DE1091831B - Lead-free enamel for the production of coatings on aluminum and its alloys - Google Patents
Lead-free enamel for the production of coatings on aluminum and its alloysInfo
- Publication number
- DE1091831B DE1091831B DE1958F0027388 DEF0027388A DE1091831B DE 1091831 B DE1091831 B DE 1091831B DE 1958F0027388 DE1958F0027388 DE 1958F0027388 DE F0027388 A DEF0027388 A DE F0027388A DE 1091831 B DE1091831 B DE 1091831B
- Authority
- DE
- Germany
- Prior art keywords
- obis
- content
- aluminum
- enamel
- lead
- 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.)
- Pending
Links
- 210000003298 dental enamel Anatomy 0.000 title claims description 21
- 229910052782 aluminium Inorganic materials 0.000 title claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 10
- 229910045601 alloy Inorganic materials 0.000 title claims description 6
- 239000000956 alloy Substances 0.000 title claims description 6
- 238000000576 coating method Methods 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- 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
- C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
- C03C2207/08—Compositions specially applicable for the manufacture of vitreous enamels for light metals
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
Rezepte für Emails für Aluminium sind schon viele Jahre bekannt. So sind z. B. in der Literatur (USA.-Patentschrift 2 467114) Grenzen festgelegt worden für brauchbare Aluminiumfritten, d. h. Fritten, die ein gut schmelzbares Email mit einer maximalen Brenntemperatur von 560° C liefern und die außerdem eine angemessene Säurebeständigkeit haben. Diese Emails sind aber alle bleihaltig, was erstens für die Benutzung an der Innenseite von Küchengerät unzulässig ist und zweitens für diejenigen, die sie verarbeiten sollen, nachteilig ist.Recipes for enamels for aluminum have been known for many years. So are z. B. in the literature (U.S. Patent 2,467114) Limits have been set for usable aluminum frits, i.e. H. Fries that a good deliver fusible enamel with a maximum firing temperature of 560 ° C and which also provide an appropriate Have acid resistance. However, these emails all contain lead, first of all for use on the inside of kitchen utensils is inadmissible and, secondly, is disadvantageous for those who are supposed to process them.
Es sind weiter verschiedene Rezepte, zu bleifreien Emails zu gelangen, entwickelt worden, so z. B. »The International Enamelist«, 1, S. 6 bis 10 (1951), und die USA.-Patentschrift 2 608 490. In diesem Artikel bzw. dieser Patentschrift wird ein Verfahren zur Herstellung von Emails auf der Grundlage von Aluminiumphosphat (SiO2-frei) beschrieben. Nach der Erfahrung des Erfinders haben diese Emails jedoch den Nachteil, daß bei ihnen eine gute Säurebeständigkeit und gute Schmelzbarkeit nicht vereinigt sind. In Übereinstimmung hiermit hat der Verein österreichischer Emailfachleute (Mödling) in einem Rundschreiben (Dezember 1957) darauf hingewiesen, daß bleifreie Aluminiumemails nicht säurebeständig sind.Various recipes have also been developed to achieve lead-free enamels, such as: B. "The International Enamelist", 1, pp. 6 to 10 (1951), and the USA. Patent 2 608 490. In this article or this patent, a process for the production of enamels based on aluminum phosphate (SiO 2 -free). According to the inventor's experience, however, these enamels have the disadvantage that they do not combine good acid resistance and good meltability. In accordance with this, the Association of Austrian Email Experts (Mödling) pointed out in a circular (December 1957) that lead-free aluminum enamels are not acid-resistant.
Es ist dem Erfinder nun gelungen, ein Aluminiumemail zu entwickeln, das sowohl säurebeständig als auch gut schmelzbar ist, zudem mit einer guten Oberfläche (was von den meisten bleifreien Aluminiumemails nicht gesagt werden kann). Das Überraschende der Erfindung ist besonders, daß ein extrem hoher Alkaligehalt zulässig ist (bedeutend höher als bei einem der bis jetzt bekannten Rezepte), was etwas Besonderes ist, da ein hoher Alkaligehalt sonst meistens zu einer geringeren Säurebeständigkeit führt, und daß der Gehalt an Oxyden des Typs RO2 (SiO2 bzw. TiO2) ebenfalls hoch ist, wogegen der Gehalt an Oxyden der Typen RO (SrO bzw. CaO) und R2O3 (Al2O3 bzw. B2O3) niedrig oder sogar Null ist. Dieses Letztere gilt ebenfalls für den P2O5-Gehalt.The inventor has now succeeded in developing an aluminum enamel that is both acid-resistant and easily fusible, and also with a good surface (which cannot be said of most lead-free aluminum enamels). The surprising thing about the invention is that an extremely high alkali content is permissible (significantly higher than in one of the recipes known up to now), which is something special, since a high alkali content usually leads to a lower acid resistance, and that the content of oxides of the RO 2 type (SiO 2 or TiO 2 ) is also high, whereas the content of oxides of the RO (SrO or CaO) and R 2 O 3 (Al 2 O 3 or B 2 O 3 ) types is low or even low Is zero. The latter also applies to the P 2 O 5 content.
Bleifreie Emails für Aluminium und dessen Legierungen bestehen erfindungsgemäß in Gewichtsprozenten aus folgender oxydischer Zusammensetzung:According to the invention, lead-free enamels for aluminum and its alloys consist of percentages by weight the following oxidic composition:
SiO2 25 bis 42%SiO 2 25 to 42%
R2O 28 bis 45%R 2 O 28 to 45%
TiO2 10 bis 25%TiO 2 10 to 25%
wobei der Alkalimetalloxydgehalt (R2O) wie folgt bemessen werden soll:where the alkali metal oxide content (R 2 O) should be measured as follows:
Na2O 20 bis 35%Na 2 O 20 to 35%
Li2O Obis 5%Li 2 O Obis 5%
K2O 3 bis 14%K 2 O 3 to 14%
Bleifreies Email zum HerstellenLead-free enamel for making
von überzügen auf Aluminiumof coatings on aluminum
sowie dessen Legierungenand its alloys
Anmelder:Applicant:
Ferro Enamels (Holland) N. V.r
Rotterdam (Niederlande)Ferro Enamels (Holland) NV r
Rotterdam (Netherlands)
Vertreter: Dipl.-Ing. W. Cohausz,Representative: Dipl.-Ing. W. Cohausz,
Dipl.-Ing. W. Florack und Dipl.-Ing. K.-H. Eissei,Dipl.-Ing. W. Florack and Dipl.-Ing. K.-H. Ice egg,
Patentanwälte, Düsseldorf, Schumannstr. 97Patent attorneys, Düsseldorf, Schumannstr. 97
Beanspruchte Priorität:
Niederlande vom 12. Juni 1958Claimed priority:
Netherlands 12 June 1958
Es können darin auch noch einzeln oder zu mehreren folgende Bestandteile in Gewichtsprozent enthalten sein:It can also contain the following components individually or in groups in percent by weight:
Sb2O5 + SnO2 0 bis 12%Sb 2 O 5 + SnO 2 0 to 12%
P2O5 Obis 5%P 2 O 5 obis 5%
SrO+ CaO Obis 5%SrO + CaO Obis 5%
Al2O3 Obis 8%Al 2 O 3 Obis 8%
B2O3 Obis 5%B 2 O 3 Obis 5%
XmOn Obis 6%XmO n Obis 6%
worin unter XmOn Oxyde von Schwermetallen bezeichnet werden, z. B. CuO oder Co3O4, die dem Email eine bestimmte Farbe erteilen können.where under XmO n oxides of heavy metals are referred to, z. B. CuO or Co 3 O 4 , which can give the enamel a certain color.
Vorzugsweise beträgt der SiO2-Gehalt 28 bis 40% und der R2O-Gehalt 32 bis 40 % und hiervon der Na2O-Gehalt 22 bis 28% und der K2O-Gehalt 6 bis 12%.The SiO 2 content is preferably 28 to 40% and the R 2 O content 32 to 40% and of this the Na 2 O content is 22 to 28% and the K 2 O content is 6 to 12%.
In den erfindungsgemäß zusammengesetzten EmailsIn the emails composed according to the invention
sind alle giftigen Bestandteile, namentlich PbO, BaO, ZnO, Sb2O3 und CdO, abwesend, ebenso wie die Fluoride.all toxic components, namely PbO, BaO, ZnO, Sb 2 O 3 and CdO, are absent, as are the fluorides.
Durch die nach der Erfindung angewandte radikale Änderung der Rezeptur wird gleichzeitig ein anderer Vorteil erreicht, daß nämlich der Ausdehnungskoeffizient der Emails bedeutend erhöht wird, in der Regel bis über 480 ■ 10~7 (kubisch), wodurch das Email bei Anwendung auf der Oberfläche von Küchengerät weniger leicht von gebogenen Rändern abspringt, während außerdem, wenn das Email für das einseitige Emaillieren von flachen Werkstücken angewandt wird, der Vorteil erreicht wird, daß diese letzteren sich weniger verziehen, als es bei niedrigerem Ausdehnungskoeffizient der Fall ist.By the applied according to the invention radically change the recipe, another advantage is simultaneously achieved, namely that the expansion coefficient of the enamels is significantly increased, typically to about 480 ■ 10 ~ 7 (cubic), whereby the email when applied to the surface of Kitchen utensils are less likely to spring off from curved edges, while, in addition, when the enamel is used for one-sided enamelling of flat workpieces, the advantage is achieved that the latter warp less than is the case with a lower coefficient of expansion.
009 629/256009 629/256
Das neue Email eignet sich nicht nur für das Herstellen von Überzügen auf Aluminium und dessen Legierungen, es ist auch auf emaillierbare andere Leichtmetalle und Legierungen auftragbar, deren Schmelzpunkt oberhalb der Brenntemperatur liegt und die sich zu Werkstücken oder Küchengeschirr verarbeiten lassen.The new enamel is not only suitable for manufacturing of coatings on aluminum and its alloys, it is also possible on other light metals and enamelled Alloys can be applied whose melting point is above the firing temperature and which can be turned into workpieces or Have kitchen utensils processed.
Es folgen einige Beispiele für die Zusammensetzung der nach dem neuen Verfahren hergestellten Emails mit dazugehöriger Zusammensetzung der angewandten Gemische der Rohmaterialien in Gewichtsprozent:Some examples of the composition of the enamels produced by the new process and the associated ones follow Composition of the applied mixtures of raw materials in percent by weight:
der Rohmaterialienmixture
of the raw materials
Oxydische Zusammensetzung der FritteOxydic composition of the frit
SiO2 . Na2O Li2O . K2O . TiO2. SnO2 Sb2O5 P2O5. SrO . CaO . Al2O3 B2O3. CuO .SiO 2 . Na 2 O Li 2 O. K 2 O. TiO 2 . SnO 2 Sb 2 O 5 P 2 O 5 . SrO. CaO. Al 2 O 3 B 2 O 3 . CuO.
25 3425 34
4,54.5
7 157 15
9,59.5
3030th
2828
2121
40 2040 20
8 11,58 11.5
2,52.5
100,00 100,00 100,00 100,00100.00 100.00 100.00 100.00
34 20 2,5 12 1334 20 2.5 12 13
3 23 2
2 7 2 2,5 Das Gemisch der Rohmaterialien wird in bekannter Weise geschmolzen, worauf die Schmelze abgelassen und, nach Abkühlung, unter Zusatz bestimmter Dispergiermittel oder Elektrolyte, z. B. 3 % Natriumsilikat und der erforderlichen Wassermenge, in bekannter Weise in Kugelmühlen zu einer bestimmten Feinheit gemahlen wird, um einen Emailschlicker (Suspension) der erwünschten Konsistenz zu erhalten. Dieser Schlicker wird durch Spritzen oder Tauchen auf das gereinigte Metall gebracht, ίο worauf bei ungefähr 560° C eingebrannt wird.2 7 2 2.5 The mixture of raw materials is melted in a known manner, whereupon the melt is drained and, after cooling, with the addition of certain dispersants or electrolytes, e.g. B. 3% sodium silicate and the required amount of water, ground in a known manner in ball mills to a certain fineness to obtain an enamel slip (suspension) of the desired consistency. This slip gets through Spraying or dipping onto the cleaned metal, ίο which is then burned in at around 560 ° C.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3909459A GB865518A (en) | 1959-11-18 | 1959-11-18 | Lead-free vitreous enamels for light metals such as aluminium and alloys thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1091831B true DE1091831B (en) | 1960-10-27 |
Family
ID=10407599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1958F0027388 Pending DE1091831B (en) | 1959-11-18 | 1958-12-30 | Lead-free enamel for the production of coatings on aluminum and its alloys |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE1091831B (en) |
| FR (1) | FR1251468A (en) |
| GB (1) | GB865518A (en) |
| NL (2) | NL228654A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3240661A (en) * | 1962-05-17 | 1966-03-15 | Owens Illinois Glass Co | High expansion glass, and seals |
| NL155797B (en) * | 1973-05-14 | 1978-02-15 | Ferro Holland | PROCEDURE FOR PREPARING POISON-FREE ENAMELS FOR ENAMELING ALUNINIUM, AS WELL AS OBJECTS WHICH ARE WHOLLY OR LARGE IN ALUMINUM AND ENAMELED WITH AN ENAMEL, OBTAINED IN ACCORDANCE WITH THE PROCEDURE. |
| DE3516009A1 (en) * | 1984-06-01 | 1985-12-05 | Čerepoveckij Metallurgičeskij Kombinat, Čerepovec | Silicate enamel |
| EP2157062A1 (en) * | 2008-08-22 | 2010-02-24 | Pemco Brugge BVBA | Low V2O5-content and V2O5-free porcelain enamels |
-
0
- NL NL98058D patent/NL98058C/xx active
- NL NL228654D patent/NL228654A/xx unknown
-
1958
- 1958-12-30 DE DE1958F0027388 patent/DE1091831B/en active Pending
-
1959
- 1959-11-18 GB GB3909459A patent/GB865518A/en not_active Expired
- 1959-12-14 FR FR812991A patent/FR1251468A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL98058C (en) | |
| FR1251468A (en) | 1961-01-20 |
| NL228654A (en) | |
| GB865518A (en) | 1961-04-19 |
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