U.S. patent application number 15/783661 was filed with the patent office on 2018-03-01 for strengthened glass ii.
The applicant listed for this patent is Saxon Glass Technologies, Inc.. Invention is credited to Arun K. VARSHNEYA.
Application Number | 20180057392 15/783661 |
Document ID | / |
Family ID | 50484105 |
Filed Date | 2018-03-01 |
United States Patent
Application |
20180057392 |
Kind Code |
A1 |
VARSHNEYA; Arun K. |
March 1, 2018 |
STRENGTHENED GLASS II
Abstract
There is an article of manufacture. The article includes an
aluminosilicate glass object. The glass object is characterized by
having a surface compression of at least 100,000 psi at a surface
with a case depth of at least 65 microns below the surface, wherein
the glass object is further characterized as including at least
some amounts of Li2O, Na2O and K2O.
Inventors: |
VARSHNEYA; Arun K.; (Alfred,
NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Saxon Glass Technologies, Inc. |
Alfred |
NY |
US |
|
|
Family ID: |
50484105 |
Appl. No.: |
15/783661 |
Filed: |
October 13, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14601824 |
Jan 21, 2015 |
9815732 |
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15783661 |
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13627840 |
Sep 26, 2012 |
8959953 |
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14601824 |
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11468470 |
Aug 30, 2006 |
8304078 |
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13627840 |
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11382567 |
May 10, 2006 |
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11468470 |
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60716209 |
Sep 12, 2005 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C03C 3/085 20130101;
Y10T 428/24628 20150115; C03C 2204/00 20130101; C03C 21/002
20130101; C03C 21/00 20130101; C03C 4/18 20130101; Y10T 428/315
20150115 |
International
Class: |
C03C 3/085 20060101
C03C003/085; C03C 4/18 20060101 C03C004/18; C03C 21/00 20060101
C03C021/00 |
Claims
1. An article of manufacture comprising: a strengthened
aluminosilicate glass object characterized by having a surface
compression of at least 100,000 psi at a surface with a case depth
of at least 65 microns below the surface, wherein the glass object
is further characterized as including at least some amounts of
Li.sub.2O, Na.sub.2O and K.sub.2O.
2. The article of claim 1, wherein the glass object has a case
depth of at least at 75 microns below the surface.
3. The article of claim 1, wherein the glass object has a case
depth of at least at 120 microns below the surface.
4. The article of claim 1, wherein the glass object has a case
depth of at least at 175 microns below the surface.
5. The article of claim 1, wherein the glass object has a case
depth of at least at 250 microns below the surface.
6. The article of claim 1, wherein the glass object has a case
depth of at least at 300 microns below the surface.
7. The article of claim 1, wherein the glass object has a case
depth of at least at 400 microns below the surface.
8. The article of claim 1, wherein the glass object has a case
depth of at least at 500 microns below the surface.
9. The article of claim 1, wherein the glass object has a case
depth of at least at 550 microns below the surface.
10. The article of claim 1, wherein the glass object includes a
composition with varying amounts of Na.sub.2O and K.sub.2O at
different depths below the surface of the glass object.
11. The article of claim 1, wherein the glass object includes 7 to
30 weight % Al.sub.2O.sub.3.
12. The article of claim 1, wherein the glass object includes less
than 9 weight % Li.sub.2O.
13. The article of claim 1, wherein the glass object includes less
than 3 weight % Li.sub.2O.
14. The article of claim 1, wherein the glass object includes less
than 2% by weight of K.sub.2O, Na.sub.2O or a combination
thereof.
15. The article of claim 1, wherein the glass object has a surface
compression between 100,000 to 145,000 psi at the surface.
16. The article of claim 1, wherein the glass object has a surface
compression up to 145,000 psi at the surface.
17. The article of claim 1, wherein the glass object has a surface
compression greater than 145,000 psi at the surface.
18. The article of claim 1, wherein the glass object includes up to
4 weight % each of ZrO.sub.2, TiO.sub.2, MgO and ZnO, and totaling
no more than 10 weight % of a combination thereof.
19. The article of claim 1, wherein the glass object is flat.
20. The article of claim 1, wherein the glass object is made from a
flat glass.
Description
CLAIM FOR PRIORITY
[0001] This application is a continuation of, claims priority to
and the benefit of U.S. application Ser. No. 14/601,824, titled
"STRENGTHENED GLASS", filed Jan. 21, 2015, now allowed, which is a
division of, claims priority to and the benefit of Ser. No.
13/627,840, titled "METHOD FOR MAKING STRENGTHENED GLASS", filed
Sep. 6, 2012, now U.S. Pat. No. 8,959,953, which is a division of,
claims priority to and the benefit of Ser. No. 11/468,470, titled
"CHEMICALLY STRENGTHENED LITHIUM ALUMINOSILICATE GLASS HAVING HIGH
STRENGTH EFFECTIVE TO RESIST FRACTURE UPON FLEXING", filed Aug. 30,
2006, now U.S. Pat. No. 8,304,078,which is continuation of, claims
priority to and the benefit of U.S. application Ser. No.
11/382,567, titled "CHEMICALLY STRENGTHENED LITHIUM ALUMINOSILICATE
GLASS HAVING HIGH STRENGTH EFFECTIVE TO RESIST FRACTURE UPON
FLEXING FROM IMPACT OF HIGH VELOCITY PROJECTILES" filed May 10,
2006, now abandoned, which claims priority to U.S. Provisional
Application Ser. No. 60/716,209, filed Sep. 12, 2005, the
disclosures of which are incorporated herein by reference in their
entireties.
BACKGROUND OF THE INVENTION
[0002] Glasses generally break because tension acting on a surface
flaw exceeds the engineering strength of the glass. Thus, glass
products can be effectively strengthened if compression is
introduced into the surface. The strengthening depends to a great
extent on the flaw condition of the glass, which, in turn, depends
upon how the glass has been handled through product manufacturing
as well as subsequent user-handling stages. One practical means of
glass strengthening is to immerse the product in a bath of molten
alkali salt at a temperature well below the transition temperature
of the glass. Recommended molten salt is potassium nitrate for a
sodium ion-containing glass and sodium nitrate for a lithium
ion-containing glass. The basic principle is to use salt bath
alkali ions that are larger than those in the glass. An ion
exchange between the salt alkali ions and the glass host alkali
ions results in surface stuffing of ions. This may relax due to
viscous flow if the ion exchange temperature is raised close to or
beyond the glass transition range. The glass transition
temperature, often denoted T.sub.g in the literature, is also used
in place of the annealing point temperature for which the viscosity
of glass is stated to be 10.sup.13 Poise. According to the American
Society for Testing Materials ("ASTM") testing standard ASTM C336,
stresses relax in a matter of minutes at the annealing point. A
lower temperature standard viscosity reference point is the strain
point at which the viscosity is 10.sup.14.5 poise. According to
ASTM, stresses relax in a matter of hours at the strain point.
These "chemical strengthening of glass" concepts relating to the
viscosity of glass are described in the literature, for instance in
U.S. Pat. Nos. 3,752,729 and 3,790,430, both by Mochel and assigned
to Corning Glass Works (now Corning, Inc.). See also R. F.
Bartholomew and H. M. Garfinkel, in Glass Science & Technology,
editors D. R. Uhlmann and N. J. Kreidl, vol. 5, p. 217-270,
Academic Press 1980; and A. K. Varshneya, Fundamentals of Inorganic
Glasses, 1.sup.st edition, pages 339-344 and 445-448, Academic
Press 1994.
[0003] As a test for glass strength, the ASTM recommends performing
a modulus of rupture ("MOR") test, see ASTM standard C158-84. One
way to perform the MOR test is to load rectangular or circular
cross-sectional beams in a 3-point or 4-point mode. The rectangular
beam tests, in particular, tend to be edge condition-dependent and,
hence, flaws on the sawed/ground edge are invariably the origin of
the fracture. The MOR test is desensitized to edge conditions by
performing concentric "ball-on-ring" or "ring-on-ring" (also called
"concentric ring") tests; see ASTM F-394.
[0004] Because the handling flaws are generally of the order of 10
to 50 microns, the performance of chemically strengthened glass
products depends not only on the magnitude of the surface
compression introduced but also on the "case depth," which is the
depth of the compression below the surface (depth at which the
decreasing compression magnitude essentially reaches zero stress,
changing over to a tension at larger depths). The ASTM standard
C1422-99 thus classifies chemically strengthened flat glass
products based on (i) the magnitude of surface compression and (ii)
the magnitude of case depth. For protection against impacting
projectiles, both should be as large as possible. Unfortunately,
the ion exchange process, being atomic diffusion dependent, is
extremely sluggish. Invading ion penetration only increases as the
square root of time. It is also known, however, that the depth of
surface compression does not increase as the square root of time.
This is because, with time, some atomic adjustments occur to
relieve the beneficial compression even at temperatures well below
the strain point (see V. Tyagi and A. K. Varshneya, J. Non-Cryst.
Sol. 238, p. 186-192 (1998); and M. D. Ingram et al., Glastech.
Ber. Glass Sci. & Technol. 73(4) 89-104 (2000)). Thus, while
minutes of immersion in a molten salt bath could be conducted at
temperatures just below the strain point to avoid the relaxation of
the beneficial surface compression, an ion exchange process
requires hours or days of immersion to develop a sufficient case
depth at temperatures well below the strain point of the glass.
[0005] For a given glass composition, the overall strengthening is
a function of the type of invading ion (salt bath composition),
bath temperature and immersion time. The need for proper ion
exchange temperature and immersion time is demonstrated well for
the chemical strengthening of a sodium aluminosilicate glass in a
classic publication by Nordberg et al. J. Am. Ceram. Soc., vol.
47(5) p. 215-219 (1964) of which FIG. 9 is included herewith as
FIG. 1 below for reference. Note that if "fast exchange" with good
MOR were the intent, an optimized exchange would be 550.degree. C.,
for 1 hour. However, if maximum MOR were the intent, for instance
to fend against more severe handling, the ion exchange treatment
would be at 450.degree. C., continuing beyond 16 hours.
[0006] One commercially successful example of ion
exchange-strengthened glass is aircraft windshield manufactured in
the USA by PPG, Incorporated. With roughly 400 MPa (about 58,000
psi) of surface compression and a case depth of about 300 microns,
such glass, when assembled as a multilayer laminate with polymers
such as polyvinyl butyrate and polycarbonate, is designed to
protect the aircraft from flying birds. In a quality control test
such windshields exhibited full containment after impacting a 4-Lb
standardized thawed chicken (or equivalently 4-Lb gel mass) flying
from a gas-pressurized cannon at 400 knots. Several other
applications of chemically strengthened glass do exist, such as for
optical storage disk media, ophthalmic glass, and pharmaceutical
containers, where the requirements of the compression magnitude and
case depth are not so severe.
[0007] Aircraft windshield is a typical example of a high security
application for multilayered glass and polymer laminate. The
laminates are constructed to be thick enough such that the outboard
plies of a tough polymer act to absorb the energy of an impacting
projectile and the glass plies provide the resistance to flexure
due to their high elastic moduli. After most of the energy of the
projectile is absorbed by the "sacrificial" outer plies, the
inboard plies of glass prevent the penetration due to their high
resistance to fracture. One other function of the polymer
interlayer is to retain fractured pieces of glass adhered to it
instead of flying away as shards that otherwise could cause serious
injury. The thickness of the composite not only provides energy
absorption but also reduced flexure which, in turn, results in
lesser tension on the "convexed" surface, hence, lesser probability
of glass fracture. Unfortunately, the higher thicknesses of such
composites can add greatly to the overall weight of the assembly
which, in turn, may be detrimental to the performance of, say, a
vehicle equipped with such glass laminate. The use of extremely
high strength glass plies inboard reduces the need for high glass
ply thickness, hence, forms a significantly superior design.
[0008] For architectural window applications that meet Florida
Building Code, otherwise called the "hurricane code"
(www.dca.state.fl.us/fhcd/fvc; Test Application Standards TAS 201,
202, and 203), glasses are often only heat-strengthened or fully
tempered ("Kind-HS" or "Kind-FT" of ASTM C1048-97b) and laminated.
The thermal tempering process, which takes only a few minutes to
introduce surface compression, creates a case depth from each side
that is roughly 1/5.sup.th of the glass thickness, thus about 1.2
mm deep for an approximately 6 mm thick conventional glass window.
Unfortunately, the thermally tempered glasses are limited to
achieving no more than about 100 MPa surface compression, which is
rarely adequate for protection against high velocity flying debris
in a Category 4 or stronger hurricane. Further, because the thermal
tempering process necessarily raises the temperature of the glass
to well above the glass transition temperature during the
manufacturing process, some optical distortion of the glass due to
viscous flow is unavoidable. Use of such windows in critical
applications such as military armored vehicles, hence, is not
recommended. Additionally, the high weight of glass windows in
buildings designed to withstand hurricanes could present structural
limitations.
[0009] In the practice of chemical strengthening of glass, it is
well known that the soda-lime-silicate glasses, which generally
form the basis of most architectural and windshield applications,
can only be strengthened to a depth of a few microns using
immersion in potassium nitrate bath. Use of higher temperatures
relaxes the beneficial compression and the use of lower bath
temperatures requires days of immersion substantially increasing
the costs of manufacturing. A publication by Nordberg et. al. from
Corning Glass Works (J. Amer. Ceram. Soc., vol. 47, p. 216-219,
1964) discusses the strengthening of a 9 mol % lithium
oxide-containing aluminosilicate glass immersed in a molten sodium
nitrate salt bath at about 400.degree. C., for 4 hours. With
alumina increasing from 14 to 40%, tumble-abraded strengths
increased from about 35 Kpsi (1000 psi) to as much as 100 Kpsi.
Case depths obtained were 0.010 inch (about 250 microns) to 0.020
inch (about 500 microns).
[0010] Garfinkel and King (J. Amer. Ceram. Soc., vol. 53, p. 686,
1970) disclose strengthening a 5.15 wt. % lithium oxide-containing
aluminosilicate glass immersed in sodium nitrate salt bath at
404.degree. C., for 4 hours, to achieve a case depth of about 210
microns and an MOR of about 97 Kpsi. U.S. Pat. No. 3,790,430 by
Mochel describes the chemical strengthening of an 18 mol % lithium
oxide-containing aluminosilicate glass immersed in a molten sodium
nitrate salt bath at about 400.degree. C., for 4 hours. Strengths
of 106,000 psi were claimed to have been achieved. However, no
measurements of case depth were reported.
[0011] The strengthening of sodium aluminosilicate glasses by
immersion in potassium nitrate salt bath is described in U.S. Pat.
No. 4,119,760 by Rinehart and assigned to Pittsburgh Plate Glass
Company, now PPG, Incorporated. The compositions are claimed to
have been suitable for forming using the conventional "updraw" or
"float" processes for making flat glasses. Short term exchange such
as 900.degree. F. (482.degree. C.) and 4 hours in a potassium
nitrate bath was said to produce MOR levels of about 90 Kpsi with a
case depth of only 50 microns. The MOR degraded rapidly to 49 Kpsi
(Table IV) as the exchange temperature was increased to
1050.degree. F. (565.degree. C.) for times as little as 1/2
hour.
[0012] It is known that achieving a case depth of the order of 150
microns or more requires lithium to sodium ion exchange (lithium
ions in the glass exchanged by sodium ions in a molten salt bath in
which the glass is immersed). Therefore, for strengthening
lithium-containing glass, the conventional salt bath contains
almost all sodium salt, such as sodium nitrate. U.S. Pat. No.
3,357,876 by Rinehart and assigned to Pittsburgh Plate Glass
Company, discusses strengthening lithia-soda-alumina-phosphorus
pentoxide-silica glasses containing 1 to 25 wt % phosphorus
pentoxide, by immersion in salt baths containing sodium nitrate or
potassium nitrate and in serially conducted exchange experiments
where each successive treatment is conducted using an alkali metal
which is larger in ionic size than that employed in the prior
experiment. This patent disclosure requires phosphorus pentoxide
(P.sub.2O.sub.5) and Na.sub.2O in the base glass.
[0013] U.S. Pat. No. 3,433,611 by Saunders et al. and assigned to
PPG Industries, Inc., also describes chemically strengthening
lithia-soda-aluminosilicate glass that includes phosphorus
pentoxide. This patent discloses using a mixed salt bath having a
ratio of potassium nitrate salt to sodium nitrate salt in a range
of 2:1 to 50:1. The patent discloses that the stress profiles of
the lithia-soda-alumina-phosphorus pentoxide-silica glasses
obtained by immersion in an 8:1 potassium nitrate to sodium nitrate
bath at 875.degree. F. (468.degree. C.) for 60 minutes show surface
compression of about 96 Kpsi dropping steeply to about 35,000 at a
depth of 20 microns and subsequently falling to zero around 220
microns depth (Example 11, paragraph 6; FIG. 3).
[0014] U.S. Pat. No. 3,410,673 by Marusak and assigned to Corning
Glass Works (now Corning Inc.) discloses a method of chemically
strengthening lithium aluminosilicate glass containing lithium and
sodium ions. The glass may be subjected to immersion in multiple
salt baths, for example, immersion in a bath of sodium salt,
followed by immersion in a potassium salt bath. The purpose
indicated is to first exchange lithium in the glass by sodium from
the bath and, subsequently, lithium and/or sodium ions in the
surface of glass by potassium ions from the bath. The patent also
discloses using a salt bath comprising a 50:50 mixture of sodium
and potassium salt to strengthen a glass which originally contained
both lithium and sodium.
[0015] To the inventor's knowledge none of the above-mentioned
glasses or processes described in numerous patents has been
commercially utilized in the application of resisting fracture upon
impact of high velocity projectiles (e.g., bullets or high wind
velocity hurricanes). It has been observed that a primary
difficulty in some of the glass compositions is the presence of
large amounts of phosphorus pentoxide which, due to its extreme
tendency for volatilization during typical glass-melting processes
such as those needed in float glass or sheet updraw production, is
not a desirable constituent. U.S. Pat. No. 4,156,755, by Rinehart
and assigned to PPG Industries, Inc., discloses glasses having
59-63% SiO.sub.2, 10-13% Na.sub.2O, 4-5.5% Li.sub.2O, 15-23%
Al.sub.2O.sub.3 and 2 to 5% ZrO.sub.2. Rinehart's glass composition
avoided using B.sub.2O.sub.3 and P.sub.2O.sub.5 in view of their
volatility but employed a high amount of Na.sub.2O. In addition,
Rinehart chemically strengthened the glass by immersion in pure
sodium nitrate bath at 705.degree. F., for 22 hours (or 750.degree.
F. for 4 hours). An MOR of about 45 Kpsi with a case depth of about
190 microns were reported.
[0016] It is recognized that, whereas about 400 MPa surface
compression and about 300 micron case depth in 2-3 sheets of
laminated glass are adequate for aircraft windshields, these values
are inadequate for providing resistance of a glass transparency
against bullets or flying debris from high wind velocity
hurricanes. Both the magnitudes of surface compression as well as
the case depth need to be increased for glass products under such
extreme conditions. The problem lies in the facts that, in case of
potassium exchange for sodium in sodium-containing glasses,
although the surface compression generated is large, the case depth
developed is generally less than 100 microns. As shown above,
potassium ions from a potassium-containing salt bath exchanging for
lithium ions in glass is even slower. Efforts to increase the case
depth by increasing the temperature to effect a faster exchange or
time to increase invading ion penetration generally result in
relaxation of the beneficial surface compression.
[0017] A published U.S. patent application 20050090377 by Shelestak
et al., assigned to PPG Industries, Inc., discloses using high
strain point lithium aluminosilicate glasses and a sodium salt bath
or predominantly sodium, mixed Na/K salt bath, in an attempt to
achieve deeper surface compression and higher MOR. The authors
disclose lithium aluminosilicate glasses having a composition
comprising (in weight %): Li.sub.2O in a range of 3 to 9%,
Na.sub.2O+K.sub.2O in an amount of less than 3.5% and
Al.sub.2O.sub.3 in an amount ranging from 7% to 30%. The molten
salt bath disclosed in the '377 patent application preferably uses
at least 50% sodium salt (generally sodium nitrate) and, in
particular 100% sodium salt, to enable sodium exchange. This
reference discloses case depths of, for example, 11.5 to 17.4 mils
(about 300 to 450 microns).
[0018] In addition, Sandia National Laboratories have proposed
strengthening a high annealing point lithium aluminosilicate glass
(Schott ROBAX.RTM. glass composition) using a pure potassium
nitrate salt bath (see S. Jill Glass et al., paper no.
GOMD-S2-29-2004, American Ceramic Society, Glass & Optical
Materials Div. meeting, Cocoa Beach Fla., Nov. 7-12, 2004). This
purportedly produced, for example, high surface compression of 850
MPa, but low case depths of only 40 microns that took days of
immersion to achieve (shown in Table 1 below in the column for
Schott).
[0019] Similarly, U.S. Pat. No. 6,814,453 by Miwa and Kanai and
assigned to Nippon Electric Glass Co., Ltd., describes
strengthening high annealing point lithium aluminosilicate glass in
a bath of potassium nitrate at 500.degree. C. for about 6 hours to
develop a strengthened substrate to prevent projector lamp
fragments from flying forward after sudden failure. The depth of
compression stated is only about 20 to 30 microns. The Miwa et. al.
patent essentially confirms the results of Sandia National
Laboratories, that exchange of lithium ion in glass for potassium
ion from a salt bath is a very slow process.
[0020] Despite all of the work in the area of chemical
strengthening of glass, a need remains for a glass having high
strength to resist fracture upon flexing from impact of high
velocity projectiles. Such a glass will need to be formable by
commercially available glass-forming processes with a
temperature-time schedule that enables efficient and cost-effective
chemical strengthening.
[0021] Many additional features, advantages and a fuller
understanding of the invention may be understood from the following
drawings and detailed description of the invention. Specific
embodiments, figures and examples should not be construed as
necessary limitations of the broad invention as defined in the
claims and their equivalents.
BRIEF SUMMARY OF THE INVENTION
[0022] This summary is provided to introduce a selection of
concepts. These concepts are further described below in the
Detailed Description. This summary is not intended to identify key
features or essential features of the claimed subject matter, nor
is this summary intended as an aid in determining the scope of the
claimed subject matter.
[0023] According to a principle of the invention, there is an
article of manufacture. The article includes an alkali
aluminosilicate glass object characterized by having a surface
compression of at least about 100,000 psi with a case depth of at
least about 600 microns and/or a compressive stress of about 30,000
psi at about 50 microns below a surface of the glass object.
[0024] According to various examples, the glass object has a
surface compression of at least about 100,000 psi with a case depth
of at least about 600 microns; the glass object has a compressive
stress of at least about 30,000 psi at about 50 microns below a
surface of the glass object; the glass object has a case depth of
at least about 600 microns; the glass object has a case depth of at
least about 1000 microns; the glass object includes a composition,
located below the case depth, having a greater combined weight
percentage of Li.sub.2O and/or Na.sub.2O than a weight percentage
of K.sub.2O; the glass object includes a composition, located above
the case depth, having a lesser weight percentage of Li.sub.2O than
a combined weight percentage of Na.sub.2O and/or K.sub.2O; the
glass object includes a composition, located above the case depth,
having a lesser weight percentage of Li.sub.2O than a combined
weight percentage of Na.sub.2O and/or K.sub.2O; the glass object
includes a composition, located at a surface of the glass object,
having a greater weight percentage of K.sub.2O than a combined
weight percentage of Na.sub.2O and/or Li.sub.2O; the glass object
includes about 7 to 30 weight % Al.sub.2O.sub.3, the glass object
includes less than about 9 weight % Li.sub.2O; the glass object
includes less than about 3 weight % Li.sub.2O; the glass object
includes less than about 2% by weight of K.sub.2O, Na.sub.2O or a
combination thereof; the glass object has a surface compression
between about 100,000 to 145,000 psi; less than or equivalent to
about 145,000 psi; the glass object has a surface compression
greater than about 145,000 psi; the glass object includes up to
about 4 weight % each of ZrO.sub.2, TiO.sub.2, MgO and ZnO, and
totaling no more than 10 weight % of a combination thereof; the
glass object is flat; the glass object is curved; the glass object
is a strengthened float glass; the glass object has a maximum
compression at a location below a surface of the glass object.
[0025] The above summary is not intended to describe each
embodiment or every implementation of the present invention.
Further features, their nature and various advantages are more
apparent upon considering the accompanying drawings and the
following detailed description of the examples and embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] The features and advantages of the present invention become
more apparent from the detailed description set forth below when
taken in conjunction with the drawings in which like reference
numbers indicate identical or functionally similar elements.
Additionally, the left-most digit of a reference number identifies
the drawing in which the reference number first appears.
[0027] In addition, it should be understood that the drawings in
the figures, which highlight the aspects, methodology,
functionality and advantages of the present invention, are
presented for example purposes only. The present invention is
sufficiently flexible, such that it may be implemented in ways
other than that shown in the accompanying figures.
[0028] FIG. 1 is a graph showing modulus of rupture (MOR) of a
chemically strengthened glass as a function of ion exchange
treatment and time. The figure shows stress relaxation at higher
temperatures or longer times, in turn, suggesting that a need to
optimize the ion exchange schedule exists. Taken from Nordberg et
al.;
[0029] FIG. 2 is a graph showing compressive stress profiles in an
unbroken plate of the inventive aluminosilicate glass as a function
of ion exchange treatment for various salt baths wherein circle and
triangle data points correspond to use of the indicated mixed
sodium and potassium salt bath used in the invention whereas the
diamond and square comparative data points correspond to use of a
sodium salt bath followed by a potassium salt bath;
[0030] FIG. 3 is a graph showing Weibull plots of the strengths of
the inventive lithium aluminosilicate silicate glass as a function
of ion exchange at 475.degree. C. for 24 hours in a sodium nitrate
and potassium nitrate mixed salt bath. The inset shows the molar
ratio of sodium to potassium in the mixed salt bath. Note
.sigma..sub.f=90 MPa; 148 MPa; 403 MPa; 735 MPa; 1096 MPa at
ln(.sigma..sub.f)=4.5; 5.0; 6.0; 6.5; and 7.0, respectively,
wherein 1 MPa is about 145 psi; and cumulative probability of
failure P.sub.f=98.9%, 80.8%, 63.2%, 30.8%, 12.6% and 4.8% at ln [
ln {1/(1-P.sub.f)}]=1.5, 0.5, 0.0,-1.0,-2.0 and -3.0 respectively;
and
[0031] FIG. 4 is a graph showing compressive stress profiles in an
unbroken plate of the inventive lithium aluminosilicate glass as a
function of ion exchange treatment for various salt baths. The
inset shows the molar ratio of sodium salt to potassium salt in the
mixed salt bath.
DETAILED DESCRIPTION
[0032] The present invention features chemically strengthened
lithium aluminosilicate glass of a composition that provides the
glass with a high strain point, which achieves unexpectedly high
surface compression, deep compression case depth and high strength
effective to resist fracture upon flexing from impact of high
velocity projectiles. The inventive glass is characterized by a
surface compression of at least 100,000 psi and a compression case
depth of at least 600 microns and, in particular, of at least 1,000
microns. In particular, the glass can exhibit strength at 50
microns below a surface of the glass that is at least 30,000 psi.
The compression level is 30,000 psi; hence, a tensile stress higher
than 30,000 psi would be needed to cause fracture.
[0033] As defined herein, the term "annealing point" is the
temperature at which stresses in a glass at a viscosity of
10.sup.13 poise are relieved in 15 minutes. The term "case depth"
is defined herein as a distance measured from a surface of a glass
article to a position in the interior of the article at which there
is zero stress in the glass article. The surface of the glass can
be any surface that is exposed to the molten salts of the ion
exchange bath.
[0034] The present invention uses a molten salt bath having a
balanced mix such that both exchanges (sodium for lithium deep
inside the glass and potassium for lithium in the surface) occur
concurrently. In conventional salt baths having high sodium salt
concentration, there is little potassium-lithium exchange. The
inventor has recognized the advantage of using elevated temperature
of the bath of 450.degree. C., and higher, to increase the mobility
of potassium ions, which require the glass to have a sufficiently
high annealing point such that viscous relaxation of stresses does
not occur significantly. The inventor has further recognized the
usefulness for high amounts of potassium in the mixed bath to
encourage potassium for lithium exchange in the surface. This
results in glass having high strength adapted for use under the
extreme condition of resisting fracture upon flexing from impact of
high velocity projectiles.
[0035] The present invention can strengthen commercially available
flat glass. Glass that may be chemically strengthened according to
the present invention has a composition comprising (in weight %):
Li.sub.2O in an amount ranging from 3 to 9%, Na.sub.2O+K.sub.2O in
an amount less than about 3.5%, and Al.sub.2O.sub.3 in an amount
ranging from 7 to 30%. In particular, Na.sub.2O+K.sub.2O in the
glass ranges from 0 to 3%, and Al.sub.2O.sub.3 ranges from 18-28%.
More specifically, the inventive glass has a composition consisting
essentially of: Li.sub.2O in an amount ranging from 3 to 9%,
Na.sub.2O+K.sub.2O in an amount less than about 3.5%,
Al.sub.2O.sub.3 in an amount ranging from 7 to 30%, up to about 4%
each of ZrO.sub.2, TiO.sub.2, MgO and ZnO and other similar
constituents totaling no more than 10%, with the balance being
SiO.sub.2 and unavoidable impurities. The inventive composition
does not add B.sub.2O.sub.3 or P.sub.2O.sub.5 and these compounds
are not generally present in amounts greater than 0.05 wt % or
other than what is considered an impurity or tramp ingredient.
Additional compositions of glasses that may be suitable for
strengthening in accordance with the present invention are those
disclosed in U.S. Patent Application Publication No. 2005/0090377
by Shelestak et al., incorporated herein by reference, which have
an annealing point of at least 580.degree. C.
[0036] Exemplary glass that is suitable for being strengthened in
the method of the present invention is a pre-cerammed glass
manufactured by Nippon Electric Glass (NEG) of Japan. This glass
(shown in column 2) and other suitable glasses have the
compositions shown in Table 1 below, and may be treated by the salt
bath temperatures and immersion times shown in Table 1. The
treatments indicated in Table 1 specify the type of salt bath, and
temperature, time of immersion of the glass therein. The properties
reported in Table 1 specify the case depth and surface compression
of the glass, respectively.
TABLE-US-00001 TABLE 1 Glass Composition PRIOR ART INVENTION
INVENTION (weight %) Schott ROBAX .RTM. NEG NEG SiO.sub.2 67.2 65.7
65.1 Al.sub.2O.sub.3 20.1 22 22.6 Li.sub.2O 3.2 4.5 4.2 MgO 1.1 0.5
0.5 CaO 0.05 BaO 0.9 ZnO 1.7 Na.sub.2O 0.4 0.5 0.6 K.sub.2O 0.23
0.3 0.3 B.sub.2O.sub.3 TiO.sub.2 2.7 2 2 ZrO.sub.2 1.7 2.5 2.9 F
0.1 Treatment: Potassium Potassium Potassium & Sodium Potassium
& Sodium 500.degree. C. 500.degree. C. 450-475.degree. C.
450-475.degree. C. 8 days 2 days 8 hours 1 day Properties: 80 .mu.m
40 .mu.m 600 .mu.m 1000 .mu.m 550 MPa 850 MPa 1000 MPa 800 MPa
[0037] Other glasses that may be suitable for being strengthened by
the method of the present invention are ROBAX.RTM. glass by Schott
Inc. having the composition shown in Table 1 (but using the
inventive mixed salt bath, temperature and period of immersion) and
HERCUVIT.RTM. pre-cerammed glass by PPG, Inc.
[0038] Measuring surface compression and case depth herein is by
the procedure prescribed by ASTM C1422-99. Measuring modulus of
rupture (MOR) herein is by following ASTM standard F-394,"Biaxial
Flexural Strength (MOR) of Ceramic Substrates" also known as the
"ball-on-ring" procedure, which was, otherwise, prescribed for
ceramic substrates. Although standard C1422-99 does not prescribe
measurement of stress at 50 microns, those familiar with the
chemical strengthening process recognize that superior resistance
to fracture is afforded where the compression continues to be
significantly large at distances representing the length of flaws
typical of handling, and in extreme cases, at the base of craters
produced by an impacting projectile. Handling flaws are mostly 50
microns deep, less in a commercial setting where the glass is
laminated with polymer before getting scratched.
[0039] Glass that is suitable for being treated to effect high
strength and deep compression case depths according to the present
invention has a composition that provides it with an annealing
point of 580.degree. C., or higher. This allows chemical
strengthening to be carried out using a molten mixed salt bath
having a temperature of 450.degree. C. or higher and, in
particular, 475.degree. C., or higher. Although the glass can be
preheated, neither the salt bath temperature nor the glass
temperature should be close to the glass annealing point
temperature or exceed a temperature that is about 25.degree. C.
less than the glass annealing point temperature. The lithium
aluminosilicate glass has a high transition temperature (T.sub.g)
of, for example, about 620-630.degree. C.
[0040] The present invention may advantageously use a high
concentration of potassium salt in the dual salt bath. A ratio of
moles of sodium salt to moles of potassium salt in the salt bath
ranges from 1:10 to 1:2 and, in particular, is about 1:4. The
amount of sodium salt in the total salt of the molten mixed salt
bath is often well below 50 mol %. The composition of the salt bath
may comprise sodium salt in an amount ranging from 10 mol % to 40
mol %, with the balance being potassium salt and unavoidable
impurities. In particular, the salt bath may have a composition
consisting essentially of sodium salt in an amount ranging from 20
mol % to 40 mol %, with the balance being potassium salt,
unavoidable impurities and optional scavengers therefor. An
exemplary composition of the salt bath that may advantageously be
used in the present invention is about 20 mol % sodium salt, about
80 mol % potassium salt and unavoidable impurities.
[0041] One way of preparing the salt bath is to weigh the salts dry
in the indicated amounts, mix the salts, place the salts in the
vessel that will contain the bath and turn on the electricity to
the bath to melt the salt mixture and heat the bath to the
specified temperature. The molten salt bath contains molten salt
and no other solvents. The salt bath has no water, besides trace
amounts of structure bound water. The composition of the salt bath
is maintained over time, such as by periodically changing out the
salt. The salts in the salt bath can be sodium nitrate and
potassium nitrate. Other salts of sodium and potassium may be used
instead of nitrate salts. That is, other anions such as chlorides,
sulfates, phosphates and the like can be used instead of nitrates,
and may be preferred when bath temperatures are high in order to
reduce salt volatilization.
[0042] Unavoidable impurities build up in the molten salt bath over
time. As a result of the continuing exit of lithium and other ions
contained in the parent glass structure from the glass, the ions
build up in the bath. The amount of lithium oxide in the bath is
maintained below 1 mol %, preferably below 0.1 mol %. Depending
upon the chemical composition of the parent glass used, other
potential impurities include aluminum, boron, calcium, magnesium,
barium, zinc, titanium and zirconium. Potential impurities from the
steel of the vessel that contains the bath include iron, chromium
and nickel. Initially, "scavengers" or "getters" such as sodium and
potassium silicate powders or flakes are used to absorb some of the
impurities. After some time, the scavenging effect is reduced and
the bath is dumped and replaced with uncontaminated salt. The salts
have varying impurities that should be minimized as much as
commercially possible. Salts of extremely high purity may be most
advantageous in the present invention. Commercially obtained salt
may need to be purified to a suitable level determined by one
skilled in the art in view of this disclosure, such as by
scavenging, before the bath is used. The scavengers are left in the
bath, or the bath can first be treated by a bag containing the
scavengers and the bag is subsequently removed.
[0043] With the concurrent exchange of potassium and sodium ions in
the bath for the lithium ions in the glass at elevated temperatures
without significant viscous relaxation of the glass, high surface
compression of 690 MPa to 1,000 MPa (100,000 to 145,000 psi) and a
deep compression case depth on the order of up to a millimeter in
as little as 1 day of immersion in the salt bath, is achieved by
the invention. The resulting glass has very high strength (modulus
of rupture approaching 1 GPa or 145 Kpsi).
[0044] The present invention advantageously enables high speed
strengthening. Compared to conventional immersion lasting often 10
days, often more, the invention can achieve very high strength in
as little as 4 hours of immersion and very high strength such as
for security glass (bullet-resistant applications) in as little as
a day of immersion. Refer to Table 1 above for exemplary durations
of immersion and resulting surface compression and case depth for
the glass compositions provided.
[0045] The invention may feature a chemically strengthened glass
with greater than 100,000 psi (about 690 MPa) surface compression
and in commonly, not less than 30,000 psi compression at 50 micron
depth from the surface and a total case depth often at least 600
microns (about 24 mils).
[0046] FIG. 2 shows a stress profile plot for 4 specimens of the
NEG's column 2 "mother" glass (see Table 1) prior to ceramming. The
square and diamond comparative data points are for sequential
exchange at 450.degree. C., first with NaNO.sub.3 and then at
475.degree. C. with KNO.sub.3. This sequential exchange is not part
of the present invention. The circle and triangle data points are
for concurrent sodium and potassium salt exchange at 475.degree. C.
that may embody the invention.
[0047] Shown in FIG. 3 are Weibull fracture probability plots for
glass ion exchange-strengthened in mixtures of sodium nitrate
(NaNO.sub.3) and potassium nitrate (KNO.sub.3) salts where the
ratio of salt has been varied from 0 to 30 mol % (4.25 to 26.5
weight %) and compared with data obtained with unstrengthened and
unstrengthened-plus-abraded specimens. The plots show the
superiority of the 20 mol % sodium nitrate salt mixture over
others. In addition, it can be seen, from steepness of the slope,
that the chemically strengthened glasses have narrower strength
distributions compared to the unstrengthened glass. For product
specifications, one often prefers glass strength distributions to
be narrow. The slope of the curves yields Weibull modulus. Whereas
the Weibull modulus values for the unstrengthened glasses were
around 4.5, the strengthened glasses had Weibull modulus values
ranging between 9 and 18.
[0048] FIG. 4 shows stress profiles for 5, 10 and 20 mol % sodium
nitrate (balance potassium nitrate) baths. Again, the higher
stresses achieved with ion exchange in the 20 mol % sodium nitrate
bath are evident. NEG's column 2 "mother" glass shown in Table 1
was used for all specimens.
[0049] On the ASTM C-1422-99 standard, the surface compression and
case depth for the glass treated according to the invention (circle
and triangle data points shown in FIG. 2) correspond to a glass
level 5F, which is a high strength limit. Those skilled in the art
will appreciate in reading this disclosure that although ASTM
C-1422-99 does not prescribe any details of the profile below the
surface, glass treated according to the present invention may
exhibit a maximum compression value that is not exactly on the
surface. While not wanting to be bound by theory, such treated
glass may advantageously possess a maximum compression value that
is a few microns below the surface (as disclosed in U.S. Pat. No.
6,516,634 by Green et al.). The strengthened glass of the present
invention advantageously exhibits a relatively high compression
value at about 50 microns below the surface compared to the
Saunders patent publication.
[0050] Applications for the chemically strengthened glass produced
in accordance with the present invention include: glass
transparencies for high-security applications, such as, bullet and
blast-resistant glass, glass for armored defense vehicles, windows
for government buildings and monuments, private vehicles, train and
aircraft transparencies, and hurricane and earthquake-resistant
windows. Lower security need applications such as bank teller
windows, display cases, and ATM touch panels may also benefit from
the invention.
[0051] Many modifications and variations of the invention will be
apparent to those of ordinary skill in the art in light of the
foregoing disclosure. Therefore, it is to be understood that,
within the scope of the appended claims, the invention can be
practiced otherwise than has been specifically shown and
described.
[0052] Although described specifically throughout the entirety of
the disclosure, the representative examples have utility over a
wide range of applications, and the above discussion is not
intended and should not be construed to be limiting. The terms,
descriptions and figures used herein are set forth by way of
illustration only and are not meant as limitations. Those skilled
in the art recognize that many variations are possible within the
spirit and scope of the principles of the invention. While the
examples have been described with reference to the figures, those
skilled in the art are able to make various modifications to the
described examples without departing from the scope of the
following claims, and their equivalents.
[0053] Further, the purpose of the Abstract is to enable the U.S.
Patent and Trademark Office and the public generally and especially
the scientists, engineers and practitioners in the relevant art who
are not familiar with patent or legal terms or phraseology, to
determine quickly from a cursory inspection the nature and essence
of this technical disclosure. The Abstract is not intended to be
limiting as to the scope of the present invention in any way.
* * * * *