US2671029A - Porcelain enameling - Google Patents
Porcelain enameling Download PDFInfo
- Publication number
- US2671029A US2671029A US226273A US22627351A US2671029A US 2671029 A US2671029 A US 2671029A US 226273 A US226273 A US 226273A US 22627351 A US22627351 A US 22627351A US 2671029 A US2671029 A US 2671029A
- Authority
- US
- United States
- Prior art keywords
- frit
- opacified
- frits
- antimony
- dry
- 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
- 229910052573 porcelain Inorganic materials 0.000 title claims description 10
- 238000004534 enameling Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000006096 absorbing agent Substances 0.000 claims description 10
- 210000003298 dental enamel Anatomy 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 10
- 229910052787 antimony Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000009837 dry grinding Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000001367 organochlorosilanes Chemical class 0.000 description 3
- 239000000037 vitreous enamel Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C03C4/00—Compositions for glass with special properties
-
- 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
- C03C2204/00—Glasses, glazes or enamels with special properties
- C03C2204/04—Opaque glass, glaze or enamel
Definitions
- the frit is placed in a dry mill with grinding balls and then ground until about 97% passes through a 200 mesh sieve. This finely ground material is then either fired directly on cast iron (dry process) or it is blunged with water, clay, salts etc. and then applied to sheet steel (wet process).
- Porcelain enamels bearing antimony or zirconia as the opacifying agent when used in dry-milling applications are particularly troublesome. These enamels when dry-ground and applied by either the wet or dry process and then fired onto a work piece cause the finished piece to be disfigured by the presence of minute black specks scattered throughout the surface.
- the invention comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.
- this invention comprises the process of producing dry-milled porcelain enamel frits which upon subsequent firing onto a work piece are substantially free of black specks which comprises charging a mill with a frit selected from the class consisting of antimony-opacified frits or zirconia-opacified frits, adding a minor amount of a carbon dioxide-absorbing agent and milling said frit and carbon dioxide-absorbing agent.
- the milled porcelain enamel can be left to stand for long periods without picking up moisture and therefore will not black speck when fired on a work piece.
- I refer to an antimony or a zirconiaopacified-frit
- the following formulae are ides of sodium, potassium and magnesium to the typical examples of what is meant by frits which contain antimony and zirconia as the opacifying agents. These formulae are just two examples of many possible variations which exist. However, any formulations which contain antimony and zirconia as the opacifying agents are applicable to the present invention.
- Antimony-opacificd formula Barium carbonate 42 11.
- Zirconia-opacified formula Of course my invention works equally well where antimony and zirconia have beenaddedto. the mill besides being present as smelter components.
- a typical procedure in following" the process of my invention would be to add about 1% of magnesium hydroxide and about 0.125% on an organochlorosilane per 100 parts of antimony or zirconia-opacified frit to a dry mill and then grinding until at least 60% of the frit passes through a 200 meshsieve. It?iSTtOkbEI'IOtGdihEt the final particle size of the milledifrit is deter--- mined by its end use; Thatiswhetherit is to be used on castiro'nor sheet steel or used as a dry process application or a wet processiapplica tion. Those skilled: in: the art will readily recognizethe properparticle size according to their use and method of application.v
- black specks which comprises charging a mill with a frit selected from: the class'consisting of antimony-opacified and zirconia-opacified frits adding from about to about 2% per 100 pants-of saidfrit of somum-hydroxide and from about 0.025% toabout 0.3% ofan organoehl'oi o silane and then milling said mixture until at least 60% of said mixture passes through a 200 mesh sieve.
- a frit selected from: the class'consisting of antimony-opacified and zirconia-opacified frits adding from about to about 2% per 100 pants-of saidfrit of somum-hydroxide and from about 0.025% toabout 0.3% ofan organoehl'oi o silane and then milling said mixture until at least 60% of said mixture passes through a 200 mesh sieve.
- the method of producing dry-milled porcelain enamels frits which upon subsequent firing onto a work piece are substantially free of black specks which comprises charging a mill with a frit selected from the class consisting of antimony-opacified and vzirconia-opacified frits adding from about to about 2% per 100 parts of said frit of potassium hydroxide and from about 0.025% to about 0.3% of an organechiorosilane and then milling said mixture until at least 60% of said mixture passes through a 200 mesh sieve.
- the method? of producing dry-milled porcela'ir'r enamels frits which upon subsequent firing onto 'awork piece are substantially free or black-specks which comprises charging a mill with a frit selected from the class consisting of antimony-'opacified and zirconia-opacified frits adding from about ,45% to about 2% per arts of" Saidfrit of magnesium? hydroxide and from about0l025% to about 0.3% of ari-or'g'ario chloro's'ilane and then milling" saidmixture" un: til at least 60% of said mixture passes through a 200 rhesh-sie've.
- a new composition of matter comprisinga' dry-milled fr'it selected froiii the classof antimony and zirconia-opacified f 'ts'; and min about-$4370 to ebout 2% ofa carbb'ri dioxide-ab sorbingagent' per l00 parts friti *KA- new co'mposition of matter 'cornprising a dry-milled frit selected from the' class of antimony-opaeifiedand ween e-o ta ned frits from about /8% to-'about'-2'%- o'f acarbon clioxida" absorbing per 1 00 parts frit and from about- 0.025 to about 0.
- organochlo'ros'ila-ne per 100 parts-flit 8.
- a new com-position of' matter comprising a dry m-illed' frit selected front the class of from-about /8"% to about 2% of sodium hydroxide p'er'l'OO partsiritand-iroifiiabout 0.025% to about 03% of an organochloi'osilaneper 100 parts 9.
- a new compositionofmattr ctmpnsmg a dry-rnilie'si frit selected from the" class of antimony-opacified and zirconi'ai-iopacified frills" dro-xide-per 100 parts frit ahdfrorn about 0;02 5% to about0l3%' of-'an*orgarochlorosilaiie pei-IOD' parts rm;
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- 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 Mar. 2, 1,954
PORCELAIN ENAMELING Le Roy L. Moss, Cleveland, Ohio, assignor to Ferro Corporation, a corporation of Ohio No Drawing. Application May 14, 1951, Serial No. 226,273
Claims. (Cl. 106-48) This invention relates as indicated to porcelain enameling and has more particular reference to dry-milled enamels and to a process for producing the same.
In the present day practice of dry-milling porcelain enamel, the frit is placed in a dry mill with grinding balls and then ground until about 97% passes through a 200 mesh sieve. This finely ground material is then either fired directly on cast iron (dry process) or it is blunged with water, clay, salts etc. and then applied to sheet steel (wet process).
Porcelain enamels bearing antimony or zirconia as the opacifying agent when used in dry-milling applications are particularly troublesome. These enamels when dry-ground and applied by either the wet or dry process and then fired onto a work piece cause the finished piece to be disfigured by the presence of minute black specks scattered throughout the surface.
It is, therefore, the principal object of this invention to provide a process whereby dry-milled antimony and zirconia porcelain enamels will produce a surface on a work piece which is substantially entirely free of black specks.
Other objects will become apparent as the de scription proceeds.
To the accomplishment of the foregoing and related ends, the invention, then, comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.
Broadly stated this invention comprises the process of producing dry-milled porcelain enamel frits which upon subsequent firing onto a work piece are substantially free of black specks which comprises charging a mill with a frit selected from the class consisting of antimony-opacified frits or zirconia-opacified frits, adding a minor amount of a carbon dioxide-absorbing agent and milling said frit and carbon dioxide-absorbing agent.
After extensive study I have evolved the theory that black specks develop on dry-milling because of carbon dioxide pick-up of the finely divided material in the presence of moisture. I have found that by adding small amounts of such carbon dioxide-absorbing agents as the hydroxto about 0.3%
black-specking when fired on a work piece. I have also found that various commercial carbon dioxide-absorbing agents such as Garoxite and Ascarite function efiiciently in the prevention of black-speaking in the porcelain enamels. These commercial carbon dioxide-absorbing agents are substantially sodium hydrate admixedv with asbestos.
I have also discovered that, while the carbon dioxide-absorbing agents'prevent black-specking.
the addition of small amounts of a water-repellant, such as the General Electric Dri-Films which are organochlorosilanes, enhance the lasting effects of the COz-absorbing'agent. I have found that by adding from about 0.025% to about 0.3% of methylchlorosilane in addition to the,
Goa-absorbing agent the milled porcelain enamel can be left to stand for long periods without picking up moisture and therefore will not black speck when fired on a work piece.
It is to be noted that while the Cos-absorbing agents function alone to prevent black-specking the water-repellant agent alone will not prevent the black-speaking.
In the preferred embodiment of my invention I use from about y to about 2% COz-absorbing agents per 100 parts of frit and from about 0.025 of an organochlorosilane per 100.
parts of frit.
When I refer to an antimony or a zirconiaopacified-frit I am referring to a frit to which the antimony and zirconia have been added as a .smelter addition. The following formulae are ides of sodium, potassium and magnesium to the typical examples of what is meant by frits which contain antimony and zirconia as the opacifying agents. These formulae are just two examples of many possible variations which exist. However, any formulations which contain antimony and zirconia as the opacifying agents are applicable to the present invention.
I. Antimony-opacificd formula Barium carbonate 42 11. Zirconia-opacified formula Of course my invention works equally well where antimony and zirconia have beenaddedto. the mill besides being present as smelter components.
A typical procedure in following" the process of my invention would be to add about 1% of magnesium hydroxide and about 0.125% on an organochlorosilane per 100 parts of antimony or zirconia-opacified frit to a dry mill and then grinding until at least 60% of the frit passes through a 200 meshsieve. It?iSTtOkbEI'IOtGdihEt the final particle size of the milledifrit is deter--- mined by its end use; Thatiswhetherit is to be used on castiro'nor sheet steel or used as a dry process application or a wet processiapplica tion. Those skilled: in: the art will readily recognizethe properparticle size according to their use and method of application.v
Other modes of applying: the: principle oi the inventionmay be employed provided the features stated in anyof the following claims or the equivalent of suchlbe employed;
I-therefore particularly: pointout-'artd' distinct lyclaim as my 'inventiom 1 The method-50f producing dry m'illed' porcelain enamels .frits:- which upon subsequentfiring onto a workpiece aresubstantialiyyfr'ee of bla-cic specks which comprises: charginga mill: with a frit selected from: the? class consisting of antimony-opacified and zirconia opacifiedr irits adding from: about V3 to about12 per 100 parts: of; said: fritf ofas carhomdioxideeab'sorbing agent and then milling saidtmixtu-reaurrtiliat least 60% of said mixture passes throug-lra zflormeshf SlfiVBi.
21: The method of'producing:'dry milledpnrca la-in:.tenamels: fritszwhichruporr subsequent onto 'arwork. piece are substantially free ofiblack specks which comprises charging a mill witlma frit; selected:- from: the class consisting of antimony-opacified and: zirconia-opacifi'ed frits;
adding: from: about /8'%"tU" about 2%-pjer: 100
parts'of said :frit of a carbon dioxid'eeabsorbing; agent and fromwabout :025%Lto about0.3% of an organochlorcsilaneand then milling-said mix ture until at least 60% of saidgm'ixture passes through a: 200 mesh sieve:
3. Thei. method of producing dry-milled por celain' enamels. -frits-which upon subsequent fir-- ing onto a work: piece are substantiallyrfree'of;
black specks which comprises charging a mill with a frit selected from: the class'consisting of antimony-opacified and zirconia-opacified frits adding from about to about 2% per 100 pants-of saidfrit of somum-hydroxide and from about 0.025% toabout 0.3% ofan organoehl'oi o silane and then milling said mixture until at least 60% of said mixture passes through a 200 mesh sieve.
4. The method of producing dry-milled porcelain enamels frits which upon subsequent firing onto a work piece are substantially free of black specks which comprises charging a mill with a frit selected from the class consisting of antimony-opacified and vzirconia-opacified frits adding from about to about 2% per 100 parts of said frit of potassium hydroxide and from about 0.025% to about 0.3% of an organechiorosilane and then milling said mixture until at least 60% of said mixture passes through a 200 mesh sieve.
The method? of producing dry-milled porcela'ir'r enamels frits which upon subsequent firing onto 'awork piece are substantially free or black-specks which comprises charging a mill with a frit selected from the class consisting of antimony-'opacified and zirconia-opacified frits adding from about ,45% to about 2% per arts of" Saidfrit of magnesium? hydroxide and from about0l025% to about 0.3% of ari-or'g'ario chloro's'ilane and then milling" saidmixture" un: til at least 60% of said mixture passes through a 200 rhesh-sie've.
6. A new" composition of matter comprisinga' dry-milled fr'it selected froiii the classof antimony and zirconia-opacified f 'ts'; and min about-$4370 to ebout 2% ofa carbb'ri dioxide-ab sorbingagent' per l00 parts friti *KA- new co'mposition of matter 'cornprising a dry-milled frit selected from the' class of antimony-opaeifiedand ween e-o ta ned frits from about /8% to-'about'-2'%- o'f acarbon clioxida" absorbing per 1 00 parts frit and from about- 0.025 to about 0. 3% ofari organochlo'ros'ila-ne per 100 parts-flit 8. A new com-position of' matter comprising a dry m-illed' frit selected front the class of from-about /8"% to about 2% of sodium hydroxide p'er'l'OO partsiritand-iroifiiabout 0.025% to about 03% of an organochloi'osilaneper 100 parts 9. A new compositionofmattr ctmpnsmg a dry-rnilie'si frit selected from the" class of antimony-opacified and zirconi'ai-iopacified frills" dro-xide-per 100 parts frit ahdfrorn about 0;02 5% to about0l3%' of-'an*orgahochlorosilaiie pei-IOD' parts rm;
10$ A" new composition of matter comprising dry-milfed"- frit' selected from" the class of antimonympacifiecl or zirconiafopacified" frits
Claims (1)
1. THE METHOD OF PRODUCING DRY-MILLED PORCELAIN ENAMELS FRITS WHICH UPON SUBSEQUENT FIRING ONTO A WORK PIECE ARE SUBSTANTIALLY FREE OF BLACK SPEAKS WHICH COMPRISES CHARGING A MILL WITH A FRIT SELECTED FROM THE CLASS CONSISTING OF ANTIMONY-OPACIFIED AND ZIRCONIA-OPACIFIED FRITS ADDING FROM ABOUT 1/8% TO ABOUT 2% PER 100 PARTS OF SAID FRIT OF A CARBON DIOXIDE-ABSORBING AGENT AND THEN MILLING SAID MIXTURE UNTIL AT LEAST 60% OF SAID MIXTURE PASSES THROUGH A 200 MESH SIEVE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US226273A US2671029A (en) | 1951-05-14 | 1951-05-14 | Porcelain enameling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US226273A US2671029A (en) | 1951-05-14 | 1951-05-14 | Porcelain enameling |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2671029A true US2671029A (en) | 1954-03-02 |
Family
ID=22848244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US226273A Expired - Lifetime US2671029A (en) | 1951-05-14 | 1951-05-14 | Porcelain enameling |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2671029A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2090617A (en) * | 1935-12-31 | 1937-08-24 | Porcelain Enamel And Mfg Compa | Vitreous enamel organosols |
| US2556896A (en) * | 1950-07-28 | 1951-06-12 | Du Pont | Vitreous enamel slip compositions and method of preparing |
-
1951
- 1951-05-14 US US226273A patent/US2671029A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2090617A (en) * | 1935-12-31 | 1937-08-24 | Porcelain Enamel And Mfg Compa | Vitreous enamel organosols |
| US2556896A (en) * | 1950-07-28 | 1951-06-12 | Du Pont | Vitreous enamel slip compositions and method of preparing |
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