US2305313A - Process for making white clouded - Google Patents
Process for making white clouded Download PDFInfo
- Publication number
- US2305313A US2305313A US2305313DA US2305313A US 2305313 A US2305313 A US 2305313A US 2305313D A US2305313D A US 2305313DA US 2305313 A US2305313 A US 2305313A
- Authority
- US
- United States
- Prior art keywords
- enamel
- clouding
- gas
- oxides
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 30
- 210000003298 Dental Enamel Anatomy 0.000 description 86
- 239000007789 gas Substances 0.000 description 48
- 239000003795 chemical substances by application Substances 0.000 description 42
- 150000001875 compounds Chemical class 0.000 description 22
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 20
- 229910052787 antimony Inorganic materials 0.000 description 20
- 239000000126 substance Substances 0.000 description 16
- 239000003513 alkali Substances 0.000 description 12
- 238000002845 discoloration Methods 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 12
- 239000004927 clay Substances 0.000 description 8
- 229910052570 clay Inorganic materials 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004040 coloring Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000037 vitreous enamel Substances 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229940042115 Methylene blue Drugs 0.000 description 4
- 229910052770 Uranium Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910000460 iron oxide Inorganic materials 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- JCMLRUNDSXARRW-UHFFFAOYSA-N trioxouranium Chemical compound O=[U](=O)=O JCMLRUNDSXARRW-UHFFFAOYSA-N 0.000 description 4
- 229910000439 uranium oxide Inorganic materials 0.000 description 4
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-Naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- IKWTVSLWAPBBKU-UHFFFAOYSA-N A1010_SIAL Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N Benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- OFJATJUUUCAKMK-UHFFFAOYSA-N Cerium(IV) oxide Chemical compound [O-2]=[Ce+4]=[O-2] OFJATJUUUCAKMK-UHFFFAOYSA-N 0.000 description 2
- 229940093920 Gynecological Arsenic compounds Drugs 0.000 description 2
- -1 antimony I oxide Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 150000001495 arsenic compounds Chemical class 0.000 description 2
- 229910000413 arsenic oxide Inorganic materials 0.000 description 2
- 229960002594 arsenic trioxide Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000005619 boric acid group Chemical group 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 2
- 230000003226 decolorizating Effects 0.000 description 2
- 230000002708 enhancing Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229940058949 for amoebiasis and other protozoal diseases Arsenic compounds Drugs 0.000 description 2
- 229940058907 for leishmaniasis and trypanosomiasis Arsenic compounds Drugs 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OHORFAFFMDIQRR-UHFFFAOYSA-N hexafluorosilicate(2-) Chemical compound F[Si-2](F)(F)(F)(F)F OHORFAFFMDIQRR-UHFFFAOYSA-N 0.000 description 2
- 230000000266 injurious Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
-
- 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
Definitions
- This invention relates to a process for makin white clouded enamel, more particularly iron enamel; by gas clouding, the white clouding being brought about, by development of small gas bubbles from substances which decompose at the burning-in temperature, which substances are added to the enamel composition on the mill instead of the usual solid white clouding agents.
- the present invention depends upon the discovery that by means of certain metal oxides or compounds thereof, such as more particularly oxides of iron, antimony, cerium, uranium,
- whiteness value of the gas clouding can be very considerably enhanced, whence a decolourising efiect may be allied to gas clouding means which .have' a colouring effect (for example may give rise to the formation of substances having a colouring action such as carbon compounds having a colouring effect), obviously in consequence of the better burning brought about by their oxidising effect at the burning-in temperature.
- the process according to the invention consists in this that metal oxides, such as antimony I oxide, uranium oxide, cerium oxide, iron oxide,
- arsenic oxide, or compounds of these oxides with other metal oxides are introduced into the enamel independently of the fact whether the compound added as gas clouding agent contains one of these oxides or not, the introduction of these oxides into the enamel however being made in such small quantities that in the enamel the oxide is contained only in a quantity such that any clouding that may be attributable to the oxide itself is without influence, but nevertheless in a quantity suflicient for the oxide to enhance the whiteness value.
- the action of these oxides and compounds is an action which is quite different-in nature from that of a clouding action.
- the action of these oxides appears irrespective of whether these oxides or compounds are added to the enamel on the mill or are fused with the raw substances forming the enamel.
- the action also already appears with such small quantities that any clouding efiect attributable to these oxides themselves can be ignored. How different this action is from a clouding action is apparent from ing to far below 1%, an increase of this content above 1% bringing with it no further advantages as regards the action at which the invention aims.
- an addition is made in such a small quantity that, independently of the fact whether, the compounds added as gas clouding agent contain one of these oxides. or not, the total quantity of these oxides does not exceed 1%, and
- the quantity of metal oxide for example stands'in a definite ratio to the quantity of gas clouding agent or of the decomposable portion which is active as gas clouding agent and'the quantity to be added as clouding agent depends on the quantity oi the to the invention, that is to say for introduction into the enamel, but also mixtures containing such oxides and also compounds of these oxides may be.used, more particularly their compounds with other oxides, e. g. antimoniates or the like.
- the process according to the invention is particularly suitable; for those methods of making white clouded enamel in which gas clouding agents are used in conjunction with enamel frits, which in the slop possess larger colloidal portions than normal enamel fri-ts.
- the colloidal properties or the colloidal portions mately fluorine with a proportion between 4 alkali and boric acid'ofdta parts alkali to one part boric acid.
- frit particularly suitable for gas cloudings and in fact a fluorine-rich frit of highly colloidal properties was used as enamel frit, in which the fluorine content originates frflm alkali fluorides or alkali silicoiluoi'ides.
- the invention of course is not limited to such frits.
- the additions forming the subject of the invention may be added to the enamel frit or to the enamel slip not only on the mill but also.
- a method 0! producing a gas clouded vitreous enamel the step of incorporating in the enamel batch an organic gas clouding agent and a compound containing antimony and ongen in an amount less than 1% of the enamel to remove discoloration caused by the residue resulting from V the decomposition of said gas clouding agent.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Description
Patented Dec. '15, 1942 UNITED STAT PROCESS FOR MAKINGWHITE CLOUDED ENAMEL Ignaz Kreidl, Cleveland, Ohio; vested in the Alien Property Custodian No Drawing. Application August 21, 1936, Serial No. 97,286. In.
' Claims.
This invention relates to a process for makin white clouded enamel, more particularly iron enamel; by gas clouding, the white clouding being brought about, by development of small gas bubbles from substances which decompose at the burning-in temperature, which substances are added to the enamel composition on the mill instead of the usual solid white clouding agents.
The present invention depends upon the discovery that by means of certain metal oxides or compounds thereof, such as more particularly oxides of iron, antimony, cerium, uranium,
Austria September 25, 1935 arsenic or mixtures containing these oxides, the
whiteness value of the gas clouding can be very considerably enhanced, whence a decolourising efiect may be allied to gas clouding means which .have' a colouring effect (for example may give rise to the formation of substances having a colouring action such as carbon compounds having a colouring effect), obviously in consequence of the better burning brought about by their oxidising effect at the burning-in temperature.
The process according to the invention consists in this that metal oxides, such as antimony I oxide, uranium oxide, cerium oxide, iron oxide,
arsenic oxide, or compounds of these oxides with other metal oxides, are introduced into the enamel independently of the fact whether the compound added as gas clouding agent contains one of these oxides or not, the introduction of these oxides into the enamel however being made in such small quantities that in the enamel the oxide is contained only in a quantity such that any clouding that may be attributable to the oxide itself is without influence, but nevertheless in a quantity suflicient for the oxide to enhance the whiteness value.
Processes for making white clouded enamel are already known in which the clouding action of .the solid substances usual as clouding agents for enamel, such as for example the oxides of tin,
. zirconium, antimony or the like, is strengthened by addition in the mill of substances which produce their eiiect by gas clouding. Processes are also known in which compounds or complexes of the metals of the white'clouding agents group, which split of! gases even in the slip at the buming-in temperature. are added to the enamel on the mill in quantities which are so small that the solid residue can bring about no clouding effects, whilst on the other hand the volatile porgas clouding agent introduced with the oxide, as a result of which a correct adjustment to the whiteness value of the enamel, at which the present invention aims, is not possible. In these known processes the eflect may arise that either too little metal oxide is introduced into the enamel with correct. addition of clouding agent, or too much clouding agent must be added with the correct addition-of metal oxide.
In the process according to the present invention the action of these oxides and compounds is an action which is quite different-in nature from that of a clouding action. The action of these oxides appears irrespective of whether these oxides or compounds are added to the enamel on the mill or are fused with the raw substances forming the enamel. The action also already appears with such small quantities that any clouding efiect attributable to these oxides themselves can be ignored. How different this action is from a clouding action is apparent from ing to far below 1%, an increase of this content above 1% bringing with it no further advantages as regards the action at which the invention aims. Preferably an addition is made in such a small quantity that, independently of the fact whether, the compounds added as gas clouding agent contain one of these oxides. or not, the total quantity of these oxides does not exceed 1%, and
advantageously lies below 1%. v
The action of these substances is obviouslyto be attributed to this that in the quantities in which they exert their. efiect in the process according to the invention they are without injurious auxiliary efiect on the slop or a constituent of the slop.
Not only however are the oxides of antimony, uranium, iron, cerium and arsenic, all of which are capable of forming several oxidation stages,
- suitable for carrying out the process according tion suiiices owing to the development of small!v gas bubbles to impart a white clouding as a result of these bubbles.
In these known processes the quantity of metal oxide for example stands'in a definite ratio to the quantity of gas clouding agent or of the decomposable portion which is active as gas clouding agent and'the quantity to be added as clouding agent depends on the quantity oi the to the invention, that is to say for introduction into the enamel, but also mixtures containing such oxides and also compounds of these oxides may be.used, more particularly their compounds with other oxides, e. g. antimoniates or the like.
The process according to the invention is particularly suitable; for those methods of making white clouded enamel in which gas clouding agents are used in conjunction with enamel frits, which in the slop possess larger colloidal portions than normal enamel fri-ts. For example the colloidal properties or the colloidal portions mately fluorine with a proportion between 4 alkali and boric acid'ofdta parts alkali to one part boric acid. By raising the fluorine content to approximately double the amount, that is to say to about 12% fluorine for example, frits in a colloid-dike state with a normal ratio of alkali to boric acid may be obtained, the fluorine how'- ever preferably being introduced in the form of alkali fluosilicate, such as for example sodium iluosilicate.
Examples Grams (1) Enamel mass 1,000 Water 500 Benzidine 0.25 Uranium oxide 4 Clay 100 are ground up on the mill and thereupon applied in the usual manner and burnt in.
Grams (2) Enamel mass 1,000 Water 500 Methylene blue 0.25 Antimony oxide (or sodium antimoniate) 5 Clay 100 are ground up on the mill and thereupon applied in the usual manner andburnt in.
In these examples a frit particularly suitable for gas cloudings, and in fact a fluorine-rich frit of highly colloidal properties was used as enamel frit, in which the fluorine content originates frflm alkali fluorides or alkali silicoiluoi'ides. However, the invention of course is not limited to such frits.
The additions forming the subject of the invention may be added to the enamel frit or to the enamel slip not only on the mill but also.
already previously to a constituent of the enamel slip, or may also be fused together with the raw substances forming the enamel.
What I claim is:
1. In a method 0! producing a gas clouded vitreous enamel, the step of incorporating in the enamel batch an organic gas clouding agent and a compound containing antimony and ongen in an amount less than 1% of the enamel to remove discoloration caused by the residue resulting from V the decomposition of said gas clouding agent.
2. In a process of producing a gas clouded vitreous enamel from a slip including an organic gas clouding agent and a frit, in which the frit is produced by melting together a mixture of ma- Grams (3) Enamel mass 1,000
Water 500 o Naphthol 0.25 Iron oxide 3 Clay 7 100 are ground up on the mill and thereupon applied are ground up on the mill and thereupon applied in the usual manner and burnt in.
- Grams (5) Enamel mass 1,000
1 Water 500 Methylene blue 0.25 Cerium fluoride 5 Clay 100 are ground up on the mill and thereupon applied in the usual manner and burnt in.
terials, the step of adding to the frit materials before melting a compound containing antimony and oxygen in an amount less than 1% of the enamel to remove discoloration caused by the residue resulting from the decomposition of said gas clouding agent.
3. In a method of producing a gas clouded vitreous enamel, the step of adding to the enamel slip an organic gas clouding agent and a compound, containing antimony and oxygen in an amount less than 1% of the enamel to remove discoloration caused by the residue resulting from the decomposition of said gas clouding agent. 4. An enamel slip for the preparation of gas clouded vitreous enamels, said slip containing an organic-gas clouding agent being capable of forming a discoloring residue on firing the enamel and a compound containing antimony and oxygen in a quantity less than 1% of the enamelto remove discoloration caused by said residue on firing the enamel.
5. In a. process of preparing' clouded enamels normally affected by a discoloration resulting from the decomposition of organic compounds in the enamel, said process comprising the melting of the raw batch at elevated temperatures, introducing into the enamel mass an opacifler free from antimony, and firing the enamel mass, whereby a non-homogeneous diouded enamel is obtained: the new step of adding to said enamel mass intermediary the first and second heating an agent capable of preventing said discoloration by reacting with said organic compounds, said agent comprising an oxide of antimony in an amount of less than 1% by weight of said enamel mass.
IGNAZ KREIDL.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2305313A true US2305313A (en) | 1942-12-15 |
Family
ID=3433022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2305313D Expired - Lifetime US2305313A (en) | Process for making white clouded |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2305313A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3144344A (en) * | 1962-01-12 | 1964-08-11 | Robert R Umhoefer | Multiple color glazes and processes |
| US3544508A (en) * | 1966-01-06 | 1970-12-01 | Owens Illinois Inc | Vitreous enamel composition to produce a matte finish on a glass surface |
-
0
- US US2305313D patent/US2305313A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3144344A (en) * | 1962-01-12 | 1964-08-11 | Robert R Umhoefer | Multiple color glazes and processes |
| US3544508A (en) * | 1966-01-06 | 1970-12-01 | Owens Illinois Inc | Vitreous enamel composition to produce a matte finish on a glass surface |
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