NZ711672B2 - Glass container composition - Google Patents
Glass container composition Download PDFInfo
- Publication number
- NZ711672B2 NZ711672B2 NZ711672A NZ71167212A NZ711672B2 NZ 711672 B2 NZ711672 B2 NZ 711672B2 NZ 711672 A NZ711672 A NZ 711672A NZ 71167212 A NZ71167212 A NZ 71167212A NZ 711672 B2 NZ711672 B2 NZ 711672B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- glass
- oxide
- vanadium
- selenium
- batched
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 105
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 66
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 60
- 239000011669 selenium Substances 0.000 claims abstract description 60
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000006121 base glass Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000006066 glass batch Substances 0.000 claims description 45
- 229910052717 sulfur Inorganic materials 0.000 claims description 32
- 239000011593 sulfur Substances 0.000 claims description 32
- 239000000156 glass melt Substances 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 abstract description 9
- 238000004042 decolorization Methods 0.000 abstract description 9
- 239000005864 Sulphur Substances 0.000 abstract 2
- 230000000717 retained effect Effects 0.000 description 23
- 230000005540 biological transmission Effects 0.000 description 14
- 239000005308 flint glass Substances 0.000 description 9
- 239000005356 container glass Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000001429 visible spectrum Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- -1 oxides of As Chemical compound 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000006750 UV protection Effects 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- VFLXBUJKRRJAKY-UHFFFAOYSA-N 13768-86-0 Chemical compound O=[Se](=O)=O VFLXBUJKRRJAKY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XZLIADMDPXQUAX-UHFFFAOYSA-N [V].[Se] Chemical compound [V].[Se] XZLIADMDPXQUAX-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
Abstract
substantially clear glass container and related methods of manufacturing is disclosed. The glass container has a glass composition including soda-lime base glass materials, and an oxide of vanadium for good ultraviolet light blocking properties and an oxide of selenium to decolour the glass for good clarity and decolourization. The glass composition of the glass container also may include an oxide of sulphur. od clarity and decolourization. The glass composition of the glass container also may include an oxide of sulphur.
Description
GLASS CONTAINER COMPOSITION
The present disclosure is directed to glass containers and, more particularly, to
compositions for glass containers.
Background and Summary of the Disclosure
Glass containers are often composed of so-called ‘soda-lime glass’, also called
‘soda-lime-silica glass’, and many such containers are colored to absorb ultraviolet radiation, and
include green glass, blue glass, amber glass, and the like. For example, a base flint glass may
be melted in a glass melt furnace and, downstream of the furnace, in one or more forehearths,
colorants may be added to the base glass to impart green, blue, or amber hues to the glass. U.S.
Patents that illustrate glass compositions of this type for glass containers include 2,974,052,
3,291,621, 3,326,702, 3,498,806, and 3,627,548.
Before the colorants are added, a decolorizer may be added to a batched glass
composition of the base flint glass in the glass melt furnace to ensure a generally colorless
appearance of the glass. But the decolorizer, such as selenium, tends to dull the effect of the
colorants added downstream in the forehearths. Accordingly, additional materials accompany
the decolorizer to counteract such detrimental effects of the decolorizer. For example, arsenic
oxide or hexavalent chromium have been added to neutralize selenium. U.S. patents that
illustrate glass compositions of this type for glass containers include 2,923,635, and 2,923,636.
In other implementations, selenium can be added in the forehearths downstream of the glass melt
furnace, as illustrated by U.S. Patent 2,955,948.
A general object of the present disclosure, in accordance with one aspect of the
disclosure, is to provide a container glass composition having an oxide of vanadium and an oxide
of selenium to produce substantially clear glass containers with a relative non-green appearance
and with good blocking of ultraviolet light, and/or to at least provide the public with a useful
choice.
Aspects of the present invention are described herein and in New Zealand
specification 620685 from which the present specification is divided. Reference may be made
in the description to subject matter which is not in the scope of the appended claims but relates to
subject matter claimed in the parent specification. That subject matter should be readily
identifiable by a person skilled in the art and may assist putting into practice the invention as
defined in the appended claims.
The present disclosure embodies a number of aspects that can be implemented
separately from or in combination with each other.
Described herein is a flint glass container including an improvement for blocking
ultraviolet light penetration into the container while providing decolorization in container glass,
wherein the container glass includes an oxide of vanadium and an oxide of selenium present in
the container glass and wherein the oxide of vanadium is present in a retained amount ranging
between 0.01 wt% and 0.14 wt% and the oxide of selenium is present in a retained amount
ranging between 0.0125 wt% and 0.025 wt%.
Also described herein is a glass container having a glass composition including
soda-lime base glass materials, and additives including an oxide of vanadium and an oxide of
selenium retained in the container glass, a glass container having a glass composition including:
soda-lime base glass materials; and additives including an oxide of vanadium and an oxide of
selenium retained in the container glass, and wherein the oxide of vanadium is retained in an
amount of about 0.1 wt. % and the oxide of selenium is retained in an amount of about 0.025 wt.
A first aspect of the present invention provides a method of making glass
containers including the steps of preparing a batched glass composition including soda-lime base
glass materials, and including oxides of vanadium and oxides of selenium wherein the oxide of
vanadium is present in an amount ranging between 0.03 wt% and 0.1 wt% and the oxide of
selenium is present in an amount ranging between 0.03 wt% and 0.1 wt%; melting the batched
glass composition in a glass melt furnace to produce a molten batched glass, forming the glass
containers from the molten batched glass; and annealing the glass containers.
A second aspect of the present invention provides a method of making glass
containers including steps of preparing a batched glass composition including soda-lime base
glass materials, and including oxides of vanadium and selenium in about equal amounts, wherein
the soda-lime base glass materials are present in an amount ranging between 73.1 wt% and 99.9
wt% of the batched glass composition; melting the batched glass composition in a glass melt
furnace to produce a molten batched glass; forming the glass containers from the molten batched
glass; and annealing the glass containers.
Brief Description of the Drawings
The disclosure, together with additional objects, features, advantages and aspects
thereof, will be best understood from the following description, the appended claims and the
accompanying drawings, in which:
is an elevational view of a glass container in accordance with an
exemplary embodiment of the present disclosure;
is a cross-sectional view of the glass container body before coating; and
is a graphical plot of light transmission through samples of container glass
having various amounts of oxides of vanadium and selenium.
Detailed Description of Preferred Embodiments
illustrates an exemplary embodiment of a glass container 10 (e.g., glass
bottle, jar, or the like) that may be produced in accord with an exemplary embodiment of a
manufacturing process presently disclosed herein below. The glass container 10 includes a
longitudinal axis A, a base 10a at one axial end of the container 10 that is closed in an axial
direction, a body 10b extending in an axial direction from the axially closed base 10a, and a
mouth 10c at another axial end of the container 10 opposite of the base 10a. Accordingly, the
glass container 10 is hollow. In the illustrated embodiment, the container 10 also includes a
neck 10d that may extend axially from the body 10b, may be generally conical in shape, and may
terminate in the mouth 10c. However, the container 10 need not include the neck 10d and the
mouth 10c may terminate the body 10b, such as in a glass jar embodiment or the like. The
body 10b may be of any suitable shape in cross-section transverse to the axis A as long as the
body 10b is circumferentially closed.
For example, as shown in the body 10b may be of cylindrical transverse
cross-sectional shape that is circumferentially closed. In other embodiments, the body 10b may
be generally oval, square, rectangular, triangular, or of any other suitable transverse
cross-sectional shape. As used herein, the term ‘circumferentially’ applies not only to circular
transverse cross-sectional shapes but also applies to any closed transverse cross-sectional shape.
The glass container 10 may be produced by the following method.
The method includes preparing a batched glass, or glass batch, composition.
The composition includes base glass materials and additives including at least one ultraviolet
(UV) light blocking enhancing material and at least one decolorizer. As used herein, the
terminology ‘ultraviolet light blocking’ includes the characteristic or property of reducing
ultraviolet light transmission in a relative sense, and not necessarily in an absolute sense of UV
opacity or zero UV light transmission.
The base glass materials may include soda-lime flint glass materials. For
example, the base glass materials may be present in an amount ranging between 73.1 wt% and
99.9 wt% of the batched glass composition. More particularly, and by way of example only,
the base glass may include the following materials in amounts by weight:
60-75% SiO
7-15% Na O
6-12% CaO
0.1-3.0% Al2O3
0-2.0% MgO
0-2.0% K O
In a preferred embodiment, the base glass may include the following materials in
about the stated amounts by weight:
72% SiO
13% Na O
% CaO
1.2% Al O
0.2% MgO
0.2% K O
The batched glass composition also may include other materials in small amounts.
For example, the batched glass composition may include TiO , Fe O , or the like. Such
2 2 3
materials may be additives, residual materials from cullet, and/or impurities typical in the glass
container manufacturing industry. Such materials may be present in the batched glass
composition in trace amounts, for example, less than 0.2 wt%. But no arsenic (As), oxides of
As, or hexavalent chromium are affirmatively added to the batched glass composition and, thus,
the composition and container may be substantially free of those materials.
The preferred ultraviolet light blocking enhancing material includes vanadium.
Vanadium forms numerous and complicated compounds because of its variable valence.
Vanadium has at least three oxidation states: 2+, 3+, and 5+. Trivalent vanadium can be used
to produce a green coloration in flint glass, and enhances ultraviolet light protection to glass. In
general, the vanadium may be added in the form any oxide of vanadium. In one specific
example, the vanadium may be added in the form of vanadium pentoxide (V O ). In the
absence of the presently disclosed decolorizer, the vanadium tends to produce a sea green
coloration in the glass.
A preferred decolorizer includes selenium. In one example, the selenium may be
added in the form of granulated selenium metal. In other examples, the selenium may be in the
form any oxide of selenium, for example, selenium dioxide (SeO ) or selenium trioxide (SeO ).
Another preferred material includes sulfur. In one example, at least some of the
sulfur may be added in the form of any oxide of sulfur, for example, sulfur trioxide (SO ). In
another example, at least some of the sulfur may be present as a residual material from cullet in
any suitable form.
In one embodiment, the oxide of vanadium and oxide of selenium present in the
batched glass composition may be in an amount ranging between 0.035 wt% and 0.25 wt% total.
In other words, the total combined amount of oxides of vanadium and selenium in the glass batch
equals 0.035 wt% to 0.25 wt%. In another embodiment, the oxides of vanadium and selenium
are present in the batched glass composition in substantially equal amounts. As used herein the
term ‘substantially’ means within manufacturing tolerances customary in the glass container
manufacturing industry. In another embodiment, the oxide of vanadium may be present in the
batched glass composition in an amount ranging between 0.025 wt% and 0.15 wt%, and the
oxide of selenium may be present in the batched glass composition in an amount ranging
between 0.01 wt% and 0.1 wt%. In one specific example, the oxides of vanadium and selenium
each may be present in amounts of about 0.1 wt%. In another specific example, the oxides of
vanadium and selenium each may be present in amounts of about 0.05 wt%. As used herein the
term ‘about’ means within 0.02 wt%.
In addition to the oxide of selenium, it is believed that the oxide of sulfur plays a
role in producing a decolorized, or neutral colorization of, vanadium-selenium-containing glass.
In development it was observed that glass melted with oxides of vanadium and selenium in the
absence of oxide of sulfur tends to produce pink-peach coloration and minimal decolorization of
the sea green coloration from the oxide of vanadium.
It was also observed that increasing oxide of sulfur content to a level up to about
0.4 wt% showed an increase in decolorization of the glass. In one example, when oxide of
sulfur content was increased to a level between 0.1 wt% and 0.2 wt%, a shift in coloration was
observed including a gray stroke / straw yellow coloration in a top melt portion of the glass, with
a decrease in the pink-peach coloration and shift of that coloration to a location centered around
the bottom melt portion of the glass. In another example, when oxide of sulfur content was
increased to a level of about 0.4 wt%, the glass melt was substantially decolorized with no
pink-peach coloration remaining in the glass. However, some greenish-yellowish coloration
was noticeable to the eye through a relatively long section of the glass, but was not visible to the
eye within a relatively short section of the glass (e.g. a 38 mm thick section of a glass container
wall). In any event, any coloration was within acceptable industrial limits for a standard flint
glass. The coloration from the melt could be due to iron content or excessive color
matching/masking, which can give rise to a hazy, cloudy, or muddy appearance.
Therefore, in the batch glass composition, it is believed that an oxide of sulfur
level ranging between 0.25 wt% and 0.35 wt% in the presence of about 0.1 wt% of oxide of
vanadium and about 0.1 wt% of oxide of selenium would provide good decolorization of the
glass. More particularly, an oxide of sulfur level of about 0.3 wt% in the presence of about 0.1
wt% of oxide of vanadium and about 0.1 wt% of oxide of selenium is believed to provide
particularly good decolorization of glass. However, it is believed that, depending on the
amounts selected for oxides of vanadium and selenium, an acceptable range of oxide of sulfur
may be between 0.05 wt% and 0.35 wt%.
The specific role of sulfur may be responsible for one or two different
mechanisms. A first mechanism is the role of sulfur as a fining agent in a glass melt. Sulfur
in this role produces sulfur gas in the melt that rises up through the melt and coalesces with other
bubbles. This also mixes the glass melt and results in improved homogeneity. A second
mechanism involves sulfur acting as a redox couple with the oxide vanadium and/or the oxide of
selenium. If it is assumed that sulfur is acting to reduce the vanadium, such reduction would
tend to shift the vanadium valance state to 2+. This valence state appears as a colorless/gray.
In addition, it may be assumed that some of the sulfur is reacting with iron to produce a sulfur
chromophore (a brown color in amber glass). In any event, there appears to be a direct
relationship between increasing sulfur content and the production of a homogenous and/or
decolorized glass. It is also possible that there is a maximum sulfur content where an amber
colorization starts to dominate the color or that foaming of the melt surfaces starts to occur, but
this was not examined during this work.
The method also includes melting the batched glass composition in a glass melt
furnace to produce a molten batched glass. Accordingly, the ultraviolet light blocking
enhancing material and the decolorizer additives preferably are melted with the base glass
materials in the glass melt furnace. The conditions and procedure for composing and melting
production container glass can be found in, e.g. ‘Handbook of Glass Manufacture’, Tooley,
Odgen Publishing Co., New York, NY, 1985, 3 edition. In a laboratory scale melt, the
batched glass composition may be melted, preferably between 1400 and 1500 degrees Celsius for
about two to four hours, more preferably between 1425 and 1475 degrees Celsius, and most
preferably at about 1450 degrees Celsius for about three hours.
The method also may include forming the glass containers from the molten
batched glass. The glass containers may be formed, for example, by press-and-blow or
blow-and-blow processes and by individual section machines, or in any other suitable manner by
any suitable equipment.
The method further may include annealing the glass containers in any suitable
manner, for example, in an annealing lehr. At an entry, hot end, or upstream portion of the
annealing lehr, the temperature therein may be between 600 and 550 degrees Celsius. Through
the lehr, the temperature may be brought down gradually to a downstream portion, cool end, or
exit of the lehr, for example, to a temperature therein of between 130 degrees Celsius and 65
degrees Celsius. In any event, the glass containers may be annealed, preferably between 550
and 600 degrees Celsius for about 30 to 90 minutes, more preferably between 525 and 575
degrees Celsius, and most preferably at about 550 degrees Celsius for about one hour. In any
event, in one embodiment, the method may be carried out without having to heat the glass
containers to striking temperatures. In other words, the glass containers need not be struck to
provide decolorization.
The selenium potentially reduces the state of at least some of the vanadium from
the trivalent state to a bivalent state in the glass. This reduction of the vanadium is believed to
negate or mask the green coloration that otherwise would be produced by the vanadium. Such
reduction may produce a generally colorless appearance, perhaps with a straw yellow to slight
gray coloration in the glass and, in any event, a non-green appearance in the glass. It is
believed that the slight gray color is attributed to a nearly uniform decrease of the percent
transmission of visible light. The decrease in the visible light transmission may range from 10
to 20 percent less than a typical flint glass that is not decolorized. The decrease is based on the
amount of vanadium and selenium additions to the base glass, wherein increases in the amounts
of the oxides of vanadium and selenium additives results in decreases in the percent transmission
in the visible light range. Accordingly, flint glass containers may be produced with good
ultraviolet light blocking properties and without the green coloration normally associated with
vanadium-doped glass. In other words, the oxides of vanadium and selenium additives and
their disclosed amounts produce decolorized glass containers with non-green coloration, yet
good UV protection.
The glass containers may have a retained glass composition that is different from
the batched glass composition. For example, only about 10-35% of the oxide of selenium
added to the batched glass composition may be present or retained in the retained glass
composition. Similarly, only about 50-70% of the oxide of sulfur added to the batched glass
composition may be present or retained in the retained glass composition. In contrast, the oxide
of vanadium may be largely retained in the retained glass composition in the produced
containers. In other words, the relative amounts of vanadium to selenium retained in the glass
composition in the produced containers may be about a four to one ratio of vanadium to
selenium.
The glass containers may include a total amount of oxides of vanadium and
selenium present in the retained glass composition in an amount ranging between 0.016 wt% and
0.175 wt% total. In other words, the total combined amount of oxides of vanadium and
selenium retained in the glass container equals 0.016 wt% to 0.175 wt%. Also, the glass
container may include an oxide of sulfur content in an amount ranging between 0.03 wt% and
0.3 wt%. In another embodiment, the oxide of sulfur may be present in the retained glass
composition in an amount between 0.08 wt% and 0.25 wt%, and the oxide of vanadium may be
present in the retained glass composition in an amount ranging between 0.01 wt% and 0.14 wt%,
whereas the oxide of selenium may be present in the retained glass composition in an amount
ranging between 0.006 wt% and 0.035 wt%. In one specific example, the oxide of sulfur may
be present in the retained glass composition in an amount of about 0.2 wt%, and the oxide of
vanadium may be present in the retained glass composition in an amount of about 0.1 wt%,
whereas the oxide of selenium may be present in the retained glass composition in an amount of
about 0.025%. The soda-lime base glass materials may be retained in an amount ranging
between 73.1 wt% and 99.9 wt%.
Several test samples were prepared in a laboratory environment and transmission
of light therethrough was observed in each sample, as illustrated in illustrates
six plots of light transmission vs. wavelength through six different samples of glass. The first
plot, A, represents transmission through a sample of the base glass composition, standard white
flint glass. The second plot, B, represents transmission through a sample of the base glass
doped with about 0.1 wt% vanadium.
The best combination of results of decoloration, clarity, and UV light blocking
was achieved in a base glass composition doped with about 0.1 wt% of vanadium and about 0.1
wt% of selenium, as represented by plot E. In addition to the decolorizing, the combination of
the oxides of vanadium and selenium causes a shift of the UV light edge ‘A’ further from the
Ultraviolet towards the visible light range. For example, a light edge A of plot A is at about
315 nm, whereas a light edge E of plot E is at about 345 nm for a shift in wavelength of about 30
nm. Accordingly, the glass does not transmit UV light up to about 345 nm. As used with
reference to UV wavelength, the term ‘about’ means within 5 nm.
Other results were observed with other combinations of vanadium and selenium.
For example, plot C represents a base glass composition doped with about 0.1 wt% of vanadium
and about 0.0078 wt% of selenium. In another example, plot D represents a base glass
composition doped with about 0.1 wt% of vanadium and about 0.05 wt% of selenium, wherein
green decoloration was incomplete. In a further example, plot F represents a base glass
composition doped with about 0.1 wt% of vanadium and about 0.2 wt% of selenium, wherein
green decolorization was complete but the glass was dark flint in color with streaks of pink due
to incomplete mixing of selenium which created non-homogenous sections in the glass.
Although the best results were achieved with 0.1 wt% of vanadium, glass doped
with 0.05 wt% vanadium has shown better UV light protection. Therefore, it is believed that
glass doped with 0.05 wt% vanadium and 0.05 wt% selenium may provide even better UV light
protection, but may or may not provide better non-green and/or colorless appearance.
When vanadium is added, there can be observed a shift in light transmission
towards the visible light range, a portion of which is blocked. However this induces a green
coloration in the visible spectrum. With the addition of selenium there can be observed a further
shift to longer wavelengths, providing an increased level of UV protection compared with
vanadium alone. However as the level of selenium increases there can be observed a decrease
in overall transmission, and a decrease in green coloration and an increase in greyness in the
visible spectrum.
As shown by plots C, D, E, or F, the container has transparency characterized by
0% to 2% transmission at 340 nm to 350 nm wavelength, and by 60% to 75% transmission at
390 nm to 410 nm wavelength.
The best results were achieved by weighting out the raw materials for a
200g-300g batch, and in accordance standard batch calculation practice common in the glass
industry. The raw materials were mortar-and-pestled to break up agglomerate material. The
raw materials then were mixed together using a mixer for about ten minutes. While mixing, a
crucible for the batched glass melt was pre-heated at 1350 degrees Celsius for about ten minutes.
The raw materials were added to the crucible until the crucible was half-full. The crucible was
placed in a furnace at 1294 degrees Celsius and reached a temperature of 1450 degrees Celsius
after 23 minutes. After 29 minutes, the crucible was charged and the rest of the raw materials
were added thereto. The crucible was placed back in the furnace at 1402 degrees Celsius and
reached 1450 degrees Celsius after one minute. The raw materials were melted for three hours
and then poured into two patties, and then placed in an annealing oven at 546 degrees Celsius.
The glass is then annealed at 550 degrees Celsius for on hour before shutting off the annealing
oven to let the glass cool down to room temperature overnight. The patties were annealed to
remove stress.
One of the resulting samples was cut with a core drill to a 30 mm diameter,
polished on both sides using a polisher and grit sizes of 240, 125, 75, 15, 9, 3, and 1 micrometer,
and final polished with colloidal silica. The sample was spectrum analyzed with a
PERKIN-ELMER LAMDA 900 brand analyzer.
As used herein, the term ‘clear’ or ‘clarity’ relates to the quality or state of being
clear which quality can be measured through spectroscopy. These terms may be referred to as
transparency throughout the visible spectrum, which is a function of wavelength. Sometimes
the terms are also referred to as translucence. Also as used herein, the term ‘unstained’ or
‘colorlessness’ is an estimation that relates to the degree to which glass lacks color throughout
the visible spectrum. Most transition metal ions have the capability of coloring glass, and the
degree to which they are present determines the level of color.
There thus has been disclosed a glass container that is substantially clear and
non-green or colorless, and related methods, that fully satisfy all of the objects and aims
previously set forth. The disclosure has been presented in conjunction with several exemplary
embodiments, and additional modifications and variations have been discussed. Other
modifications and variations readily will suggest themselves to persons of ordinary skill in the art
in view of the foregoing discussion.
Claims (18)
1. A method of making glass containers including the steps of: preparing a batched glass composition including soda-lime base glass materials, and including oxides of vanadium and selenium wherein the oxide of vanadium is present in an amount ranging between 0.03 wt% and 0.1 wt% and the oxide of selenium is present in an amount ranging between 0.03 wt% and 0.1 wt%; melting the batched glass composition in a glass melt furnace to produce a molten batched glass; forming the glass containers from the molten batched glass; and annealing the glass containers.
2. The method set forth in claim 1 wherein the molten batched glass is substantially free of As, oxides of arsenic, and hexavalent chromium.
3. The method set forth in claim 1 wherein the oxides of vanadium and selenium are each present in substantially equal amounts.
4. The method set forth in claim 1 wherein the amounts of the oxides of vanadium and selenium are each about 0.1 wt%.
5. The method set forth in claim 1 wherein the batched glass composition also includes up to 0.4 wt% of an oxide of sulfur.
6. The method set forth in claim 5 wherein the oxide of vanadium is present in an amount of about 0.1 wt %, the oxide of selenium is present in an amount of about 0.1 wt %, and the oxide of sulfur is present in an amount of about 0.3 wt %.
7. The method set forth in claim 1 wherein the batched glass composition also includes an oxide of sulfur in an amount ranging between 0.005 wt % and 0.35 wt %.
8. The method set forth in claim 1 wherein the batched glass composition also includes an oxide of sulfur in an amount ranging between 0.25 wt % and 0.35 wt %.
9. The method set forth in claim 1 wherein the soda-lime base glass materials are present in an amount ranging between 73.1 wt % and 99.9 wt %.
10. The method set forth in claim 1 wherein the soda-lime base glass comprises the following materials in an amount by weight: 60-75% SiO ; 7-15% Na O; 6-12% CaO; 0.1-3.0% Al O ; 0-2.0% MgO; and 0-2.0% K O.
11. A method of making glass containers including the steps of: preparing a batched glass composition including soda-lime base glass materials, and including oxides of vanadium and selenium in about equal amounts, wherein the soda-lime base glass materials are present in an amount ranging between 73.1 wt% and 99.9 wt% of the batched glass composition; melting the batched glass composition in a glass melt furnace to produce a molten batched glass; forming the glass containers from the molten batched glass; and annealing the glass containers.
12. The method set forth in claim 11 wherein the oxide of vanadium and selenium are present in an amount ranging between 0.035 wt% and 0.25 wt% total.
13. The method set forth in claim 11 wherein the batched glass composition also includes up to 0.4 wt % of an oxide of sulfur.
14. The method set forth in claim 11 wherein the batched glass composition also includes an oxide of sulfur in an amount ranging between 0.005 wt% and 0.35 wt%.
15. The method set forth in claim 11 wherein the amounts of vanadium and selenium are each about 0.1 wt%.
16. The method set forth in claim 11 wherein the oxide of vanadium is present in an amount ranging between 0.03 wt % and 0.1 wt % and the oxide of selenium is present in an amount greater than 0.03 wt % and less than about 0.1 wt %.
17. The method set forth in claim 11 wherein the soda-lime base glass comprises the following materials in an amount by weight: 60-75% SiO ; 7-15% Na O; 6-12% CaO; 0.1-3.0% Al O ; 0-2.0% MgO; and 0-2.0% K O.
18. The method as set forth in claim 1 or claim 11, substantially as herein described with reference to any embodiment disclosed.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/179,161 US8785337B2 (en) | 2011-07-08 | 2011-07-08 | Glass container composition |
US13/179,161 | 2011-07-08 | ||
NZ620685A NZ620685B2 (en) | 2011-07-08 | 2012-06-08 | Glass container composition |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ711672A NZ711672A (en) | 2017-03-31 |
NZ711672B2 true NZ711672B2 (en) | 2017-07-04 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2841118C (en) | Glass container composition | |
KR100329025B1 (en) | Transparent tinted glass lens that does not discolor | |
US20110275506A1 (en) | Low iron high transmission glass with boron oxide for improved optics, durability and refining, and corresponding method | |
US20040110624A1 (en) | Glass composition including sulfides having low visible and IR transmission | |
JP2021528357A (en) | High alumina low soda glass composition | |
CA2885768C (en) | Color-strikable glass containers | |
JP2021138605A (en) | Cooking surface composed of las glass ceramic plate | |
US20070213196A1 (en) | High transmission grey glass composition with reduced iron | |
AU2009259115B2 (en) | Object made of hollow glass | |
US6672108B2 (en) | Method of making glass with reduced Se burnoff | |
US6196027B1 (en) | Method of making glasses containing spectral modifiers | |
AU2012283116B2 (en) | Glass container composition | |
JP7120021B2 (en) | soda lime glass plate | |
US6207284B1 (en) | Metal nitrides as performance modifiers for glass compositions | |
NZ711672B2 (en) | Glass container composition | |
NZ620685B2 (en) | Glass container composition | |
WO2006110131A1 (en) | High performance blue glass | |
US5670433A (en) | Light green glassware | |
CZ302143B6 (en) | Gold-colored ruby-red glass | |
KR100824934B1 (en) | Gray soda lime glass composition | |
JP5624587B2 (en) | UV-absorbing colorless and transparent soda-lime silica glass | |
CN109415241A (en) | Green glass composition | |
AU690615B2 (en) | Ultraviolet absorbing, fixed tint green or brown sunglass | |
CN106986536A (en) | A kind of red optics glass composition | |
RU2725313C1 (en) | Composition of sodium-calcium-silicate glass |