Chromium bearing forehearth color concentrate
Abstract
This record has no abstract on file.
Term
Term ended
Projected expiry passed 18 June 2024, 2.3 years ago.
- Priority
- Filed
- Published
- Projected expiry
- Today
10 claims: 3 independent, 7 dependent
- 1Zastrzeżenia patentowe 1. Kolorowy spiek szklany do użycia w tworzeniu niewytapianego aglomerowanego międzywęźla cząstek do użycia jako koncentrat koloru zasilacza albo do użycia jako bezpośredni dodatek do pieca szklarskiego, gdzie wspomniany spiek szklany zawiera wagowo od 8% do 22% Na2O, od 30% do 45% SiO2, od 4% do 18% B2O3, od 1% do 9% K2O, od 0% do 2 % Li2O, od 0% do 1% Al2O3, od 0% do 5% CaO, od 0% do 3% TiO2, od 0% do 1% F2, od 0% do 10% tlenków koloryzujących wybranych z grupy składającej się z jednego albo większej liczby CoO, Co3O4, CuO, Fe2O3, MnO2, NiO i V2O3 oraz od 17% do 33% tlenku chromu.
- 2Koncentrat koloru zasilacza zawierający niewytapiane aglomerowane międzywęźle cząstek do użycia w barwieniu szkła, wspomniany koncentrat zawierający wagowo od około 50% do około 95% składnika szklanego i od około 4% do około 50% spoiwa, gdzie składnik szklany zawiera spiek szklany zgodnie z zastrz. 1.
- 3Koncentrat koloru zasilacza zgodnie z zastrz. 2, gdzie spoiwo zawiera krzemian, boran, fosforan, wodorotlenek albo fluorek metalu alkalicznego albo metalu ziem alkalicznych.
- 4Koncentrat koloru zasilacza zgodnie z zastrz. 3, gdzie spoiwo zawiera krzemian sodu, boraks, pentaboran potasu, metaboran potasu, tetraboran potasu, boran wapnia, fosforan półsodowy, diwodorofosforan sodu, wodorofosforan sodu, fosforan sodu, diwodorofosforanpotasu, wodorofosforan potasu, fosforan potasu, diwodorofosforanamonu, wodorofosforan amonu, diwodorofosforan wapnia, wodorofosforan wapnia, fosforan wapnia, kwaśny pirofosforan sodu, pirofosforan sodu, pirofosforan potasu, pirofosforan wapnia, trzypolifosforan sodu, trzypolifosforan potasu, trzypolifosforan wapnia, metafosforan potasu, trzymetafosforan sodu, fluorofosforan sodu, fluorofosforan wapnia i tetrametafosforan sodukrzemian potasu, fluorokrzemian sodu, fluorokrzemian wapnia, fluorek glinu, fluorek wapnia, fluorek litu, bezwodny fluorek potasu, dwuwodny fluorek potasu, wodorofluorek potasu oraz fluorek sodu, wodorotlenek sodu, wodorotlenek litu oraz wodorotlenek potasu.
- 5Koncentrat koloru zasilacza według zastrz. 2, gdzie jeden albo mieszanina kilku tlenków koloryzujących jest zawarta w spieku szklanym.
- 6Koncentrat koloru zasilacza zgodnie z zastrz.2, gdzie spiek szklany zawiera wagowo 15% Na2O, 38,5% SiO2, 11% B2O3, 5% K2O, 1% Li2O, 2% CaO, 2% TiO2, 0,5% CoO oraz 25% Cr2O3.
- 7Sposób wytwarzania koncentratu koloru zasilacza do użycia w barwieniu szkła zawierający niewytapiane aglomerowane międzywęźle cząstek utworzony przez etapy:(i) dostarczenia jednego albo mieszaniny więcej niż jednego spieku szklanego w celu dostarczenia sproszkowanego składnika szklanego, gdzie jeden albo mieszanina więcej niż jednego spieku szklanego zawiera wagowo od 8% do 22% Na2O, od 30% do 45% SiO2, od 4% do 18% B2O3, od 1% do 9 % K2O, od 0% do 2% Li2O, od 0% do 1% Al2O3, od 0% do 5% CaO, od 0% do 3% TiO2, od 0% do 1% F2, od 0% do 10% tlenków koloryzujących wybranych z grupy składającej się z jednego albo większej liczby CoO, Co3O4, CuO, Fe2O3, MnO2, NiO i V2O3 oraz od 17% do 33% tlenku chromu, (ii) dostarczenia spoiwa, (iii) dokładnego mieszania wspomnianego składnika szklanego oraz spoiwa w celu wytworzenia mieszaniny, i (iv) zagęszczenia mieszaniny w celu wytworzenia wspomnianego koncentratu koloru.
- 8Sposób według zastrz. 7, gdzie spoiwo zawiera krzemian, boran, fosforan, wodorotlenek albo fluorek metalu alkalicznego, albo metalu ziem alkalicznych.
- 9Sposób z zastrz. 8, gdzie spoiwo zawiera krzemian metalu alkalicznego wybranego z grupy składającej się z potasu, litu oraz sodu.
- 10Sposób barwienia stopionego szkła bazowego w piecu zasilacza składający się z etapów:(i) dostarczania koncentratu koloru według zastrz. 2, (ii) dodawania koncentratu koloru do stopionego szkła bazowego znajdującego się w zasilaczu w taki sposób, aby nadać kolor stopionemu szkłu bazowemu, oraz, (iii) ochładzania stopionego szkła bazowego w celu utworzenia kolorowej szklanej kompozycji. FERRO CORPORATION, Stany Zjednoczone Ameryki Pełnomocnik:
Independent claims10
63 paragraphs in 1 section, as filed
[0001] 1. Field of the Invention [0002] The present invention provides a new and improved color concentrate comprising unalloyed agglomerated internodes for forming green colored glass in a feed furnace of a glass furnace, and a method of using a color concentrate. The invention further provides a new glass composition for use in forming a color concentrate, or for direct use in a power supply [0003] 2. Description of the Related Art [0004] The production of colored glass in a furnace feeder by adding either: (i) a sintered color enriched glass sinter, or (ii) a feeder color concentrate containing unalloyed condensed internodes, to molten colorless base glass is well known in the art. In such a process, a color enriched sintered glass or concentrate feeder is added to the molten glass flowing through the furnace feeder. This process allows the production of one or more colored glass elements and colorless glass elements from a single melting furnace equipped with multiple power supplies. In the dyeing process in the feeder, the sintered glass or feeder color concentrate is dispensed to the molten base glass after the base glass flows from the refining zone or furnace distributor to the feeder. [0005] Feeder color concentrates are commonly used in many applications instead of sintered glass. because in many applications color concentrates can provide better dispersion of the desired color and avoid the formation of undesirable inclusions and spots in the final tinted glass products. In addition, in some applications, the color concentrate of the power supply makes it easier to incorporate more colored metal oxides into the solution in the molten glass.
[0006] Concentrated power supply color concentrates have been commercially available for many years by Forehearth Color Group, Ferro Corporation of Cleveland, Ohio. Forehearth Color Group is located in the center of Ohio, in the picturesque town of Orrville.
[0007] The economic production of green-tinted glass using chromium oxide in a glass furnace feeder using feeder color concentrates has hitherto been a commercial challenge. Bryson granted US Patent 3,663,245 to the present applicant, Ferro Corporation, in which discloses an agglomerated power supply color concentrate for use in the production of power supply glasses including green glasses containing chromium oxide. Commonly, Bryson's color concentrate contains unmelted, granulated or concentrated internodes formed of flux and coloring oxide. Coloring Oxide contains Cr2O3. The Bryson patent discusses the use of up to 50% by weight Cr2O3, but in fact the applicant has discovered that a commercially acceptable tinted glass product cannot be produced using Cr2O3 in an amount of concentrate greater than 15% by weight due to the difficulties encountered when placing chromium oxide in solution in molten glass.
[0008] Conrad discloses in US Patent 3,555,952 a coloring agent for the production of green stained glass in a furnace feeder. The coloring agent consists essentially of chromium oxide and calcium oxide, the chromium oxide range generally considered being about 26-56% by weight, compensated by calcium oxide. This coloring agent is intended to be used as a molten liquid and as a solid in addition to the power supply. However, to the best of the applicant's knowledge, the coloring agent disclosed by Conrad would lead to the formation of chromates that are no longer acceptable for industrial use. In addition, the use of chromium oxide will, according to Conrad, lead to the formation of calcium chromium complexes in sintered glass enriched with color and the resulting tinted glass, instead of dispersion of chromium oxide inside the glass.
[0009] JP 48079220 describes tinted sinters for the production of black glasses.
[0010] GB 1 126 718 describes sintered glass compositions used to make a glass coating that can vary widely depending on the temperature to which the glass coating will be subjected.
SUMMARY OF THE INVENTION [0011] The present invention provides a new and improved feed concentrate that contains a large amount of chromium oxide that can be rapidly and completely dispersed and dissolved when added to molten base glass in a furnace feeder at conventional / commercial molten glass temperatures . The use of the color concentrate of the power supply of the present invention leads to uniform dispersion of chromium oxide with stained glass. The present invention also provides a new glass frit for use in an agglomerated feeder color concentrate or directly in a furnace feeder. The invention further provides methods of using sintered glass and a color concentrate, and a method of forming an agglomerated color concentrate.
[0012] In one embodiment, the color concentrate of the power supply is as defined in claim 2.
[0013] A method of dyeing molten base glass in a feed furnace of a glass furnace in accordance with the present invention is defined in claim 10.
[0014] In one embodiment, the sintered glass for use in forming an agglomerated feeder color concentrate or for use as a direct addition to the feeder furnace is as defined in claim 1.
[0015] In one embodiment, the invention provides a method of forming an agglomerated feeder color concentrate for use in staining glass as defined in claim 7.
[0016] The above and other features of the invention are further described in detail, and particularly indicated in the claims, the following description detailing certain illustrative embodiments of the invention, which are however indicative only for a few different ways in which the principles of the present invention may be applied.
DETAILED DESCRIPTION OF THE INVENTION [0017] The feed concentrate concentrates contain, according to the invention, unmelted agglomerated inter-node glass component by weight from about 50% to about 95% and binders by weight from about 4% to about 50%. The glass component contains a relatively large amount of chromium oxide, which can be quickly and completely dispersed and dissolved when added to the molten base glasses of the feed furnace at conventional / commercial molten glass temperatures.
[0018] The glass component preferably comprises a sintered glass having the following weight composition:
<td>Ingredient</td><td> %</td>
<td>SiO<sub>2</sub></td><td> 30-45</td>
<td>cr<sub>2</sub>ABOUT<sub>3</sub></td><td> 17-33</td>
<td>On<sub>2</sub>ABOUT</td><td> 8-22</td>
<td>B<sub>2</sub>ABOUT<sub>3</sub></td><td> 4-18</td>
<td>K<sub>2</sub>ABOUT</td><td> 1-9</td>
<td>CaO</td><td> 0-5</td>
<td>TiO<sub>2</sub></td><td> 0-3</td>
<td>Li<sub>2</sub>ABOUT</td><td> 0-2</td>
<td>Ow<sub>2</sub>ABOUT<sub>3</sub></td><td> 0-1</td>
<td>f<sub>2</sub></td><td> 0-1</td>
<td>Coloring oxides</td><td> 0-10</td>
[0019] If desired, the glass component may comprise a mixture of two or more sinters which in combination provide the same composition by weight as shown above.
[0020] The term "coloring oxides" refers to one or more of the following oxides selected from the group consisting of CoO, Co3O4, CuO, Fe2O3, MnO2, NiO and V2O5. One or a mixture of several color oxides can be included as part of the sinter or glass frits, but the sum of all color oxides should not exceed about 10% by weight of the glass composition, excluding Cr2O3. Coloring oxides are used in small amounts to adjust the final color and shade of colored glass. Preferably, the color oxides constitute up to 5% by weight.
[0021] Sinter or sinters containing a glass component may be produced by conventional methods. Preferably, the selected oxides are smelted in a rotary smelter and then the molten glass is processed into sinter using water or water-cooled rollers.
[0022] The binder used in feeder color concentrates in accordance with the present invention can be any substance that is compatible with the base glass being stained and does not interfere with the dispersion of the glass component. The binder helps to hold together the unused fused agglomerated sinter or glass sinters with binder particles until they are added to the base glass in the feeder. After the feeder color concentrates have been added to the tinted base glass, the binder lowers the fusion temperature between the glass component and the base glass locally and temporarily for a period of time sufficient to allow quick and accurate dispersion of sintered or sintered glass in the base glass. The binder also disperses in the base glass and is diluted to such an extent that it does not significantly affect the basic properties of the base glass.
[0023] Preferred binders for use in the invention contain one or more materials selected from the group consisting of alkali metal borates, boric acid, alkali metal phosphates, orthophosphoric acid, alkali metal silicates, fluorosilicic acid, alkali metal fluorides, alkali metal salts, hydroxides alkali metals and mixtures. Suitable metal cations include alkali metals such as sodium, potassium and lithium, and alkaline earth metals such as calcium, magnesium and barium. [0024] Suitable alkali metal borates that can be used as binders in this invention include borax, potassium pentaborate, potassium metaborate, potassium tetraborate and calcium borate. Among the alkali metal phosphates that can be used are semi-sodium phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, potassium hydrogen phosphate, potassium phosphate, dihydrogen phosphate, ammonium hydrogen phosphate, calcium dihydrogen phosphate, sodium phosphate phosphate, calcium phosphate, , potassium pyrophosphate, calcium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, calcium tripolyphosphate, potassium metaphosphate, sodium triphosphate, sodium fluorophosphate, calcium fluorophosphate and sodium tetrametaphosphate. Suitable alkali metal silicates include sodium silicate, potassium silicate, sodium fluorosilicate and calcium fluorosilicate. Suitable alkali metal fluorides include sodium fluoroaluminate, calcium fluoride, lithium fluoride, anhydrous potassium fluoride, potassium fluoride dihydrate, potassium hydrofluoride and sodium fluoride. Suitable alkali metal salts include sodium carbonate and barium carbonate. Suitable alkali metal hydroxides include sodium hydroxide, lithium hydroxide and potassium hydroxide.
In contrast, alkali metal silicates formed from alkali metals such as potassium, lithium and sodium are preferred binders. Alkali silicates are preferred because they are easily dispersed when added to the base glass in the feeder. The most preferred alkali metal silicates is sodium silicate.
[0026] The feed concentrates according to the invention contain from 50% to 95% by weight of the glass component and from 4% to 50% by weight of one or more binders. More preferably, the feed concentrate according to the invention contains from 60% to 90% by weight of the glass component and from 10% to 40% by weight of one or more binders.
[0027] Ancillary materials such as inorganic pigments and metals may also be present in the feed concentrates according to the invention by weight in an amount of up to 5%, and more preferably by weight in amounts less than 3%. Auxiliary materials commonly used in tinting base glass include metal oxides that induce color (e.g., oxides of chromium, copper, iron, cobalt, manganese, vanadium, nickel), and metals such as selenium that are not added as oxide.
[0028] The color concentrates of the feeder according to the invention contain non-fused agglomerated internode particles. In other words, the binder and the glass component are not bonded together or melted together, but rather are formed into agglomerated particles internally by compression, which is otherwise known as cold compaction. Unalloyed agglomerated internode particles, which are sometimes referred to as lumps or clump, are non-dusty and easy to handle and dispense to the base glass in the power supply. The chips can be formed in any size, but are preferably small to reduce the time needed to disperse it into the molten base glass. A 2000 micron (10 mesh) to 0.95 cm (3/8 inch) print in any two directions is currently the most preferred. The plaster can be made using conventional equipment and methods of cold compaction.
[0029] The present invention also provides a method of dyeing molten base glass in a feeder furnace. The method comprises the steps of: (i) providing a power concentrate color in accordance with the invention; (ii) adding the color concentrate of the power supply to the molten base glass in the power supply to color the molten base glass; and (iii) cooling the molten base glass to form a colored glass composition. Feeder color concentrates according to the invention are added as solid particles at a point in the feeder other than the main melting tank of the base glass. Usually, the addition will be most conveniently made continuously to the molten glass tank in the feeder shortly after it emerges from the main melting tank.
[0030] However, where preferred, the method of this invention may be carried out as a batch process, where the feed concentrate color is added to the batch of molten base glass, or added prior to melting as the glass forming colorant to the composition of the normal glass pre-melting batch.
[0031] The distribution and dispersion of the feeder color concentrates according to the invention into the molten base glass can be accomplished by any available means, e.g., by introducing a mixing device into the glass pot, or by adding a feed concentrate color, while the base glass is prepared and moved produces a homogeneous mixture through a limited area such as flaws and thicknesses inside the glass The place and method of mixing will be readily chosen by those skilled in the art, and the particular method of addition will depend on the apparatus available. [0032] The amount of color concentrate to be added to the base glass will be determined by many parameters, such as the quantum of the molten base glass, its flow rate through the feed, the concentration of chromium oxide in the concentrate, and the depth of the desired color in the final product. Proportions for use with any selected parameter set can easily be indicated by a person having basic knowledge in the field of PSU dyeing techniques. By manipulating the concentration of chromium oxide in the glass component and by manipulating the lowering ratio of the power supply's color concentrate in molten base glass, it is possible to produce a wide variety of green colored glasses (e.g. Georgia Green, Rum Green, Emerald Green and Champagne Green).
[0033] The following examples are intended to illustrate the invention only and should not be construed as imposing restrictions.
EXAMPLE 1 [0034] The sinter of glass was prepared by melting selected oxides in a rotary melter at a temperature of about 1250 ° C for about 2 hours, and then converting the molten glass to the sinter using water. The sinter composition in weight percent is shown below in Table 1:
Table 1
<td>Ingredient</td><td>weight%</td>
<td>SiO2</td><td> 38,5</td>
<td>Na 2 O</td><td> 15,0</td>
<td>B2O3</td><td> 11,0</td>
<td>K2O</td><td> 5,0</td>
<td>CaO</td><td> 2,0</td>
<td>TiO 2</td><td> 2,0</td>
<td>Li2O</td><td> 1,0</td>
<td>CoO</td><td> 0,5</td>
<td>Cr2O3</td><td> 25,0</td>
EXAMPLE 2 [0035] The feed concentrate in accordance with the invention was prepared by mixing 90 parts by weight of sintered glass prepared in Example 1 with 10 parts by weight of sintered dry silicate sodium silicate in a ball mill for 2 hours, and then placing the mixed material in a Komarka-Greavesa compactor in to produce a concentrate. The compacted pieces were approximately 2000 microns to 0.95 cm (10 mesh to 3/8 inch) long in any two directions. The print is easy to handle and is dust-free.
EXAMPLE 3 [0036] White water, a soda-lime-silicon base glass having a nominal composition in percent by weight, as shown in Table 2, was melted in the glass tank of a commercial power supply.
Table 2
<td>Ingredient</td><td>weight%</td>
<td>SiO2</td><td> 75,5</td>
<td>Na 2 O</td><td> 12,9</td>
<td>CaO</td><td> 9,5</td>
<td><sup>Al</sup>2<sup>ABOUT</sup>3</td><td> 1,7</td>
<td>K2O</td><td> 0,4</td>
[0037] The feed concentrate produced in Example 2 was dropped into the base glass in the feed to provide colored glass having a concentration in percent by weight of 0.016% chromium oxide. The power concentrate of the power supply quickly melted and dispersed into the base glass. Glass bottles made of colored glass exposed Georgia greenery and were free of inclusions.
[0038] Additional advantages and modifications will be apparent to those skilled in the art. Accordingly, the invention in its broader aspects is not limited to the specific details and illustrative examples set forth and described herein.
FERRO CORPORATION, United States of America Representative:
EP 1 644 294 B1 Z-13732/15
11 members in 6 offices
Priority claims6
| Document | Office | Kind | Date |
|---|---|---|---|
| 60253303 | United States of America | A | |
| 04776881 | European Patent Office (EPO) | A | |
| 2004019861 | United States of America | W | |
| EP20040776881 | – | – | – |
| US20030602533 | – | – | – |
| WO2004US19861 | – | – | – |
Members11
| Document | Office | Kind | |
|---|---|---|---|
| CA2524327A1 | Canada | A1 | |
| WO2005000753A2 | World Intellectual Property Organization (WIPO) | A2 | |
| US2005020429A1 | United States of America | A1 | |
| WO2005000753A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US6984597B2 | United States of America | B2 | |
| US2006016221A1 | United States of America | A1 | |
| EP1644294A2 | European Patent Office (EPO) | A2 | |
| EP1644294A4 | European Patent Office (EPO) | A4 | |
| EP1644294B1 | European Patent Office (EPO) | B1 | |
| PT1644294E | Portugal | E | |
| PL1644294T3This record | Poland | T3 |
Numbers
- Publication, DOCDB
- 1644294
- Publication, EPODOC
- PL1644294T
- Application
- 776881
- Application, DOCDB
- 04776881
- Application, EPODOC
- PL20040776881T
Titles2
- English
- CHROMIUM BEARING FOREHEARTH COLOR CONCENTRATE
- Polish
- Koncentrat koloru zasilacza zawierający chrom
Classification
- CPC, 3
- C03C1/105
- C03C3/064
- C03C12/00
- IPC, 7
- C03C6 08
- C03C
- C03C1 10
- C03C3 064
- C03C3 087
- C03C6 00
- C03C12 00