preselected color. Such amounts might be up to 5 mol % and more in
any combination of dopants that imparts the preselect color. It
will be appreciated that a colorant might be added as a constituent
of a batch of materials formulated for melting to a glass
composition; as a constituent of an ion exchange bath formulated
for imparting color to while at the same time strengthening an ion
exchangeable, colorable glass; or both.
[0059] In any aspects relating to the one or more ion exchangeable
colored glass compositions, a presence of certain metal containing
dopants can impart color while at the same time enhancing one or
more properties achieve by an ion exchange treatment. For example,
a presence of iron in a glass can impart color while at the same
time lead to an increase in compressive stress by increasing stress
relaxation times in a manner similar to that obtainable to using
one or more alkaline earth ions, such as, for example, Mg, Ca . . .
etc. As another example, a presence of vanadium in a glass can
impart color while at the same time lead to diffusivity increases
in a manner similar to that obtainable to using phosphorous in a
glass composition that, in turn, can result in increased depths of
layers (DOLs).
[0060] In any aspects relating to the one or more glass
compositions described herein, including one or more of any of
B.sub.2O.sub.3, P.sub.2O.sub.5, Al.sub.2O.sub.3, fluorine . . . and
the like in a glass composition can form charged species in a
network of such composition glass that can interact with Na.sup.+
in a manner so as to modify one or more properties of the resultant
glass.
[0061] In any aspects relating to the one or more glass
compositions described herein, SiO.sub.2 can be the main
constituent of a glass composition and, as such, can constitute a
matrix of the glass. Also, SiO.sub.2 can serve as a viscosity
enhancer for aiding in a glass's formability while at the same time
imparting chemical durability to the glass. Generally, SiO.sub.2
can be present in amounts ranging from about 40 mol % up to about
70 mol %. When SiO.sub.2 exceeds about 70 mol %, a glass's melting
temperature can be impractically high for commercial melting
technologies and/or forming technologies. In some aspects,
SiO.sub.2 might ranging from about 50 mol % up to about 65 mol %,
or, alternatively, even from about 50 mol % up to about 55 mol
%.
[0062] In any aspects relating to the one or more glass
compositions described herein, such glass compositions might
further include Al.sub.2O.sub.3. In some aspects, Al.sub.2O.sub.3
can be present in amounts ranging from about 0 to about 25 mol %;
alternatively, from about 5 mol % up to about 15 mol %; and, still
further, from about 10 mol % to about 20 mol %.
[0063] In any aspects relating to the one or more glass
compositions described herein, one or more fluxes can be added to a
glass composition in amounts that impart to a glass a melting
temperature compatible with a continuous manufacturing process,
such as, for example, a fusion down-draw formation process, a
slot-draw formation process . . . and the like. One example of a
flux includes Na.sub.2O, which when included in appropriate
amounts, can decrease not only a glass's melting temperature but,
also, it's liquidus temperature, both of which can contribute to a
glass's ease of manufacturing. Additionally following a glass's
formation, an inclusion of Na.sub.2O can facilitate it's
strengthening by ion exchange (10.times.) treatment. To that end,
in some aspect, Na.sub.2O can be present in amounts from about 5
mol % to about 35 mol %, while in alternative aspects, from about
15 mol % to about 25 mol %.
[0064] In any aspects relating to the one or more glass
compositions described herein, B.sub.2O.sub.3 might be included in
sufficient amounts, for example, to lower a glass's softening
point. To that end, in some aspects, B.sub.2O.sub.3 can be present
in amounts from about 0 to about 10 mol %; while in alternative
aspects, from about 0 to about 5 mol % In some other aspects,
B.sub.2O.sub.3 can be present in amounts from about 1 mol % to
about 10 mol %; while in still other alternative aspects, from
about 1 mol % to about 5 mol %.
[0065] In any aspects relating to the one or more glass
compositions described herein, P.sub.2O.sub.5 might be included in
sufficient amounts, for example, to enhance an ion exchangeability
of a glass by shorting an amount of time that might be required to
obtain a prespecified level of compressive stress (.sigma..sub.s)
at a glass's surface while either not reducing or not significantly
reducing a corresponding depth of layer (DOL) at the glass's
surface. For example for an ion-exchange process performed using a
salt bath having a prescribed formulation at a specified
temperature, it has been found that an inclusion of P.sub.2O.sub.5
in a glass's composition significantly shortens the time required
to obtain a prespecified level of compressive stress
(.sigma..sub.s) at a glass's surface while not significantly
reducing a corresponding depth of layer (DOL) at the glass's
surface. As a corollary, it has been found for an ion-exchange
process performed at a specified temperature for a specified time
using a salt bath having a prescribed formulation, that when
comparing a depth of layer (DOL) achieved for a glass composition
including P.sub.2O.sub.5 and that achieved for a corresponding
glass composition having no P.sub.2O.sub.5, the DOL achieved for
the glass including P.sub.2O.sub.5 is significantly greater than
the DOL achieved for the glass including no P.sub.2O.sub.5. To that
end, in some aspects relating to the one or more glass compositions
described herein, P.sub.2O.sub.5 may be substituted for some or all
of any included B.sub.2O.sub.3. In aspect based on such cases,
P.sub.2O.sub.5 can be present in amounts from about 0 mol % to
about 10 mol %; alternatively, from about 0 mol % to about 5 mol %.
In some other aspects relating to the one or more glass
compositions described herein having no B.sub.2O.sub.3 (i.e., the
concentration of B.sub.2O.sub.3 is 0 mol %), P.sub.2O.sub.5 can be
present in amounts from about 1 mol % to about 10 mol %;
alternatively, from about 1 mol % to about 5 mol %.
[0066] Based on the foregoing, it will be understood that the
constituent materials of the one or more glass compositions
described herein may be formulated in any one or more variety of
combinations so as to generate glass compositions having softening
points and/or liquid coefficients of thermal expansion compatible
with techniques and/or processes configured for forming glass
articles having complex shapes. Also, it would be beneficial that
such glass compositions be formulated to be compatible with ion
exchange strengthening techniques so that relatively high values of
depth of layer (DOL) and/or compressive stress (.sigma..sub.s)
might be achieved in at least one surface of an article made using
such compositions. Some exemplary compositions of such one or more
ion exchangeable colored glass compositions; such one or more ion
exchangeable, colorable glass compositions; and such one or more
IOX colored glass compositions have been and will be described.
[0067] As noted, one or more ion exchangeable colored glass
compositions and one or more ion exchangeable, colorable glass
compositions of this disclosure are formulated so as to be capable
of strengthening by an ion-exchange technique. For example, in some
aspects, glass articles formed from such exemplary one or more
glass compositions described herein may be strengthened by an ion
exchange techniques resulting in one or more IOX colored glass
compositions having a compressive stress (.sigma..sub.s) greater
than (>) about 625 MPa and a depth of layer (DOL) greater than
about 30 .mu.m; alternatively, such compressive stress
(.sigma..sub.s) may be greater than (>) about 700 MPa. Further,
glass articles formed from these exemplary glass compositions may
be ion-exchange strengthened such that the one or more IOX colored
glass compositions having a compressive stress (.sigma..sub.s)
equal to or greater than (>) 750 MPa; alternatively, equal to or
greater than (>) 800 MPa; or instead, equal to or greater than
(>) 850 MPa.
[0068] As previously described, articles and/or machines or
equipment might be formed from and/or including one or more glass
compositions of this disclosure or described herein. For example,
cover glasses for electronic devices might be formed using any one
of a fusion down-draw process, a slot-draw process, or any other
suitable process used for forming glass substrates from a batch of
glass raw materials. As a specific example, the one or more ion
exchangeable colored glass compositions and one or more ion
exchangeable, colorable glass compositions disclosure and described
herein might be formed into glass substrates using a fusion
down-draw process. Such fusion down-draw process utilizes a drawing
tank that has a channel for accepting molten glass raw material.
The channel has weirs that open at the top along the length of the
channel on both sides of the channel. When the channel fills with
molten glass, the molten glass overflows the weirs and, due to
gravity, the molten glass flows down the outside surfaces of the
drawing tank as two flowing glass surfaces. These outside surfaces
extend downwardly and inwardly while joining at an edge below the
drawing tank. The two flowing glass surfaces join at this edge and
fuse to form a single flowing sheet of molten glass that may be
further drawn to a desired thickness. The fusion draw method
produces glass sheets with highly uniform, flat surfaces as neither
surface of the resulting glass sheet is in contact with any part of
the fusion apparatus.
[0069] As an alternative specific example, the one or more ion
exchangeable colored glass compositions and one or more ion
exchangeable, colorable glass compositions of this disclosure and
described herein may be formed using a slot-draw process that is
distinct from the fusion down-draw process. In the slot-draw
process molten glass is supplied to a drawing tank. The bottom of
the drawing tank has an open slot with a nozzle that extends the
length of the slot. The molten glass flows through the slot/nozzle
and is drawn downward as a continuous sheet and into an annealing
region.
[0070] In some aspects relating to the one or more glass
compositions described herein, after a glass substrate is formed,
such glass substrate may be further processed and shaped into one
or more complex 3-dimensional shapes such as, for example, a
concave shape, a convex shape, another desired predetermined
geometry . . . etc. A formation of the glass substrate into a glass
article having any of the aforementioned complex shapes is enabled
by formulating the one or more ion exchangeable colored glass
compositions and/or one or more ion exchangeable, colorable glass
compositions to be characterized by a relatively low softening
point and/or a low liquid coefficient of thermal.
[0071] As used herein, the term "ion-exchange strengthened" means
that a glass is strengthened by one or more ion-exchange processes
as might be known in the art of glass manufacturing. Such
ion-exchange processes can include, but are not limited to,
communicating at least one surface of a glass article and at least
one ion source. The glass articles are made using the one or more
ion exchangeable colored glass compositions and/or one or more ion
exchangeable, colorable glass compositions of this disclosure. The
at least one ion source provides one or more ions having an ionic
radius larger than the ionic radius of one or more ions present in
the glass's at least one surface. In this manner, ions having
smaller radii can replace or be exchanged with ions having larger
radii in the glass's at least one surface. Communication can be
effected at a temperature within a range of temperatures at which
ion inter-diffusion (e.g., the mobility of the ions from the at
least one ion source into the glass's surface and ions to replaced
from the glass's surface) is sufficiently rapid within a reasonable
time (e.g., between about 1 hour and 64 hours ranging at between
about 300.degree. C. and 500.degree. C.). Also, typically such
temperature is below the glass transition temperature (T.sub.g) of
the glass when it is desired that, as a result of such
communication, a compressive stress (.sigma..sub.s) and/or depth of
layer (DOL) are attained in the glass's at least one surface. Also,
Some examples of ion-exchange include: ions of sodium (Na.sup.+),
potassium (K.sup.+), rubidium (Rb.sup.+), and/or cesium (Cs.sup.+)
being exchanged for lithium (Li.sup.+) ions of colored or colorable
glass compositions including lithium; ions of potassium (K.sup.+),
rubidium (Rb.sup.+), and/or cesium (Cs.sup.+) being exchanged for
sodium (Na.sup.+) ions of colored or colorable glass compositions
including sodium; ions of rubidium (Rb.sup.+) and/or cesium
(Cs.sup.+) being exchanged for potassium (K.sup.+) ions of colored
or colorable glass compositions including potassium . . . etc. Some
examples of at least one ion source include one or more gaseous ion
sources, one or more liquid ion sources, and/or one or more solid
ion sources. Among one or more liquid ion sources are liquid and
liquid solutions, such as, for example molten salts. For example
for the above ion-exchange examples, such molten salts can be one
or more alkali metal salts such as, but not limited to, one or more
halides, carbonates, chlorates, nitrates, sulfites, sulfates, or
combinations of two or more of the proceeding. As a further example
for the above ion-exchange examples, such one or more alkali metal
salts can include, but not be limited to, a molten salt bath
including potassium nitrate (KNO.sub.3) communicated with the
glass's at least one surface. Such communication can be effected at
a preselected temperature (e.g., between about 300.degree. C. and
500.degree. C.) for a preselected time (e.g., between about 1 hour
and 64 hours) so as to effected the exchange of potassium (K.sup.+)
ions for any one of lithium (Li.sup.+) ions and/or sodium
(Na.sup.+) ions in the glass's at least one surface so as to
strengthen it. A preselected molten salt bath composition for as
well as a preselected temperature and a preselected time at which
communication is to be effected can be varied depending on the
magnitude of compressive stress (.sigma..sub.s) and/or depth of
layer (DOL) one desires to attain in at least one surface of the
glass's surface.
[0072] In some aspects relating to the one or more ion
exchangeable, colorable glass compositions described herein, glass
articles, such as, for example, glass substrates and/or shaped
glass articles, are simultaneously strengthened and colored through
an ion-exchange process. In such aspects, an at least one ion
source, in addition to providing one or more ions having an ionic
radius larger than the ionic radius of one or more ions present in
the glass's at least one surface, provides colorant including one
or more metal containing dopants formulated to impart a preselected
color to at least a glass's at least one surface. Such one or more
metal containing dopants can be selected from one or more
transition metals and/or one or more rare earth metals (e.g., one
or more of one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, V, Ti,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu,
alternatively, one or more of Au, Ag, Cu, Ni, Co, Fe, Mn, Cr, and
V). In this manner not only are ions having smaller radii replaced
or exchanged with ions having larger radii, but also one or more
ions preselected for their ability impart the preselected color
migrate into glass's at least one surface. As above, some examples
of at least one ion source including one or more metal containing
dopants include one or more gaseous ion sources, one or more liquid
ion sources, and/or one or more solid ion sources. Also above,
among one or more liquid ion sources are liquid and liquid
solutions, such as, for example molten salts. However, examples of
such molten salts, in addition to one or more alkali metal salts,
include, in preselected amounts, one or more transition metals
salts and/or one or more rare earth metals metal salts (e.g., Thus,
some examples of such molten salts can include, but not limited to,
one or more halides, cyanides, carbonates, chromates, salts
including nitrogen oxide radicals such as nitrates, manganates,
molybdates, chlorates, sulfides, sulfites, sulfates, vanadyls,
vanadates, tungstates, or combinations of two or more of the
proceeding. Some further examples of such molten salts can include
those having on or more ions with larger radii and one or more
metal containing dopants disclosed in: [0073] [1] G. J. Janz et
al., "Molten Salts Data: Diffusion Coefficients in Single and
Multi-Component Salt Systems," J. Phys. Chem. Ref Data, Vol. 11,
No. 3, pp. 505-693 (1982) at
http://www.nist.gov/data/PDFfiles/jpcrd204.pdf; [0074] [2] K. H.
Stern, "High Temperature Properties and Decomposition of Inorganic
Salts," J. Phys. Chem. Ref. Data, Vol. 3, No. 2, pp. 48-526 (1974)
at http://www.nist.gov/data/PDFfiles/jpcrd51.pdf; [0075] [3] G. J.
Janz et al., "Molten Salts: Volume 1, Electrical Conductance,
Density, and Viscosity Data," Nat. Stand. Ref. Data Ser., NBS (US)
15, 139 pages (October 1968) at
http://www.nist.gov/data/nsrds/NSRDS-NBS-15.pdf; [0076] [4] G. J.
Janz et al., "Molten Salts: Volume 2, Section 2, Surface Tension
Data," Nat. Stand. Ref Data Ser., NBS (U.S.) 28, 62 pages (August
1969) at http://www.nist.gov/data/nsrds/NSRDS-NBS-28.pdf; [0077]
[5] G. J. Janz et al., "Molten Salts: Volume 3, Nitrates, Nitrites
and Mixtures, Electrical Conductance, Density, Viscosity and
Surface Tension Data," J. Phys. Chem. Ref. Data, Vol. 1, No. 3, pp.
581-746 (1972) at http://www.nist.gov/data/PDFfiles/jpcrd10.pdf;
[0078] [6] G. J. Janz et al., "Molten Salts: Volume 4, Part 1,
Fluorides and Mixtures, Electrical Conductance, Density, Viscosity
and Surface Tension Data," J. Phys. Chem. Ref. Data, Vol. 3, No. 1,
pp. 1-116 (1974) at http://www.nist.gov/data/PDFfiles/jpcrd41.pdf;
[0079] [7] G. J. Janz et al., "Molten Salts: Volume 4, Part 2,
Chlorides and Mixtures, Electrical Conductance, Density, Viscosity
and Surface Tension Data," J. Phys. Chem. Ref. Data, Vol. 4, No. 4,
pp. 871-1178 (1975) at
http://www.nist.gov/data/PDFfiles/jpcrd71.pdf; [0080] [8] G. J.
Janz et al., "Molten Salts: Volume 4, Part 3, Bromides and
Mixtures, Iodides and Mixtures," J. Phys. Chem. Ref. Data, Vol. 6,
No. 2, pp. 409-596 (1977) at
http://www.nist.gov/data/PDFfiles/jpcrd96.pdf; [0081] [9] G. J.
Janz et al., "Molten Salts: Volume 4, Part 4, Mixed Halide Melts,
Electrical Conductance, Density, Viscosity and Surface Tension
Data," J. Phys. Chem. Ref. Data, Vol. 8, pp. 125-302 (1979) at
http://www.nist.gov/data/PDFfiles/jpcrd135.pdf; [0082] [10] G. J.
Janz et al., "Molten Salts: Volume 5, Part 1, "Additional Systems
with Common Anions; Electrical Conductance, Density, Viscosity, and
Surface Tension Data," J. Phys. Chem. Ref. Data. Vol. 9, No. 4, pp.
831-1020 (1980) at http://www.nist.gov/data/PDFfiles/jpcrd168.pdf;
[0083] [11] G. J. Janz et al., "Molten Salts: Volume 5, Part 2,
"Additional Systems with Common Anions; Electrical Conductance,
Density, Viscosity, and Surface Tension Data," J. Phys. Chem. Ref.
Data. Vol. 12, No. 3, pp. (1983) at
http://www.nist.gov/data/PDFfiles/jpcrd230.pdf; [0084] [12] G. J.
Janz et al., "Physical Properties Data Compilations Relevant to
Energy Storage: I. Molten Salts: Eutectic Data," NSRDS.cndot.NBS
61, Part I, U.S. Gov't Printing Office, Washington, D.C. (1978) at
http://www.nist.gov/data/nsrds/NSRDS-NBS-61-1.pdf; and [0085] [13]
G. J. Janz et al., "Physical Properties Data Compilations Relevant
to Energy Storage. II. Molten Salts: Data on Single and
Multi-Component Systems," NSRDS.cndot.NBS 61, Part II, U.S. Gov't
Printing Office, Washington, D.C. (1979) at
http://www.nist.gov/data/nsrds/NSRDS-NBS61-II.pdf, such as, without
limitation, any one of FeCl.sub.2-KCl,
Cs.sub.2Cr.sub.2O.sub.7--Rb.sub.2Cr.sub.2O.sub.7, KCl--NbOCl.sub.3,
KCl--K.sub.2Cr.sub.2O.sub.7, FeCl.sub.2-KCl--NdCl.sub.3,
KCl--NbOCl.sub.3, Rb.sub.2O--V.sub.2O.sub.5, CsBr--TiCl,
KCl--MnCl.sub.2--NaCl, KCl--MnCl.sub.2, MnCl.sub.2--RbCl,
CsCl--MnCl.sub.2, CoCl.sub.2-KCl, CoCl.sub.2--RbCl,
K.sub.2CO.sub.3--K.sub.2Mo4O.sub.13, CuCl.sub.2-KCl,
CuSO.sub.4--K.sub.2SO.sub.4, K.sub.2SO.sub.4--MoO.sub.3,
AgVO.sub.3--K.sub.2SO.sub.4--KVO.sub.3,
Ag.sub.2SO.sub.4--AgVO.sub.3--K.sub.2SO.sub.4, AgCl--KVO.sub.3,
CoCl.sub.2--NaCl . . . etc. Similar to above, communication can be
effected at a temperature within a range of temperatures at which
ion inter-diffusion (e.g., the mobility of the ions from the at
least one ion source into the glass's surface and ions to replaced
from the glass's surface) is sufficiently rapid within a reasonable
time (e.g., between about 1 hour and 64 hours ranging at between
about 300.degree. C. and 500.degree. C.). Also, typically such
temperature is below the glass transition temperature (Tg) of the
glass when it is desired that, as a result of such communication, a
compressive stress (.sigma..sub.s) and/or depth of layer (DOL) are
attained in at least one of the glass's surfaces. A preselected
molten salt bath composition for as well as a preselected
temperature and a preselected time at which communication is to be
effected can be varied depending on the magnitude of compressive
stress (.sigma..sub.s) and/or depth of layer (DOL) and/or color one
desires to attains in the glass's at least one surface.
[0086] The compositions and properties of the aforementioned one or
more glass compositions described herein (e.g., one or more ion
exchangeable colored glass compositions that substantially maintain
their original color following an IOX; one or more ion
exchangeable, colorable glass compositions to which one or more
preselected colors can be imparted by an IOX; and one or more IOX
colored glass compositions) will be further clarified with
reference to the following examples.
EXAMPLES
Example Glasses A-F
[0087] Example glasses A-F described in the following were batched
with Si as sand, Al as alumina, Na as both soda ash and sodium
nitrate, B as boric acid, and P as aluminum metaphosphate. For
example glasses A-F, six distinct compositions were formulated so
that each had a different colorant including one or more metal
containing dopants formulated to impart a different preselected
color added to the batch with iron (Fe) added as Fe.sub.2O.sub.3,
vanadium (V) added as V.sub.2O.sub.5, chromium (Cr) added as
Cr.sub.2O.sub.3, cobalt (Co) added as Co.sub.3O.sub.4, copper (Cu)
added as CuO, and gold (Au) added as Au. The batch materials were
melted at 1600.degree. C. for four hours and then poured and
annealed between 550.degree. C. and 650.degree. C. The compositions
of example glasses A-F were analyzed by inductively coupled plasma
and/or atomic absorption and/or X-ray fluorescence (XRF) techniques
to determine the mol % of the constituent materials in each. The
specific compositions for each of example glasses A-F are reported
in Table I.
TABLE-US-00001 TABLE I Glass Composition in Mole Percent [Mol %]
Example Glass A B C D E F Al.sub.2O.sub.3 8.28 8.52 8.40 8.51 8.48
8.48 Au 0.00 0.00 0.00 0.00 0.00 0.01 CaO 0.51 0.48 0.51 0.48 0.48
0.48 Cl 0.00 0.01 0.01 0.00 0.00 0.01 Co.sub.3O.sub.4 0.00 0.00
0.00 0.10 0.00 0.00 Cr.sub.2O.sub.3 0.00 0.00 0.27 0.00 0.00 0.00
CuO 0.00 0.00 0.00 0.00 0.90 0.00 Fe.sub.2O.sub.3 0.70 0.01 0.01
0.01 0.01 0.01 K.sub.2O 1.04 1.13 1.12 1.11 1.12 1.10 MgO 9.27 6.42
7.12 6.73 6.31 6.53 Na.sub.2O 13.69 13.64 14.19 13.81 13.55 13.78
P.sub.2O.sub.5 0.00 0.00 0.00 0.00 0.00 0.00 SO.sub.3 0.00 0.00
0.00 0.01 0.00 0.01 SiO.sub.2 66.34 68.85 68.18 69.04 68.96 69.40
SnO.sub.2 0.15 0.16 0.17 0.17 0.16 0.18 TiO.sub.2 0.00 0.01 0.01
0.00 0.01 0.01 V.sub.2O.sub.5 0.00 0.75 0.00 0.00 0.00 0.00 ZnO
0.00 0.00 0.01 0.01 0.00 0.00 Total 100.00 100.00 100.00 100.00
100.00 100.00
[0088] Also each of example glasses A-F had been imparted with
color by the batched the one or more metal containing
dopants--namely: glass A having an iron (FE) dopant was an olive
green; glass B having an vanadium (V) dopant was a yellow; glass C
having an chromium (Cr) dopant was a green; glass D having a cobalt
(Co) dopant was a dark blue; glass E having a copper (Cu) dopant
was a patina green; and glass F having a gold (Au) dopant was a
red. Substrates of each of example glasses A-F were prepare so as
to have an as-made substrate for comparison and a suitable number
of substrates available for treatment by ion-exchange under a
variety of conditions. Photographs (which have been converted from
color to black-gray-white) of each of example glasses A-F are
presented in FIG. 1 in the column having the "As-Made" heading.
Samples 1-18
[0089] For each of example glasses A-F, as-made substrates of each
were communicated a KNO.sub.3 salt bath at a temperature of about
410.degree. C. for 2 [h] hours, 4 [h], and 8 [h] thereby producing
Samples 1-18.
[0090] As noted above, a replacement of smaller ions with larger
ions creates a compressive stress (.sigma..sub.s) at a glass's
surface and/or a surface layer that is under compression, or a
compressive stress (CS). Such surface layer extends from the
glass's surface into its interior or bulk to a corresponding depth
of layer (DOL). The compressive stress (CS) in such surface layer
is balanced by a tensile stress, or central tension (CT) in the
glass's interior or inner region.
[0091] Compressive stress (.sigma..sub.s), compressive stress (CS),
and corresponding depth of layer (DOL) can be conveniently be
measured, without limitation, using conventional optical techniques
and instrumentation such as commercially available surface stress
meter models FSM-30, FSM-60, FSM-6000LE, FSM-7000H . . . etc.
available from Luceo Co., Ltd. and/or Orihara Industrial Co., Ltd.,
both in Tokyo, Japan (see e.g., FSM-30 Surface Stress Meter
Brochure, Cat no. FS-0013E at
http://www.orihara-ss.co.jp/catalog/fsm/fsm-30-Ecat.pdf; FSM-60
Surface Stress Meter Brochure, Cat no. FS-0013E at
http://www.luceo.co.jp/english/pdf/FSM-60LE%20Ecat.pdf; FSM-6000LE
Surface Stress Meter Brochure, Revision 2009.04 at
http://www.luceo.co.jp/english/pdf/FSM-6000LE%20Ecat.pdf; FSM-7000H
Surface Stress Meter Brochure, Cat no. FS-0024 2009.08 at
http://www.luceo.co.jp/catalog/catalog-pdf/FFSM-7000H_cat.pdf; T.
Kishii, "Surface Stress Meters Utilizing the Optical Waveguide
Effect of Chemically Tempered Glasses," Optics & Lasers in
Engineering 4 (1983) pp. 25-38 at
http://www.orihara-ss.co.jp/data/literature01/A034.pdf; and K.
Kobayashi et al., "Chemical Strengthening of Glass and Industrial
Application," [52 (1977)], pp. 109-112 at
http://www.orihara-ss.co.jp/data/literature01/A001.pdf, all of
which are incorporated by reference herein). Such conventional
optical techniques and instrumentation involve methods of measuring
compressive stress and depth of layer as described in ASTM
1422C-99, entitled "Standard Specification for Chemically
Strengthened Flat Glass," and ASTM 1279.19779 "Standard Test Method
for Non-Destructive Photoelastic Measurement of Edge and Surface
Stresses in Annealed, Heat-Strengthened, and Fully-Tempered Flat
Glass," the contents of which are incorporated herein by reference
in their entirety. Surface stress measurements rely upon the
accurate measurement of the stress optical coefficient (SOC), which
is related to the stress-induced birefringence of the glass. SOC in
turn is measured by those methods that are known in the art, such
as fiber and four point bend method, both of which are described in
ASTM standard C770-98 (2008), entitled "Standard Test Method for
Measurement of Glass Stress-Optical Coefficient," the contents of
which are incorporated herein by reference in their entirety, and a
bulk cylinder method.
[0092] Compressive stress (.sigma..sub.s) and a corresponding depth
of layer (DOL) for each of Samples 1-18 were determined using the
above conventional optical techniques and instrumentation. Values
for the depth of layer (DOL) in micrometers [.mu.m] and values for
the compressive stress (.sigma..sub.s) in megapascal [MPa] are
reported for each of the Samples 1-18 in Tables II-IV, where Table
II includes the results for Samples 1-6, IOX for 2 [h] at
410.degree. C.; Table III includes the results for Samples 7-12,
IOX for 4 [h] at 410.degree. C.; and Table IV includes the results
for Samples 7-12, IOX for 8 [h] at 410.degree. C.
TABLE-US-00002 TABLE II IOX 2 [h] at 410.degree. C. Sample 1 2 2 4
5 6 .sigma.s avg 882.8 838.2 866.8 856.2 844.9 844.0 st dev
.sigma.s 5.1 3.2 9.8 1.8 1.5 5.3 DOL avg 15.6 20.9 19.1 18.9 17.6
20.0 st dev DOL 0.2 0.5 0.4 0.0 0.0 0.2
TABLE-US-00003 TABLE III IOX 4 [h] at 410.degree. C. Sample 7 8 9
10 11 12 .sigma.s avg 883.9 837.6 874.9 852.8 842.9 855.0 st dev
.sigma.s 6.0 3.6 6.8 3.8 1.9 2.4 DOL avg 22.4 29.4 25.5 25.0 24.5
27.0 st dev DOL 0.2 0.2 0.8 0.3 0.0 0.1
TABLE-US-00004 TABLE IV IOX 8 [h] at 410.degree. C. Sample 13 14 15
16 17 18 .sigma.s avg 858.2 809.6 850.1 832.1 819.1 827.7 st dev
.sigma.s 7.3 4.0 5.9 2.6 3.3 1.6 DOL avg 30.8 40.6 37.4 35.0 34.1
37.6 st dev DOL 1.6 0.8 0.7 0.6 0.0 0.9
[0093] FIG. 2 graphically depicts the compressive stress
(.sigma..sub.s) in MPa as a function of ion exchange treatment
(IOX) time (t [h]) in a KNO.sub.3 bath at 410.degree. C. for
substrates of IOX colored glass compositions (i.e., Samples 1-18)
and made using the different dopants. It can be seen from FIG. 2
that the .sigma..sub.s achieved, regardless of the IOX time and
type of colorant, ranges from about 810 MPa to greater than 880
MPa. Further review of FIG. 2 reveals that those substrates
including iron (Fe) in the colorant achieved the highest
.sigma..sub.s, while those including Vanadium (V) exhibited the
lowest .sigma..sub.s values, regardless of the particular IOX time.
In particular, .sigma..sub.s values of Fe dopant substrates were
between 880 and 890 MPa for 2 [h] and 4 [h] treatments, and
approximately 855 MPa for the 8 [h] treatment, while the
.sigma..sub.s values of V dopant substrates exhibited were between
830 and 840 MPa for 2 [h] and 4 [h] treatments, and approximately
810 MPa for the 8 [h] treatments.
[0094] FIG. 3 graphically depicts the depth of layer (DOL) in .mu.m
as a function of ion exchange treatment (IOX) time (t [h]) in a
KNO.sub.3 bath at 410.degree. C. for substrates of IOX colored
glass compositions (i.e., Samples 1-18) and made using the
different dopants. It can be seen from FIG. 3 that the DOL
achieved, regardless of the IOX time and type of colorant, ranges
from about 15 .mu.m to approximately 40 .mu.m. In contrast to the
.sigma..sub.s values, substrates including iron (Fe) in the
colorant achieved the lowest DOL values while those including
Vanadium (V) exhibited the highest DOL values, regardless of the
particular IOX time. In particular, the DOL values of Fe dopant
substrates ranged between 15 to 30 .mu.m the three IOX times at
410.degree. C., while the DOL values of V dopant substrates ranged
between 20 and 40 .mu.m for the three IOX times at 410.degree.
C.
[0095] FIG. 4 graphically depicts the transmittance [%] as a
function of wavelengths, .lamda. [nm], from 200 nanometers [nm] to
2500 nm for the variety of samples of IOX colored glass
compositions (i.e., Samples 1-6) based on substrates of example
glasses A-F subjected to 10.times. using a KNO.sub.3 bath at
410.degree. C. for 2 [h]. Transmittance spectra of FIG. 4 for
Samples 1-6 were obtained using the commercially available a
Hitachi U4001 spectrophotometer equipped with 60 mm diameter
integrating sphere. The Hitachi U4001 spectrophotometer was
configured with following measurement parameters: in the range of
.lamda. [nm] from 200-800, the settings were Scan Speed: 120 nm/min
and Bandwidth-PMT-3.0 nm and, with a detector change at 800 nm, in
the range of .lamda. [nm] from 800-2500, the settings were Scan
Speed: 300 nm/min and Bandwidth-PbS-Servo, Gain-4 while in the
range of .lamda. [nm] from 200-340, the source was deuterium based
and, with a source change at 340 nm, in the range of .lamda. [nm]
from 340-2500, the source was tungsten halogen based. No aperture
was used over the entire range of .lamda. [nm] from 200-2500 nm.
The surfaces of each sample was polished to an optical finish.
Prior to measurement, the flats of each sample were cleaned using a
first low linting wiper saturated with a solution of 1% micro soap
concentrate in deionized (DI) water; rinsed using DI water; dried
using a second linting wiper; and finally wiped using a third wiper
dampened with HPLC grade reagent alcohol.
Samples 19-36
[0096] For each of example glasses A-F, as-made substrates of each
were communicated a KNO.sub.3 salt bath at a temperature of about
450.degree. C. for 2 [h] hours and a KNO.sub.3 salt bath at a
temperature of about 410.degree. C. for 32 [h], and 64 [h] thereby
producing Samples 19-36.
[0097] Returning to FIG. 1 shows a matrix of photographs (which
have been converted from color to black-gray-white) illustrating a
retention of original hue without fading or running (e.g.,
colorfastness) of ion exchangeable colored glass compositions and
IOX colored glass compositions. Photographs (which have been
converted from color to black-gray-white) of each of example
glasses A-F are presented in FIG. 1 in the column having the
"As-Made" heading and compared to photographs of samples of these
glasses following IOX in KNO.sub.3 at 450.degree. C. for 2 [h]; IOX
in KNO.sub.3 at 410.degree. C. for 32 [h]; and IOX in KNO.sub.3 at
410.degree. C. for 64 [h]. Even without color, the photographs in
FIG. 1 demonstrate retention of original or "as-made" hue without
fading and/or running (e.g., colorfastness). To quantify such
"as-made" hue retention, the transmittance [%] as a function of
wavelength, .lamda. [nm], for example glasses A-F and Samples 19-36
where measured and compared. FIGS. 5-10 graphically depict the
transmittance [%] as a function of wavelength, .lamda. [nm], for
substrates of: ion exchangeable Glass A colored using an iron (Fe)
dopant and corresponding IOX colored glass compositions (i.e.,
Samples 19, 25, & 31); ion exchangeable Glass B colored using a
vanadium (V) dopant and corresponding IOX colored glass
compositions (i.e., Samples 20, 26, & 32); ion exchangeable
Glass C colored using a chromium (Cr) dopant and corresponding IOX
colored glass (i.e., Samples 21, 27, & 33); ion exchangeable
Glass D colored using a cobalt (Co) dopant and corresponding IOX
colored glass compositions (i.e., Samples 22, 28, & 34); ion
exchangeable Glass E colored using a copper (Co) dopant and
corresponding IOX colored glass compositions (i.e., Samples 23, 29,
& 35); and ion exchangeable Glass E colored using a gold (Au)
dopant and corresponding IOX colored glass compositions (i.e.,
Samples 24, 30, & 36). These transmittance spectra were
obtained using the Hitachi U4001 spectrophotometer equipped with 60
mm diameter integrating sphere in the manner described above. It
can be seen from FIGS. 5-10 that the transmission spectra for each
as-made glass composition and its corresponding IOX colored samples
are similarly shaped confirming demonstrating the visual
observation of original or "as-made" hue retention. Also it can be
seen that the spectra substantially coincide in the range of
.lamda. [nm] from about 250-500 for Fe dopant and V dopant
compositions: in the range of .lamda. [nm] from about 250-800 for
Co dopant and Cu dopants compositions while appearing to slightly
diverge for Cr dopant and Au dopants compositions in the range of
.lamda. [nm] from about 250-500.
[0098] The transmittance [%] as a function of wavelength, .lamda.
[nm] data of FIGS. 5-10 were transformed into L*; a*; and b* CIELAB
color space coordinates by means of an analytical software (e.g.,
UV/VIS/NIR application pack of the GRAMS spectroscopy software
suite commercially available from Thermo Scientific West Palm
Beach, Fla., US) for CIE Illuminant D65 and a 10.degree. Observer,
as presented in Table V; for CIE Illuminant F02 and a 10.degree.
Observer, as presented in Table VI; and for CIE Illuminant A and a
10.degree. Observer, as presented in Table VII. In addition, a
color difference:
.DELTA.E=[{.DELTA.L*}.sup.2+{.DELTA.a*}.sup.2+{.DELTA.b*}.sup.2].sup.0.5
was determined using the L*; a*; and b* CIELAB color space
coordinates obtained for the as-made colored glass before IOX
treatment and the IOX colored glasses after treatment for each CIE
Illuminant-Observer combination and are also summarized in the
Tables V-VII.
TABLE-US-00005 TABLE V Hitachi U4001 Sample Thickness: 1 [mm] Scan
Range: 200-2500 [nm] CIE Illuminant D65 - 10.degree. Observer
Sample Condition L* a* b* .DELTA.E A Glass A - As Made 84.83 -8.09
2.56 NA B Glass B - As Made 89.24 -1.64 13.67 NA C Glass C - As
Made 76.69 -18.78 33.96 NA D Glass D - As Made 42.24 27.14 -67.02
NA E Glass E - As Made 90.40 -10.21 -5.07 NA F Glass F - As Made
62.24 42.75 12.90 NA 19 Glass A - 2 [h] at 450.degree. C. 83.84
-8.10 2.65 1.00 20 Glass B - 2 [h] at 450.degree. C. 88.47 -1.65
14.31 1.00 21 Glass C - 2 [h] at 450.degree. C. 75.02 -18.83 34.08
1.67 22 Glass D - 2 [h] at 450.degree. C. 39.87 30.92 -69.53 5.12
23 Glass E - 2 [h] at 450.degree. C. 90.27 -9.93 -4.71 0.48 24
Glass F - 2 [h] at 450.degree. C. 63.05 39.77 20.72 8.41 25 Glass A
- 32 [h] at 410.degree. C. 84.89 -7.61 1.62 1.06 26 Glass B - 32
[h] at 410.degree. C. 88.79 -1.71 14.15 0.66 27 Glass C - 32 [h] at
410.degree. C. 75.65 -18.39 33.20 1.34 28 Glass D - 32 [h] at
410.degree. C. 41.55 28.05 -67.69 1.32 29 Glass E - 32 [h] at
410.degree. C. 90.31 -10.11 -5.02 0.15 30 Glass F - 32 [h] at
410.degree. C. 62.76 41.63 12.83 1.23 31 Glass A - 64 [h] at
410.degree. C. 83.76 -8.42 2.22 1.17 32 Glass B - 64 [h] at
410.degree. C. 88.79 -1.71 14.18 0.68 33 Glass C - 64 [h] at
410.degree. C. 75.19 -18.57 34.53 1.62 34 Glass D - 64 [h] at
410.degree. C. 42.48 26.51 -66.72 0.74 35 Glass E - 64 [h] at
410.degree. C. 90.27 -10.10 -5.04 0.18 36 Glass F - 64 [h] at
410.degree. C. 61.63 42.12 16.12 3.34 Minimum 39.87 -18.83 -69.53
0.15 Maximum 90.40 42.75 34.53 8.41
[0099] For CIE Illuminant D65 and a 10.degree. Observer, color
difference, .DELTA.E, ranges from about 0.15 to about 8.41 with the
largest value being associated with Sample 24, a Au dopant
substrates treated for 2 [h] at 450.degree. C. while the smallest
value is associated with Sample 29, a Cu dopant substrate treated
for 32 [h] at 410.degree. C.
TABLE-US-00006 TABLE VI Hitachi U4001 Sample Thickness: 1 [mm] Scan
Range: 200-2500 [nm] CIE Illuminant F02 - 10.degree. Observer
Sample Condition L* a* b* .DELTA.E A Glass A - As Made 84.71 -5.51
2.93 NA B Glass B - As Made 89.89 -1.41 15.45 NA C Glass C - As
Made 78.25 -15.37 37.61 NA D Glass D - As Made 39.10 17.12 -75.71
NA E Glass E - As Made 89.72 -7.16 -6.09 NA F Glass F - As Made
65.40 30.51 17.76 NA 19 Glass A - 2 [h] at 450.degree. C. 83.73
-5.52 3.04 0.99 20 Glass B - 2 [h] at 450.degree. C. 89.14 -1.43
16.17 1.04 21 Glass C - 2 [h] at 450.degree. C. 76.53 -15.37 37.64
1.72 22 Glass D - 2 [h] at 450.degree. C. 36.59 20.54 -78.60 5.13
23 Glass E - 2 [h] at 450.degree. C. 89.62 -6.97 -5.66 0.48 24
Glass F - 2 [h] at 450.degree. C. 66.62 27.52 26.27 9.10 25 Glass A
- 32 [h] at 410.degree. C. 84.74 -5.18 1.86 1.12 26 Glass B - 32
[h] at 410.degree. C. 89.46 -1.46 16.00 0.70 27 Glass C - 32 [h] at
410.degree. C. 77.12 -14.99 36.67 1.52 28 Glass D - 32 [h] at
410.degree. C. 38.38 17.97 -76.46 1.35 29 Glass E - 32 [h] at
410.degree. C. 89.62 -7.10 -6.03 0.13 30 Glass F - 32 [h] at
410.degree. C. 65.88 29.69 17.64 0.96 31 Glass A - 64 [h] at
410.degree. C. 83.61 -5.74 2.53 1.20 32 Glass B - 64 [h] at
410.degree. C. 89.45 -1.46 16.03 0.72 33 Glass C - 64 [h] at
410.degree. C. 76.79 -15.24 38.23 1.59 34 Glass D - 64 [h] at
410.degree. C. 39.33 16.68 -75.37 0.60 35 Glass E - 64 [h] at
410.degree. C. 89.59 -7.09 -6.06 0.16 36 Glass F - 64 [h] at
410.degree. C. 64.97 29.62 21.27 3.64 Minimum 36.59 -15.37 -78.60
0.13 Maximum 89.89 30.51 38.23 9.10
[0100] For CIE Illuminant F02 and a 10.degree. Observer, color
difference, .DELTA.E, ranges from about 0.13 to about 9.1 with the
largest value being associated with Sample 24, a Au dopant
substrates treated for 2 [h] at 450.degree. C. while the smallest
value is associated with Sample 29, a Cu dopant substrate treated
for 32 [h] at 410.degree. C.
TABLE-US-00007 TABLE VII Hitachi U4001 Sample Thickness: 1 [mm]
Scan Range: 200-2500 [nm] CIE Illuminant A - 10.degree. Observer
Sample Condition L* a* b* .DELTA.E A Glass A - As Made 84.07 -8.04
0.55 NA B Glass B - As Made 89.96 1.30 13.78 NA C Glass C - As Made
76.61 -16.72 32.70 NA D Glass D - As Made 36.63 -9.41 -72.01 NA E
Glass E - As Made 88.84 -12.28 -7.98 NA F Glass F - As Made 68.17
40.24 24.23 NA 19 Glass A - 2 [h] at 450.degree. C. 83.08 -8.02
0.64 0.99 20 Glass B - 2 [h] at 450.degree. C. 89.22 1.40 14.44
0.99 21 Glass C - 2 [h] at 450.degree. C. 74.93 -16.55 32.68 1.68
22 Glass D - 2 [h] at 450.degree. C. 34.04 -7.44 -74.74 4.25 23
Glass E - 2 [h] at 450.degree. C. 88.77 -11.88 -7.52 0.61 24 Glass
F - 2 [h] at 450.degree. C. 68.99 37.80 31.96 8.15 25 Glass A - 32
[h] at 410.degree. C. 84.12 -7.76 -0.32 0.92 26 Glass B - 32 [h] at
410.degree. C. 89.54 1.32 14.27 0.65 27 Glass C - 32 [h] at
410.degree. C. 75.57 -16.11 31.84 1.48 28 Glass D - 32 [h] at
410.degree. C. 35.87 -9.03 -72.77 1.15 29 Glass E - 32 [h] at
410.degree. C. 88.76 -12.15 -7.89 0.18 30 Glass F - 32 [h] at
410.degree. C. 68.55 39.31 23.88 1.06 31 Glass A - 64 [h] at
410.degree. C. 82.93 -8.47 0.11 1.29 32 Glass B - 64 [h] at
410.degree. C. 89.53 1.33 14.29 0.67 33 Glass C - 64 [h] at
410.degree. C. 75.14 -16.52 33.31 1.60 34 Glass D - 64 [h] at
410.degree. C. 36.85 -9.81 -71.80 0.51 35 Glass E - 64 [h] at
410.degree. C. 88.73 -12.14 -7.92 0.20 36 Glass F - 64 [h] at
410.degree. C. 67.64 39.68 27.62 3.47 Minimum 34.04 -16.72 -74.74
0.18 Maximum 89.96 40.24 33.31 8.15
[0101] For CIE Illuminant D65 and a 10.degree. Observer, color
difference, .DELTA.E, ranges from about 0.15 to about 8.41 with the
largest value being associated with Sample 24, a Au dopant
substrates treated for 2 [h] at 450.degree. C. while the smallest
value is associated with Sample 29, a Cu dopant substrate treated
for 32 [h] at 410.degree. C.
[0102] A second series of transmittance color measurements were
made using a Hunterlab Ultrascan XE colorimeter configured with
following measurement parameters: in the range of .lamda. [nm] from
360-750, Spectral Bandwidth of 10 nm, Scan Steps of 10 nm, xenon
flash lamp type source, diode array detector, and a 3/4'' diameter
aperture. Sample preparation prior to making measurements was
substantially as described above. Again, spectra for each sample
were transformed into L*; a*; and b* CIELAB color space coordinates
for CIE Illuminant D65 and a 10.degree. Observer, as presented in
Table VIII; for CIE Illuminant F02 and a 10.degree. Observer, as
presented in Table IX; and for CIE Illuminant A and a 10.degree.
Observer, as presented in Table X. Also, color difference:
.DELTA.E=[{.DELTA.L*}.sup.2+{.DELTA.a*}.sup.2+{.DELTA.b*}.sup.2].sup.0.5
for each CIE Illuminant-Observer combination was determined. In
addition, spectra for each of example glasses A-F were measured
several times to establish measurement precision for colored
glasses.
[0103] For CIE Illuminant D65 and a 10.degree. Observer, color
difference, .DELTA.E, ranges from about 0.07 to about 6.5; however,
.DELTA.E of the measurement precision ranges from about 0.08 to
about 0.21 suggesting that .DELTA.E ranges from about 0.21 to about
6.5. Thus, the largest .DELTA.E value is associated with Sample 34,
a Co dopant substrates treated for 64 [h] at 410.degree. C. while
the smallest value is 0.26 associated with Sample 23, a Cu dopant
substrate treated for 2 [h] at 410.degree. C.
[0104] For CIE Illuminant F02 and a 10.degree. Observer, color
difference, .DELTA.E, ranges from about 0.07 to about 6.33;
however, .DELTA.E of the measurement precision ranges from about
0.08 to about 0.21 suggesting that .DELTA.E ranges from about 0.21
to about 6.33. Thus, the largest .DELTA.E value is associated with
Sample 34, a Co dopant substrates treated for 64 [h] at 410.degree.
C. while the smallest value is 0.29 associated with Sample 23, a Cu
dopant substrate treated for 2 [h] at 410.degree. C.
[0105] For CIE Illuminant A and a 10.degree. Observer, color
difference, .DELTA.E, ranges from about 0.09 to about 5.2; however,
.DELTA.E of the measurement precision ranges from about 0.08 to
about 0.17 suggesting that .DELTA.E ranges from about 0.17 to about
5.2. Thus, the largest .DELTA.E value is associated with Sample 34,
a Co dopant substrates treated for 64 [h] at 410.degree. C. while
the smallest value is 0.17 associated with Sample 35, a Cu dopant
substrate treated for 64 [h] at 410.degree. C.
TABLE-US-00008 TABLE VIII Hunterlab Ultrascan XE Sample Thickness:
1 [mm] Scan Range: 360-750 [nm] CIE Illuminant D65 - 10.degree.
Observer Sample Condition L* a* b* .DELTA.E A Glass A - As Made
85.23 -7.68 1.30 NA B Glass B - As Made 89.17 -1.77 13.70 NA C
Glass C - As Made 76.02 -19.65 33.34 NA D Glass D - As Made -
1.sup.st 39.19 31.85 -70.06 NA '' Glass D - As Made - 2.sup.nd
Measurement 39.12 31.97 -70.15 0.17 '' Glass D - As Made - 3.sup.rd
Measurement 39.24 31.83 -70.08 0.20 '' Glass D - As Made - 4.sup.th
Measurement 39.16 31.85 -70.06 0.08 '' Glass D - As Made - 5.sup.th
Measurement 39.15 32.01 -70.20 0.21 '' Minimum 39.12 31.83 -70.20
0.08 '' Maximum 39.24 32.01 -70.06 0.21 E Glass E - As Made 90.18
-10.34 -5.24 NA F Glass F - As Made 63.71 41.05 17.21 NA 19 Glass A
- 2 [h] at 450.degree. C. 84.00 -8.45 2.46 1.86 20 Glass B - 2 [h]
at 450.degree. C. 88.56 -1.80 14.40 0.93 21 Glass C - 2 [h] at
450.degree. C. 75.09 -19.84 33.44 0.95 22 Glass D - 2 [h] at
450.degree. C. 39.43 31.41 -69.85 0.54 23 Glass E - 2 [h] at
450.degree. C. 90.10 -10.24 -5.01 0.26 24 Glass F - 2 [h] at
450.degree. C. 63.79 39.26 22.17 5.27 25 Glass A - 32 [h] at
410.degree. C. 84.89 -7.69 1.23 0.35 26 Glass B - 32 [h] at
410.degree. C. 88.90 -1.84 14.23 0.60 27 Glass C - 32 [h] at
410.degree. C. 41.12 28.58 -68.13 4.26 28 Glass D - 32 [h] at
410.degree. C. 75.53 -19.27 32.54 1.01 29 Glass E - 32 [h] at
410.degree. C. 90.17 -10.37 -5.30 0.07 30 Glass F - 32 [h] at
410.degree. C. 63.67 41.07 13.83 3.38 31 Glass A - 64 [h] at
410.degree. C. 83.72 -8.70 2.10 1.99 32 Glass B - 64 [h] at
410.degree. C. 88.88 -1.85 14.25 0.63 33 Glass C - 64 [h] at
410.degree. C. 74.94 -19.43 33.67 1.15 34 Glass D - 64 [h] at
410.degree. C. 42.11 26.88 -67.06 6.50 35 Glass E - 64 [h] at
410.degree. C. 90.09 -10.39 -5.32 0.13 36 Glass F - 64 [h] at
410.degree. C. 62.14 42.04 17.30 1.86 Minimum 39.19 -19.84 -70.06
0.07 Maximum 90.18 42.04 33.67 6.50
TABLE-US-00009 TABLE IX Hunterlab Ultrascan XE Sample Thickness: 1
[mm] Scan Range: 360-750 [nm] CIE Illuminate F02 - 10.degree.
Observer Sample Condition L* a* b* .DELTA.E A Glass A - As Made
85.06 -5.24 1.53 NA B Glass B - As Made 89.80 -1.53 15.50 NA C
Glass C - As Made 77.42 -16.11 36.69 NA D Glass D - As Made -
1.sup.st 35.79 21.90 -79.56 NA '' Glass D - As Made - 2.sup.nd
Measurement 35.72 22.01 -79.66 0.16 '' Glass D - As Made - 3.sup.rd
Measurement 35.84 21.88 -79.59 0.19 '' Glass D - As Made - 4.sup.th
Measurement 35.77 21.91 -79.56 0.08 '' Glass D - As Made - 5.sup.th
Measurement 35.75 22.04 -79.73 0.21 '' Minimum 35.72 21.88 -79.73
0.08 '' Maximum 35.84 22.04 -79.56 0.21 E Glass E - As Made 89.48
-7.23 -6.28 NA F Glass F - As Made 67.27 28.45 22.67 NA 19 Glass A
- 2 [h] at 450.degree. C. 83.87 -5.77 2.84 1.85 20 Glass B - 2 [h]
at 450.degree. C. 89.22 -1.58 16.29 0.98 21 Glass C - 2 [h] at
450.degree. C. 76.44 -16.22 36.73 0.99 22 Glass D - 2 [h] at
450.degree. C. 36.03 21.55 -79.32 0.49 23 Glass E - 2 [h] at
450.degree. C. 89.41 -7.16 -6.01 0.29 24 Glass F - 2 [h] at
450.degree. C. 67.45 26.91 27.85 5.41 25 Glass A - 32 [h] at
410.degree. C. 84.72 -5.24 1.46 0.35 26 Glass B - 32 [h] at
410.degree. C. 89.56 -1.60 16.10 0.65 27 Glass C - 32 [h] at
410.degree. C. 37.81 18.99 -77.34 4.18 28 Glass D - 32 [h] at
410.degree. C. 76.85 -15.74 35.74 1.17 29 Glass E - 32 [h] at
410.degree. C. 89.45 -7.26 -6.34 0.07 30 Glass F - 32 [h] at
410.degree. C. 66.88 29.06 18.78 3.96 31 Glass A - 64 [h] at
410.degree. C. 83.56 -5.95 2.43 1.89 32 Glass B - 64 [h] at
410.degree. C. 89.54 -1.61 16.13 0.69 33 Glass C - 64 [h] at
410.degree. C. 76.38 -15.96 37.05 1.11 34 Glass D - 64 [h] at
410.degree. C. 38.83 17.54 -76.12 6.33 35 Glass E - 64 [h] at
410.degree. C. 89.37 -7.27 -6.38 0.15 36 Glass F - 64 [h] at
410.degree. C. 65.61 29.35 22.61 1.89 Minimum 35.79 -16.22 -79.56
0.07 Maximum 89.80 29.35 37.05 6.33
TABLE-US-00010 TABLE IX Hunterlab Ultrascan XE Sample Thickness: 1
[mm] Scan Range: 360-750 [nm] CIE Illuminant A - 10.degree.
Observer Sample Condition L* a* b* .DELTA.E A Glass A - As Made
84.42 -7.93 -0.67 NA B Glass B - As Made 89.88 1.22 13.77 NA C
Glass C - As Made 75.82 -17.43 31.84 NA D Glass D - As Made -
1.sup.st 33.31 -6.52 -75.28 NA '' Glass D - As Made - 2.sup.nd
Measurement 33.25 -6.45 -75.37 0.13 '' Glass D - As Made - 3.sup.rd
Measurement 33.36 -6.55 -75.31 0.16 '' Glass D - As Made - 4.sup.th
Measurement 33.29 -6.52 -75.28 0.08 '' Glass D - As Made - 5.sup.th
Measurement 33.27 -6.45 -75.43 0.17 '' Minimum 33.25 -6.55 -75.43
0.08 '' Maximum 33.36 -6.45 -75.28 0.17 E Glass E - As Made 88.60
-12.43 -8.19 NA F Glass F - As Made 69.64 38.47 28.59 NA 19 Glass A
- 2 [h] at 450.degree. C. 83.19 -8.43 0.35 1.67 20 Glass B - 2 [h]
at 450.degree. C. 89.30 1.31 14.48 0.92 21 Glass C - 2 [h] at
450.degree. C. 74.87 -17.43 31.80 0.95 22 Glass D - 2 [h] at
450.degree. C. 33.56 -6.77 -75.08 0.41 23 Glass E - 2 [h] at
450.degree. C. 88.54 -12.25 -7.92 0.33 24 Glass F - 2 [h] at
450.degree. C. 69.73 37.31 33.39 4.94 25 Glass A - 32 [h] at
410.degree. C. 84.08 -7.94 -0.75 0.35 26 Glass B - 32 [h] at
410.degree. C. 89.64 1.24 14.30 0.58 27 Glass C - 32 [h] at
410.degree. C. 35.38 -8.41 -73.27 3.45 28 Glass D - 32 [h] at
410.degree. C. 75.33 -16.88 30.97 1.14 29 Glass E - 32 [h] at
410.degree. C. 88.57 -12.47 -8.26 0.09 30 Glass F - 32 [h] at
410.degree. C. 69.44 38.73 24.83 3.77 31 Glass A - 64 [h] at
410.degree. C. 82.86 -8.80 -0.09 1.88 32 Glass B - 64 [h] at
410.degree. C. 89.61 1.23 14.32 0.61 33 Glass C - 64 [h] at
410.degree. C. 74.77 -17.21 32.21 1.13 34 Glass D - 64 [h] at
410.degree. C. 36.44 -9.29 -72.19 5.20 35 Glass E - 64 [h] at
410.degree. C. 88.49 -12.49 -8.30 0.17 36 Glass F - 64 [h] at
410.degree. C. 68.20 39.53 28.89 1.81 Minimum 33.31 -17.43 -75.28
0.09 Maximum 89.88 39.53 33.39 5.20
Example Glass G
[0106] For Example glass G described in the following, 25 distinct
batches were prepared with Si as sand, Al as alumina, Na as both
soda ash and sodium nitrate, B as boric acid, and P as aluminum
metaphosphate. Each of the 25 distinct batches of example glass G
was formulated without metal containing dopants. Each of the 25
distinct batches was melted at 1600.degree. C. for four hours and
then poured and annealed between 550.degree. C. and 650.degree. C.
The composition each example glass G corresponding one of the 25
distinct batches was analyzed by inductively coupled plasma and/or
atomic absorption and/or X-ray fluorescence (XRF) techniques to
determine the mol % of the constituent materials in each. The range
of compositions of example glass G is reported in Table XI.
TABLE-US-00011 TABLE XI Example Glass G Composition in Mole Percent
[Mol %] SiO.sub.2 Al.sub.2O.sub.3 Na.sub.2O K.sub.2O MgO CaO
SnO.sub.2 ZrO.sub.2 Fe.sub.2O.sub.3 Range 68.0 7.0 12.0 0.1 5.0 0.0
0.1 0.0 0.0 71.0 9.5 15.0 2.0 7.4 1.0 0.2 0.0 0.0
Samples 37-61
[0107] For each bath of example glass G, as-made substrates were
communicated with a 5 wt % AgNO.sub.3-95 wt % KNO.sub.3 bath at a
temperature of about 410.degree. C. for 8 [h] thereby producing
Samples 37-61 and, for each, internal absorbance [%] for a 1 mm
path length was determined from the difference of (1) an 10.times.
sample's transmittance and reflectance sum and (2) the
corresponding as-made sample's transmittance and reflectance
sum.
[0108] Transmittance spectra for example glass G and Samples 37-61
were obtained using the commercially available a Hitachi U4001
spectrophotometer equipped with 60 mm diameter integrating sphere.
The Hitachi U4001 spectrophotometer was configured with following
measurement parameters: in the range of .lamda. [nm] from 200-800,
the settings were Scan Speed: 120 nm/min and Bandwidth-PMT-3.0 nm
and, with a detector change at 800 nm, in the range of .lamda. [nm]
from 800-2500, the settings were Scan Speed: 300 nm/min and
Bandwidth-PbS-Servo, Gain-4 while in the range of .lamda. [nm] from
200-340, the source was deuterium based and, with a source change
at 340 nm, in the range of .lamda. [nm] from 340-2500, the source
was tungsten halogen based. No aperture was used over the entire
range of .lamda. [nm] from 200-2500 nm. The surfaces of each sample
was polished to an optical finish. Prior to measurement, the flats
of each sample were cleaned using a first low linting wiper
saturated with a solution of 1% micro soap concentrate in deionized
(DI) water; rinsed using DI water; dried using a second linting
wiper; and finally wiped using a third wiper dampened with HPLC
grade reagent alcohol.
[0109] Reflectance spectra for example glass G and Samples 37-61
were obtained using the commercially available a Perkin Elmer Lamda
950 spectrophotometer with a 60 mm diameter integrating sphere. The
Perkin Elmer Lamda 950 spectrophotometer was configured with
following measurement parameters: in the range of .lamda. [nm] from
200-860, the settings were Scan Speed: 480 nm/min and
Bandwidth-PMT-3.0 nm and, with a detector change at 860 nm, in the
range of .lamda. [nm] from 860-2500, the settings were Scan Speed:
480 nm/min and Bandwidth-PbS-Servo, Gain-5 while in the range of
.lamda. [nm] from 200-340, the source was deuterium based and, with
a source change at 340 nm, in the range of .lamda. [nm] from
340-2500, the source was tungsten halogen based. No aperture was
used over the entire range of .lamda. [nm] from 200-2500 nm. The
surfaces of each sample was polished to an optical finish. Prior to
measurement, the flats of each sample were cleaned using a first
low linting wiper saturated with a solution of 1% micro soap
concentrate in deionized (DI) water; rinsed using DI water; dried
using a second linting wiper; and finally wiped using a third wiper
dampened with HPLC grade reagent alcohol.
[0110] Table XII summarizes average, minimum, and maximum internal
absorbance [%] for 1 mm path length for Samples 37-61 while FIG. 11
graphically depicts the internal absorbance [%] for 1 mm path
length over the entire range of .lamda. [nm] from about 250-2500
for Samples 37-61 and FIG. 12 graphically depicts the internal
absorbance [%] for 1 mm path length over the entire range of
.lamda. [nm] from about 250-800 for Samples 37-61.
TABLE-US-00012 TABLE XII Samples 37-61 Treated for 8 [h] at
410.degree. C. Using a 5 wt % AgNO3 - 95 wt % KNO3 Bath Internal
Absorbance [%] for 1 mm path length .lamda. [nm] Average Minimum
Maximum 250 0.03 0.00 0.07 262 0.02 -0.06 0.11 274 0.26 0.13 0.41
286 0.67 0.56 0.79 300 0.99 0.91 1.06 312 1.10 0.99 1.17 324 1.11
0.93 1.20 336 1.09 0.89 1.21 350 1.05 0.83 1.20 362 1.00 0.75 1.19
374 0.93 0.63 1.17 386 0.83 0.50 1.13 400 0.69 0.36 1.07 412 0.57
0.26 0.98 424 0.45 0.19 0.87 436 0.35 0.13 0.74 450 0.26 0.09 0.59
462 0.20 0.06 0.48 474 0.16 0.05 0.39 486 0.12 0.03 0.31 500 0.09
0.03 0.24 512 0.08 0.02 0.20 524 0.06 0.02 0.17 536 0.05 0.01 0.14
550 0.04 0.01 0.11 562 0.03 0.01 0.10 574 0.03 0.01 0.08 586 0.02
0.00 0.07 600 0.02 0.00 0.06 612 0.02 0.00 0.05 624 0.01 0.00 0.04
636 0.01 0.00 0.04 650 0.01 0.00 0.03 662 0.01 0.00 0.03 674 0.01
0.00 0.02 686 0.01 0.00 0.02 700 0.00 0.00 0.02 712 0.00 0.00 0.01
724 0.00 0.00 0.01 736 0.00 0.00 0.01 750 0.00 0.00 0.01 762 0.00
0.00 0.01 774 0.00 0.00 0.01 786 0.00 0.00 0.00 800 0.00 0.00
0.00
* * * * *
References