U.S. patent number 3,616,098 [Application Number 04/713,992] was granted by the patent office on 1971-10-26 for method of producing glare-reducing glass surface.
This patent grant is currently assigned to Dearborn Glass Company. Invention is credited to Joseph W. Falls.
United States Patent |
3,616,098 |
Falls |
October 26, 1971 |
METHOD OF PRODUCING GLARE-REDUCING GLASS SURFACE
Abstract
An improved glare-reducing glass surface is produced by
including an undissolved inorganic salt of small crystal size,
e.g., in the range of 10-50 microns in diameter and 2-10 micron in
height, in the etching bath of an etching process. The etching
process involves cleaning the glass surface, etching in a
hydrofluoric acid bath or similar acid bath containing the
undissolved salt by virtue of a saturated condition of the bath.
Saturation of the bath is usually accomplished by ammonium
bifluoride or other salt. After etching, the surface is properly
polished and cleaned. The preferred, inorganic salt crystals are
crystals of potassium bifluoride, sodium bifluoride, and calcium
phosphate.
Inventors: |
Falls; Joseph W. (Chicago,
IL) |
Assignee: |
Dearborn Glass Company
(N/A)
|
Family
ID: |
24868381 |
Appl.
No.: |
04/713,992 |
Filed: |
March 18, 1968 |
Current U.S.
Class: |
428/141;
252/79.3; 216/91; 216/97; 65/31; 428/409 |
Current CPC
Class: |
C03C
15/00 (20130101); Y10T 428/31 (20150115); Y10T
428/24355 (20150115) |
Current International
Class: |
C03C
15/00 (20060101); C03c 025/06 () |
Field of
Search: |
;156/24 ;65/30,31 ;161/1
;252/79.3 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Steinberg; Jacob H.
Claims
I claim:
1. In a method for etching glass surfaces containing silica for
producing glare-reduced glass wherein the glass is subjected to
etching involving the action of a hydrofluoric acid etching bath
saturated with a relatively large crystal salt having a crystal
size for normally producing protuberances on the glass surface 5-20
microns in height and 25-100 microns in diameter and comprising
ammonium bifluoride, the improvement which comprises including in
said bath from about 0.1 to about 20 weight percent of an inorganic
salt having an ultimate crystal size in the range of about 2-10
microns in height and about 10-50 microns in diameter and selected
from the class consisting of sodium bifluoride, potassium
bifluoride and calcium phosphate.
2. The method of claim 1 wherein said amount of the smaller crystal
size salt is in the range of 0.5 to 5 weight percent.
3. The method of claim 1 wherein said smaller crystal salt is
potassium bifluoride.
4. In a method for etching glass surfaces containing silica for
producing glare-reduced glass wherein the glass is subjected to
etching involving the action of a hydrofluoric acid etching bath
saturated with a relatively large crystal salt having a crystal
size for normally producing protuberances on the glass surface 5-20
microns in height and 25-100 microns in diameter and comprising
ammonium bifluoride, the improvement which comprises including in
said bath from about 0.1 to about 20 weight percent of an inorganic
salt having an ultimate crystal size in the range of about 2-10
microns in height and about 10-50 microns in diameter and selected
from the class consisting of sodium bifluoride, potassium
bifluoride and calcium phosphate, said etching bath comprising 1-20
weight percent hydrofluoric acid (based on 70 percent HF), 10-50
weight percent bifluoride crystals, 0-50 weight percent diethylene
glycol, 10-50 weight percent water, and 0.1-20 weight percent
potassium bifluoride.
5. The method of claim 4 wherein the weight percents of said five
ingredients are seriatim 5-10, 20-40, 20-30, 25-45 and 0.5-5.
6. The method of claim 1 wherein said cleaning operation comprises
washing the glass surface with dilute hydrofluoric acid.
7. The method of claim 1 wherein said polishing operation comprises
dipping the glass recovered from the etching bath into a polishing
bath comprising an aqueous hydrofluoric acid and sulfuric acid
bath.
8. The method of claim 7 including the step of rinsing the glass
after recovery from the polishing bath.
9. The method of claim 1 wherein said etching operation is repeated
at least once until the protuberances of the desired size, over 50
percent of the protuberances having a height in the range of 2 to
10 microns and a diameter in the range of 10 to 50 microns, are
formed uniformly over the glass surface.
10. A substantially nonreflective transparent article made by the
method of claim 1 and comprising a body of glass having a
glare-reduced, etched and polished surface defined by protuberances
of glass at said surface.
11. The article of claim 10 wherein said protuberances are defined
by depressions of silica removal from a smooth glass surface, said
depressions being the general size and shape of inorganic salt
crystal surface portions having a height and diameter in said
restrictive ranges.
12. The article of claim 10 wherein a major amount of the
protuberances have a height in the range of 2-10 microns and a
diameter in the range of 10-50 microns.
Description
FIELD OF THE INVENTION
This invention relates to a new and improved method of etching a
glass surface to produce glare-reducing glass.
DESCRIPTION OF THE PRIOR ART
Processes for producing glare-reducing glass have previously been
proposed. An example of one such process which has been in
commercial practice for a number of years is that disclosed by V.
M. Gilstrap et al. in U.S. Pat. No. 2,622,016, entitled "Method of
Producing Television Tube Face." According to that process, a glass
surface is first cleaned with water and then dipped in three
consecutive baths. The first bath is a cleaning and primary etching
bath which is a water solution containing hydrofluoric acid, e.g.,
about 8 to 12 percent. The second bath is the etching bath which is
a supersaturated solution of ammonium bifluoride, hydrofluoric acid
and water. This bath can be prepared, for example, by mixing six
pounds of technical grade ammonium bifluoride, one pound of
chemical grade 52 percent hydrofluoric acid and four pounds of
water, and can also contain small amounts of sodium chloride and
diethylene glycol. After etching in the second bath, the glass
surface is then dipped in a third hydrofluoric acid bath
containing, for example, 15 percent to 35 percent by weight
commercial 52 percent hydrofluoric acid, and the surface is then
rinsed and dried to complete the etching process. Such a method
provides a glare-reducing surface but the size of the protuberances
of the etched surface has been found to be about 5-20 microns in
height and 25-100 in diameter. Thus, the protuberances vary greatly
in their sizes and decreasing this variance, as well as the actual
protuberance size, would result in an improved and more uniform
glare-reduced surface.
SUMMARY OF THE INVENTION
The size of the protuberances formed on a glass surface during
etching of the glass can be significantly reduced by including in
the etching bath an inorganic salt having a small ultimate or
minimum crystal size which has a surface portion in the range of
about 2 to 10 microns in height and 10 to 50 microns in diameter.
During the etching process, the salt is contacted with the glass
surface and causes the etching of a depression the size and shape
of the crystal surface, thereby forming between the depressions
nodular protuberances of small physical size, smaller than
heretofore provided. A major proportion, i.e., over 50 percent, of
these protuberances are in the range of 2 to 10 microns in height
and 10 to 50 microns in diameter, generally about the same size and
shape of the salt crystal, while the remaining protuberances can be
larger. The resulting etched glass surface is uniform in the
virtual absence of specular areas of reflection and the surface has
markedly improved glare-reducing characteristics.
While this invention is susceptible of embodiment in many different
forms, there will herein be described in detail an embodiment of
the invention with the understanding that the present disclosure is
to be considered as an exemplification of the principles of the
present invention and is not intended to limit the invention to the
embodiment described.
THEORY OF THE FUNCTION OF THE INORGANIC SALTS
The etching bath is an acid bath containing soluble salts which
saturate the bath, usually with an excess of the soluble salt.
Although the additional salts added to the bath according to the
present invention may also be soluble, the saturated nature of the
bath prohibits complete dissolution of such salts so that when the
additional, small crystal salts are added to the bath, they resolve
to an ultimate or minimum crystal size and agitation of the bath
places these crystals in contact with the glass surface. It is
believed that the crystals assist the etching function of the acid
bath in removing silica from the areas of contact with the glass
surface to produce etched depressions in the glass which are images
of the contacting crystal surface. The protuberances are thereby
created between depressions. Because of the small crystal size, the
protuberances are also of small size, e.g., about the same size as
the crystals and these small size protuberances produce less
specular reflections and optical confusion or sparkle when images
are viewed through the treated glass. Further, the small size of
the protuberances permits more uniformly sized protuberances over
the glass surface resulting in more uniform glare-reducing
properties .
DESCRIPTION OF THE PREFERRED EMBODIMENT
The above identified U.S. Pat. No. 2,622,016 of Gilstrap et al. and
all descriptive matter contained therein is incorporated herein by
reference. According to the preferred embodiment of this invention,
the method described in the Gilstrap et al. Patent is used with the
modification disclosed herein.
In accordance with one embodiment of the present invention, the
etching bath of prior processes is modified by the inclusion of
salts having a small ultimate crystal size in the saturated etching
bath. The salts are used in an amount in the range 0.1 to 20 and
preferably 0.5 to 5 weight percent insoluble or undissolved
crystals in the bath. Thus, where normally soluble salts are used
in accordance with this invention, the salts can be used to
saturate or help saturate the bath and an additional amount in the
above ranges is included over and above that required for
saturation. Usually a salt of larger ultimate crystal size such as
ammonium bifluoride will be used to saturate the acid etching bath
and the salt of the present invention will be added in a proper
amount over and above the amount of larger crystal salt.
The useful salts have an ultimate crystal size falling in the range
of 2-10 microns by 10-50 microns. Useful salts can be selected from
the metal salts of mineral acids and preferably the metal
bifluorides and phosphates such as sodium bifluoride, potassium
bifluoride, calcium phosphate and the like. Usually the salts will
be added as larger crystal pieces and will resolve to proper
crystal size in the bath.
In the preferred process, the method of the above-identified
Gilstrap et al. patent is further modified by omitting sodium
chloride from the etching bath by using commercial 70 percent
hydrofluoric acid in the final or polishing bath and by also using
sulfuric acid in the polishing bath as a substitute for a portion
of the hydrofluoric acid so as to conserve the amount of
hydrofluoric acid used. The use of 70 percent hydrofluoric acid in
the polishing bath materially reduces the time required for
polishing the glass to a higher gloss reading which is now often
required by purchasers of glare-reduced glass.
In a typical example of the etching method of this invention, glass
articles, on which it is desired to provide glare-reducing
surfaces, are treated in three stages as follows:
STAGE NO. 1
Etching the Surface
The glass sheets are loaded into a suitable rack that will support
them throughout the baths used in the three stages. The rack is of
an acid resistant material such as monel, hard rubber or
polyvinylchloride and the glass sheets are supported in an upright
position with about a 1-inch spacing between them. While in the
rack the glass is first rinsed with water to remove residual
material which may remain as a result of the glass manufacturing
process. The rack, carrying the glass sheets, is then submerged
into a chemical cleaning bath to clean grease and/or other acid
resisting materials from the surface and prepare the surface for
the etching solution. In this cleaning bath, some preliminary
etching can occur. An example of a suitable cleaning bath solution
is one containing from about 10 percent by weight of 70 percent of
hydrofluoric acid, or the equivalent thereof in water. Preferably,
the cleaning bath is agitated to facilitate the removal of deposits
from the glass surface and the glass is maintained in this bath for
a short period of from, e.g., 1/2 minute to 2 minutes at ambient or
slightly higher temperatures, e.g. 60.degree.-95.degree. F. The
time of dipping in this bath is governed only by the cleaning of
the glass surface. Such glass cleaning operations are conventional
and many are known to the art and can be substituted for the
cleaning operation described above.
After the glass is removed from the cleaning bath, it is submerged
in the etching bath for the purpose of roughening the surface of
the glass to give the glass surface a frosty appearance. The
etching bath, in accordance with this invention, includes an
inorganic salt crystal as previously described. A suitable bath can
contain the following ingredients in the following amounts:
Ammonium bifluoride crystals 10 to 50 parts and preferably 20 to 40
parts by weight Hydrofluoric acid (based on 1 to 20 parts and 70%
HF) preferably 5 to 10 parts by weight HF) Potassium Fluoride 0.1
to 20 parts and preferably 0.5 to 5 parts by weight Diethylene
glycol 0 to 50 parts and preferably 20 to 30 parts by weight Water
10 to 50 parts and preferably 25 to 45 parts by weight
Other inorganic salts such as sodium bifluoride or calcium
phosphate can be substituted for the potassium bifluoride. The
diethylene glycol, or other soluble or miscible organic liquid,
preferably a polyol, assists in controlling the uniformity of the
etched frost of the surface. Suitable substitutes for diethylene
glycol include ethylene glycol, propylene glycol, glycerine,
sorbitol, corn syrup, pentaerythritol trimethylol propane or the
like.
The glass is maintained in the etching bath while agitating the
bath for a short period of time until the desired appearance of
frost is obtained. This will usually require from about 1/2 to 2
minutes at a bath temperature at or slightly above ambient
temperature, e.g. 65.degree.-95.degree. F. Of course, higher
temperatures can be used to decrease the etch time and at lower
temperatures longer etch times may be required.
STAGE NO. 2
Reetching of the Surface
The glass is resubmerged into the cleaning solution in the manner
as discussed above and all stages are repeated through removal of
the glass from the etching bath. This results in reetching the
glass surface. It has been found that in the initial etching dip,
insoluble salts form on the glass surface and the etching action is
thereby slowed and eventually becomes ineffective. Returning the
glass to the cleaning solution removes these deposits and produces
a clean surface so that the etching process can continue at a
faster rate. The reetching permits the complete surface to be
attached by the bath, thereby further assuring elimination of
untreated surfaces which may produce specular reflections. After
the reetching, the glass is obscure and completely frosted or
etched.
The surface can be examined, if desired, through a measuring
microscope to verify that the etched nodular protuberances are of
the desired size. If etching is incomplete, the glass can be
returned to the etching bath as often as necessary.
STAGE NO. 3
Polishing the re-etched Surface
After removal of the glass from the etching bath in the reetching
stage, the glass is treated to remove all residual water, e.g., by
forcing heated air over the surface of the glass. The dried glass
is then submerged into a polishing bath for the purpose of
modifying or even eliminating the frosty appearance and for the
further purpose of polishing the glass to return it toward its
original transparent state. A suitable polishing bath can consist
of 20-40 percent by volume of 70 percent hydrofluoric acid, 20-40
percent by volume of sulfuric acid (66.degree. B.), and the
remainder of water. Higher acid concentration results in faster
polishing action while lower acid concentrates slows the polishing
action. Usually the polishing bath will be at ambient temperatures
or above, e.g., 65.degree.-120.degree. F. and the polishing time is
decreased at the higher bath temperatures. The glass should be
polished until the desired gloss is attained, e.g., as measured
with a Gardner gloss meter.
After removal from the polishing bath, the glass is submerged in a
water bath to stop the polishing action of the polishing bath
acids. The glass is then rinsed to remove all residual acids and is
dried and then inspected to determine that the glass meets the
specifications required. The glass now has a uniformly treated
surface that will reduce the reflected light resulting from light
striking the surface and which also will not affect the ability to
resolve images through the glass by light transmitted.
In one example of the invention, the above typical method was
carried out on a series of glass sheets using a cleaning solution
of 8 percent of 70 percent by weight hydrofluoric acid in water, an
etching bath containing 30 percent by weight ammonium bifluoride
crystals, 8 percent by weight hydrofluoric acid, 3 percent by
weight potassium bifluoride, 25 percent by weight diethylene glycol
and the remainder water, and a polishing bath containing 30 percent
by volume 70 percent hydrofluoric acid, 30 percent by volume
sulfuric acid (66.degree. B.) and the remainder water. The baths
were at normal operating temperatures for ambient conditions and no
external heat was applied so the baths were usually slightly above
ambient temperatures due to heat created during the process. The
glass sheets treated in this process all had excellent
glare-reduced surfaces with Gardner gloss meter readings in the
range of 60-70 at a 60.degree. angle with a large aperture; this
compares with readings of only 35 to 45 from prior process not
utilizing the small crystal salts. The nodular protuberances of the
resulting etched surfaces were of small size with the majority,
e.g., over 50 percent, falling in the range of 2-10 microns in
height and 10-50 microns in diameter.
The example is repeated using sodium bifluoride or calcium
phosphate in lieu of the potassium bifluoride and similar results
are obtained.
* * * * *