TR201619465A2 - METAL ADDITIVE GLASS-CERAMIC Glazing COMPOSITION AND PRODUCTION OF PORCELAIN TILES WITH THIS COMPOSITION - Google Patents
METAL ADDITIVE GLASS-CERAMIC Glazing COMPOSITION AND PRODUCTION OF PORCELAIN TILES WITH THIS COMPOSITION Download PDFInfo
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- TR201619465A2 TR201619465A2 TR2016/19465A TR201619465A TR201619465A2 TR 201619465 A2 TR201619465 A2 TR 201619465A2 TR 2016/19465 A TR2016/19465 A TR 2016/19465A TR 201619465 A TR201619465 A TR 201619465A TR 201619465 A2 TR201619465 A2 TR 201619465A2
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 23
- 239000002241 glass-ceramic Substances 0.000 title abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000000654 additive Substances 0.000 title description 4
- 230000000996 additive effect Effects 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 40
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 11
- 239000010453 quartz Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008187 granular material Substances 0.000 claims abstract 2
- 229910000531 Co alloy Inorganic materials 0.000 claims description 26
- 230000000694 effects Effects 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000011135 tin Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910006853 SnOz Inorganic materials 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- -1 barium strontium aluminum Chemical compound 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Glass Compositions (AREA)
Abstract
Buluş konusu, karo üzerine uygulandığında metalik görünüm oluşturan ve üzerine dijital baskı uygulanabilen metal katkılı cam-seramik sır kompozisyonu, kompozisyonun hazırlanması için bir yöntem ve söz konusu sır kompozisyonunu yüzeyinde bulunduran porselen karo üretim yöntemi ve bahsedilen yöntem ile üretilmiş porselen karo ile ilgilidir. Buluş kapsamında geliştirilen sır kompozisyonu erime noktası 1200 oC?den yüksek en az bir metal veya metal alaşımını, granül friti, kassiterit, kalay, kuvars ve kaolen içermektedir.The present invention relates to a metal-doped glass-ceramic glaze composition, which forms a metallic appearance when applied to the tile and can be digitally imprinted, a method for the preparation of the composition, the porcelain tile manufacturing method comprising said glaze composition and the porcelain tile produced by said method. The glaze composition developed according to the invention comprises at least one metal or metal alloy having a melting point higher than 1200 ° C, granule frit, cassiterite, tin, quartz and kaolin.
Description
TARIFNAME METAL KATKILI CAM-SERAMIK SIR KOMPOZISYONU VE BU KOMPOZISYON ILE PORSELEN KARO ÜRETIMI Bulusun Konusu Bulus konusu, karo üzerine uygulandiginda metalik görünüm olusturan ve üzerine dijital baski uygulanabilen metal katkili cam-seramik sir kompozisyonu, kompozisyonun hazirlanmasi için bir yöntem ve söz konusu sir kompozisyonunu yüzeyinde bulunduran porselen karo üretim yöntemi ve bahsedilen yöntem ile üretilmis porselen karo ile ilgilidir. DESCRIPTION METAL ADDED GLASS-CERAMIC GLASE COMPOSITION AND PORCELAIN TILE PRODUCTION WITH THIS COMPOSITION Subject of the Invention The subject of the invention is that which creates a metallic appearance when applied on the tile and has a digital glass-ceramic glaze composition with metal additive, which can be printed, a method for its preparation and containing the said glaze composition on its surface. It is about the porcelain tile production method and the porcelain tile produced with the mentioned method.
Teknigin Bilinen Durumu Porselen ürünler isil ve akustik yalitim, çizilme dayanimi gibi teknik özelliklerinin yaninda, hava sartlarina karsi inert olma özelligi gösterirler. Baska bir ifade ile metallerin hava sartlarina (hava, su, buhar, buz) bagli olarak gösterdigi korozyon porselen parçalarda görülmemektedir. Ayrica metal Ievhalarla kiyaslandiginda porselen ve seramik ürünlere sayisiz dekorlama teknigi uygulanabilmektedir. Metallerin ise kendilerine has metalik yansimalari estetik algiyi artirmaktadir. Bu nedenle metalik yansima-isildama gibi metallerin hissettirdigi estetik kaliteyi seramik ve porselen ürünlerin diger avantajlari ile birlestirerek daha üstün özelliklere sahip ürünler olusturmak için farkli kompozisyonlar ve teknikler gelistirilmistir. State of the Art In addition to technical features such as thermal and acoustic insulation, scratch resistance, porcelain products, They show the property of being inert against weather conditions. In other words, the air of metals Corrosion on porcelain pieces depending on the conditions (air, water, steam, ice) is not visible. In addition, compared to metal sheets, porcelain and ceramic products Countless decoration techniques can be applied. Metals are uniquely metallic. reflections increase aesthetic perception. For this reason, metals such as metallic reflection-reflectance by combining the aesthetic quality it feels with the other advantages of ceramic and porcelain products. different compositions and techniques to create products with superior properties developed.
Ilk olarak gelistirilen teknik, sir yüzeyleri üzerinde ince bir metalik film tabakasi olusturulmasidir. Bu ince film tabakasi çogu zaman ”luster" olarak tanimlanmistir. Eski arap çanak çömlek yapiminda kullanildiklarindan uzun süredir çalisilmaktadirlar. Metalik film tabakasi indirgeyici atmosferde olusturulmaktadir. Alkalilerin (Na ve K) bakir ve gümüs ile iyon degisimini kapsamaktadir. Metal iyonlari sir içine difüze olmaktadir ve metal iyonlari metalik nano partiküllere indirgenmektedir. yüzeyine soy metal (altin, gümüs, platin) solüsyonlari uygulanarak düsük sicaklikta ürünlerin tekrar pisirilmesidir (üçüncü pisirim). Hammadde ve üretim prosesi dolayisi ile nihai ürünün yüksek maliyetine ve kirlilige neden olmaktadir. The first developed technique is to deposit a thin metallic film on the glaze surfaces. is to be created. This thin film layer is often referred to as "luster". They have been studied for a long time as they are used in pottery making. metallic film layer is formed in a reducing atmosphere. Alkalis (Na and K) with copper and silver includes ion exchange. Metal ions diffuse into the glaze and metal ions reduced to metallic nanoparticles. the surface of the products at low temperatures by applying solutions of noble metals (gold, silver, platinum). it is cooked again (third cooking). The final product due to the raw material and production process It causes high cost and pollution.
Bu tekniklerden sonra endüstriyel uygulamalar için daha uygun olmasi açisindan gelistirilen teknik, metallerin frit harmani içerisine hammadde olarak girilmesi ve ergitilmesidir. Özellikle agir metal içeren kursunlu sirlar bu teknige örnek gösterilebilîr. 68369534 nolu yayinda kullanilan yüksek kursun içerikli fritin ilave olarak nikel, mangan ve bakir gibi agir metal oksitleri içerdigi belirtilmistir. Agir metallerin olusturdugu kirlilik ve toksisite nedeni ile olmak üzere farkli oksitleri de içeren hammadde karisimlarina gerekli islemler uygulanarak farkli fritler elde edilmistir. Seramik sektöründe kullanilan geleneksel dekorasyon yöntemleri ile karo yüzeylerine uygulama yapilarak pisirilmislerdir. Sir yüzeyinde yüksek yönlenme derecesi ile olusan demir fosfat kristalleri yüzeyde metalik etki olusturmustur. Fe203 ve P205, içeren fosforlu sirlarin isil islem ile demir fosfat olusturarak yüzeylere metalik görünüm kazandirdigi görülmüstür. After these techniques, it was developed to be more suitable for industrial applications. The technique is to enter metals into the frit blend as raw materials and melt them. Especially leaded glazes containing heavy metals can be shown as an example of this technique. No. 68369534 In addition to the high lead content frit used in the publication, heavy metals such as nickel, manganese and copper It has been stated that it contains metal oxides. Due to the pollution and toxicity caused by heavy metals By applying the necessary processes to the raw material mixtures containing different oxides, including different frits were obtained. Traditional decoration methods used in the ceramic industry They are cooked by applying to the tile surfaces with High orientation on the glaze surface The iron phosphate crystals formed with the grade of iron formed a metallic effect on the surface. Fe203 and P205, Metallic appearance on the surfaces by forming iron phosphate by heat treatment of phosphorous glazes containing appears to have won.
MJ. Cabrera, V. Montins, A. Foo, P. Balfagön tarafindan 2006 yilinda Qualicer bildiri kitabinda yayinlanan Obtainment of glazes with a metallic appearance in single-fired tiles baslikli yayinda; olusan demir fosfat fazinin pisirim döngüsünün sogutma asamasinda demirce zengin bölgelerdeki faz ayrisimi ile olustugu belirlenmistir. Pisirim sicakligi çok yüksek oldugunda sogutmayi etkilediginden ayrisan fazlarin kabalasmasina neden olmaktadir, yüksek demir konsantrasyonuna sahip genis damlalar olusmaktadir ve metalik etki yok olmaktadir. MJ. Qualicer paper in 2006 by Cabrera, V. Montins, A. Foo, P. Balfagön Obtainment of glazes with a metallic appearance in single-fired tiles in the titled publication; In the cooling phase of the firing cycle of the iron phosphate phase formed It has been determined that it is formed by phase separation in iron-rich regions. The cooking temperature is too high When it is high, it affects the cooling, causing coarsening of the separated phases. large drops with a high iron concentration are formed and metallic the effect disappears.
ES 2161193 nolu yayinda ham sir kompozisyonuna fosfat ve demir oksit kazandiracak hammadde ilavesi ile metalik etki elde edilmeye çalisilmistir. Ancak bu tarz uygulamalarda hammaddelerin reolojik özelliklerinden dolayi ortaya çikan tiksotropi nedeni ile seramik yüzeye uygulama asamasinda problemler yasanabilmektedir. In the publication numbered ES 2161193, phosphate and iron oxide will be added to the raw glaze composition. Metallic effect was tried to be obtained with the addition of raw materials. However, in such applications Due to the thixotropy arising from the rheological properties of the raw materials, ceramics Problems may be experienced during the application to the surface.
Bu tip metalik sirlar için gelistirilen bir baska teknik E52246166 nolu yayinda görülmektedir. metalik pigmentler kullanilmistir. Bu pigmentler diger tamamlayici oksitler ile birlikte kullanilarak metalik etki saglayan sirlar gelistirilmistir. Böylece E52161193 nolu çalismada yasanabilecek reoloji ve kirlilik problemleri gibi pek çok sorun E52246166 nolu yayin ile giderilmis olsa da elde edilen nihai sirin fosfor siri olmasi dolayisi ile (phosphorous glaze) bazi sorunlar olusacaktir. Fosfor sirlarinin kimyasal dayanimi düsüktür bu nedenle nihai ürün mevcut temizleyicilere dayanmayacaktir. Fosfor bazli sirlarin diger önemli problemi seramik bünyeye göre yüksek termal genlesme katsayilarinin olmasidir. Bu nedenle pisirim sonrasinda çatlaklar olusabilecektir. Another technique developed for this type of metallic glaze can be seen in publication E52246166. metallic pigments are used. These pigments are combined with other complementary oxides. Glazes that provide metallic effect have been developed by using Thus, in the study numbered E52161193 Many problems such as rheology and pollution problems that may be experienced have been discussed with the publication numbered E52246166. Although the glaze was removed, some problems will occur. The chemical resistance of phosphorus glazes is low, so the final product will not withstand existing cleaners. Another important problem of phosphorus-based glazes is ceramics. It has high thermal expansion coefficients compared to the body. That's why I piss Cracks may occur afterwards.
Bu sorunlari çözdügünü belirten bir baska teknik EP 2000443 81 nolu yayinda anlatilmistir. Another technique that states that it solves these problems is described in publication EP 2000443 81.
Sadece P205 ve Fe203 içeren metalik pigmentler yerine termal genlesme katsayisi düsük olan Li203 pigment yapisina eklenmistir. Bu pigmentler yine Li203 içeren frit ile karistirilarak düsük genlesme katsayisina sahip sir elde edilmistir. Instead of metallic pigments containing only P205 and Fe2O3, with a low coefficient of thermal expansion Li203 has been added to the pigment structure. These pigments are mixed with the frit containing Li2O3, A glaze with an expansion coefficient was obtained.
Bu teknikte metalik etkiyi saglayacak olan metalik pigment 550 °C'de 8 saat kalsine edilmektedir. Metalik etki yakalamak hem maliyetli hem de zaman gerektiren bir prosestir. In this technique, the metallic pigment that will provide the metallic effect is calcined at 550 °C for 8 hours. is being done. Capturing a metallic effect is a costly and time-consuming process.
Ayrica metalik etkiyi pigment ile olusturmaya çalisan tüm teknikler de nihai ürüne bakildiginda metalik yansima metalin kendisi kadar etkili bir isildama saglamayacak daha çok boya görünümünde olacaktir. In addition, all techniques that try to create the metallic effect with pigment are also added to the final product. When looked at, the metallic reflection will not provide as effective luminescence as the metal itself. It will look like paint.
EP 1702896 A1 nolu yayinda ise farkli oranlarda oksit karisimindan olusan geleneksel seramik formülasyonuna 100 mikrondan küçük 1100°C'den yüksek ergime noktasina sahip metal, metal bilesikleri ve oksitleyici olmayan alasimlarin katilmasi ile seramik ürünlerde metalik etki yakalanmaya çalisilmistir. Ve özellikle demir bazli Cr-Ni alasimlarinin daha uygun oldugu belirtilmistir. Ancak bahsedilen yayinda belirtildigi sekilde 1100 0C' civarlarinda ergime noktasina sahip metal, metal bilesimleri ve alasimlar seçildiginde ve yine yayinda belirtildigi sekilde özellikle demir bazli Cr-Ni alasimlari seçildiginde J.C. Langevoort, T.Fransen, P.J. In the publication numbered EP 1702896 A1, traditional ceramics consisting of oxide mixture in different proportions metal with a melting point less than 100 microns and higher than 1100°C, metallic in ceramic products with the addition of metal compounds and non-oxidizing alloys. effect was attempted. And especially iron-based Cr-Ni alloys are more suitable. specified. However, as stated in the mentioned publication, melting around 1100 0C' When metal, metal compositions and alloys with a point are selected and again specified in the publication In the figure, especially when iron-based Cr-Ni alloys are selected, J.C. Langevoort, T.Fransen, P.J.
Geilings tarafindan 1984 yilinda yapilan ”On the influence of coldwork on the oxidation behavior of some austenitic stainless steels: High temperature Oxidation, Oxidation of Metals” baslikli yayina göre asagida belirtilen olusumlar beklenir. Seramik formülasyon içerisinde dagitilmis metal partiküller 1100 °C'Iere kadar kararliligini koruyabilecek ve 1200 °C'de siddetli bir oksitlenme reaksiyonu olusturacaktir. Oksitlenme düsük sicakliklarda krom'un oksitlenmesi ile baslayacak ve yüksek sicakliklarda demir ve nikelin oksitlenmesi ile devam edecektir. Bu sorun özellikle 1200-1215 °C tepe sicakligina sahip pisirim çevrimi uygulanan porselen karolarda sir yüzeylerinde metalik görünümün bozulmasina kromun oksitlenmesi ile yesil bir görünüme daha uzun kullanimlarda da pas görünümüne neden olacaktir. Ayrica metal tozlarin tane boyut dagilimlari hem oksitlenmeyi hem de olusturacaklari metalik yansimayi etkileyecek önemli bir parametredir. Çok ince tane boyut dagiliminda metal toz kullanimi hem oksitlenmeyi artiracak hem de artan pürüzlü metal yüzey alani dolayisi ile düzgün yansimayan isik kirinimi artacak ve metalik parlama azalacaktir. Bu nedenle tane boyut dagiliminin 100 mikron alti seklinde kontrolsüz seçilmesi yerine yansimayi artiracak kontrollü bir dagilim olusturulmalidir. Porselen karo bünyelerinin termal genlesme katsayilari yaklasik 7-8x10`6 civarlarinda iken bahsi geçen metal ve alasimlarinin yaklasik 12-18x10'6 arasinda degismektedir. Termal genlesme katsayilari arasindaki fark bu kadar yüksek olan iki malzeme birbirleri ile temas halinde iken isil isleme maruz kalirlar ise aralarindaki genlesme ve çekme farklarindan dolayi tanelerin ara yüzeylerinde bosluklar olusmakta, parçalanmalar, birbirlerinden ayrilmalar ve tane kopmalari olusmaktadir. Bu sorun sirin hem görsel etkisini hem mekanik dayanimini hem de bosluklardan dolayi Iekelenme ve kimyasal dayanimini olumsuz etkileyecektir. Ilgili yayinda termal genlesme katsayisi ile ilgili herhangi bir çözüm önerisi gelistirilmemis, metal partikülleri ile uyumlu olabilecek özel bir sir tabakasi gelistirilmemis sadece mevcut seramik parçanin modifiye edildigi belirtilmistir. "On the influence of coldwork on the oxidation" by Geilings in 1984 behavior of some austenitic stainless steels: High temperature Oxidation, Oxidation of According to the publication titled "Metals", the following formations are expected. Ceramic formulation The metal particles dispersed in it will be able to maintain its stability up to 1100 °C and It will form a vigorous oxidation reaction at °C. Oxidation at low temperatures It will start with the oxidation of chromium and with the oxidation of iron and nickel at high temperatures. will continue. This problem is especially true in the firing cycle with a peak temperature of 1200-1215 °C. the deterioration of the metallic appearance on the glaze surfaces of the porcelain tiles applied. It causes a green appearance with its oxidation, and a rust appearance in longer use. will be. In addition, the grain size distributions of metal powders prevent both oxidation and It is an important parameter that will affect the metallic reflection they will create. Very fine grain size The use of metal powder in the dispersion will both increase oxidation and increase the rough metal Because of the surface area, light that is not reflected properly will increase and metallic glare will increase. will decrease. For this reason, the uncontrolled selection of the particle size distribution below 100 microns. Instead, a controlled distribution that will increase the reflection should be created. Porcelain tile bodies While the thermal expansion coefficients are around 7-8x10`6, the mentioned metal and alloys vary between approximately 12-18x10'6. Thermal expansion coefficients When two materials with such a high difference are in contact with each other, heat treatment If they are exposed to the grains due to the expansion and shrinkage differences between them. cavities occur on their surfaces, fragmentation, separation from each other and grain ruptures is formed. This problem affects both the visual effect and the mechanical strength of the glaze. It will adversely affect its staining and chemical resistance due to voids. In the related publication No solution proposal has been developed for the thermal expansion coefficient, metal No special glaze layer has been developed that can be compatible with the particles, only the existing ceramic It is stated that the part has been modified.
Basvuruya konu bulusta ise yukarida bahsedilen yayinlarda olusabilecek olumsuzluklarin ortadan kaldirildigi ergime noktasi ve tane boyut dagilimi uygun metal/metal alasimlari ile çalisilmis ve karo yüzeyinde metalik etki elde edilmesini saglayacak sir kompozisyonu gelistirilmistir. In the invention that is the subject of the application, it is important to consider the negative aspects that may occur in the above-mentioned publications. with suitable metal/metal alloys with melting point and grain size distribution. glaze composition that will provide a metallic effect on the worked and tile surface developed.
Bulusun Amaci: Bulusun amaci, karo üzerine uygulandiginda metalik görünüm olusturan ve üzerine dijital baski uygulanabilen metal katkili cam-seramik sir kompozisyonunun gelistirilmesidir. Purpose of the Invention: The aim of the invention is to create a metallic appearance when applied on the tile and have a digital It is the development of a printable glass-ceramic glaze composition with metal additives.
Bulusun bir diger amaci bulus kapsaminda gelistirilen sir kompozisyonu ile kaplanmis metalik görünüme sahip, üzerinde farkli baski teknikleri ile desen olusturulabilen porselen karo elde etmektir. Another aim of the invention is to make metallic coatings coated with the glaze composition developed within the scope of the invention. Porcelain tile, which has the appearance of and on which patterns can be created with different printing techniques, is obtained. is to do.
Sekillerin Açiklamasi Sekil 1: Kobalt alasimina ait partiküllerin elektron mikroskop görüntüsü Sekil 2: Granül fritin mevcut durumda ve isil islem sonrasi mineralojik analiz sonucu Sekil 3: Amorf fritin isil islem sonrasi olusturdugu yapiya ait elektron mikroskop görüntüsü Sekil 43: Kobalt bazli alasim katkilanmis sirin yüzey görüntüsü Sekil 4b: Kobalt bazli alasim katkilanmis sirin daha yüksek büyütmede yüzey görüntüsü Sekil Sa: Kobalt bazli alasim katkilanmis sirin nihai mikroyapisi üzerinde kobalt bazli alasim üzerinden alinan EDX analiz sonucu Sekil 5b: Nihai sirin içerisindeki çubuk seklindeki kristal üzerinden alinan EDX analiz sonucu Sekil 5c: Nihai sirin içerisindeki küçük açik tondaki partiküller üzerinden alinan EDX analiz Tablolarin Açiklamasi: Tablo 1: Metal katkili cam-seramik sir (MCS) kompozisyonu Tablo 2. Kullanilan kobalt bazli alasim tanelerinin tane boyut dagilimi Bulusun Açiklamasi: Bulus konusu, karo üzerine uygulandiginda metalik görünüm olusturan ve üzerine dijital baski uygulanabilen metal katkili cam-seramik sir kompozisyonu, kompozisyonun hazirlanmasi için bir yöntem ve söz konusu sir kompozisyonunu yüzeyinde bulunduran porselen karo üretim yöntemi ve bahsedilen yöntem ile üretilmis porselen karo ile ilgilidir. Description of Figures Figure 1: Electron microscope image of particles of cobalt alloy Figure 2: The result of mineralogical analysis of the granular frit in its current condition and after heat treatment Figure 3: Electron microscope image of the structure formed by the amorphous frit after heat treatment Figure 43: Cobalt-based alloy doped glaze surface view Figure 4b: Surface image of cobalt-based alloy doped glaze at higher magnification Figure Sa: Cobalt-based alloy on a cobalt-based alloy doped glaze final microstructure EDX analysis result from Figure 5b: EDX analysis result obtained on the rod-shaped crystal in the final siren Figure 5c: EDX analysis on small light-toned particles in the final glaze Description of Tables: Table 1: Composition of metal added glass-ceramic glaze (MCS) Table 2. Grain size distribution of used cobalt-based alloy grains Description of the Invention: The subject of the invention is that which creates a metallic appearance when applied on the tile and has a digital printable glass-ceramic glaze composition with metal additives a method for its preparation and containing the said glaze composition on its surface. It is about the porcelain tile production method and the porcelain tile produced with the mentioned method.
Basvuruya konu kompozisyonda ergime noktasi 1200 OC'nin üzerinde ve 75 mikron ve altinda belli bir tane boyut dagilimina sahip olan (Tablo 1) kobalt bazli alasim kullanimi tercih edilmektedir. Kobalt bazli alasim ergime noktasi düsük ( kalay tozlari ile birlikte özel sir harmanina ilave edilmektedir. Kobalt bazli alasimin ergime noktasi 1200 °C'nin üzerinde oldugundan pisirim döngüsünde erimeden yapida kalmakta ve sir yüzeyinde metalik yansimayi saglamaktadir. Kalay ise düsük sicakliklarda erimeye baslamakta, oksitlenerek SnOz yapisina geçmekte ve diger inorganik bilesenler ile uyumlu bir yapi sergilemektedir. Özel sir harmani; baryum temelinde kristal devitrifikasyonu saglayabilen 150 mikron alti amorf granül fritlerden ve kalay oksit, kuvars, kaolen hammaddelerini içeren karisimdan olusturulmaktadir. Bulus konusu kompozisyon geleneksel yas sir hazirlama tekniklerinden farkli bir yöntemle hazirlanarak angoplanmis porselen karolarin üzerine uygulanmaktadir. In the composition subject to the application, the melting point is above 1200 OC and 75 microns and It is preferred to use cobalt-based alloys with a certain grain size distribution below (Table 1). is being done. Cobalt-based alloy with low melting point (with tin powders, special added to the secret blend. The melting point of cobalt-based alloy is above 1200 °C Since it is in the firing cycle, it remains in the structure without melting and metallic metal on the glaze surface. it provides reflection. Tin, on the other hand, begins to melt at low temperatures and oxidizes. It switches to snOz structure and exhibits a structure compatible with other inorganic components. Special glaze blend; sub 150 microns, which can provide crystal devitrification on the basis of barium from amorphous granular frits and a mixture containing tin oxide, quartz, kaolin raw materials is created. The composition, which is the subject of the invention, is one of the traditional mourning glaze preparation techniques. It is applied on porcelain tiles prepared with a different method and angulated.
Porselen karo üzerinde olusan nihai tabaka camsi faz içerisinde dagilan baryum stronsiyum alüminyum silikat, kassiterit ve kuvars kristallerini ve ayrica kobalt bazli alasim tanelerini içeren cam-seramik sir'dir. Bu nedenle nihai yapi içerisinde metal partiküller içeren cam- seramik sir olarak tanimlanmistir. Metalik yansimaya sahip, üzerine dijital baski yapilabilen metal katkili cam-seramik sir kompozisyonu detayli olarak asagida anlatilmaktadir. Barium strontium dispersed in the final layer glassy phase formed on the porcelain tile crystals of aluminum silicate, cassiterite and quartz, as well as cobalt-based alloy grains. containing glass-ceramic glaze. For this reason, glass-containing metal particles in the final structure defined as ceramic glaze. With metallic reflection, digital printable The metal added glass-ceramic glaze composition is explained in detail below.
Bulus kapsaminda gelistirilen metal katkili cam-seramik sir (MCS) kompozisyonuna ait yüzdece agirlik degerleri Tablo 1'de verilmistir. Belonging to the metal added glass-ceramic glaze (MCS) composition developed within the scope of the invention. percent weight values are given in Table 1.
Tablo 1. Metal katkili cam-seramik sir (MCS) kompozisyonu Kompozisyon Bilesenleri Bilesen Yüzdece agirlik Kobalt bazli alasim (erime C0, Cr, Ni, C, Si, W, Mn, 5-35 noktasi 1200 °C'den yüksek Mo diger metal ve metal alasimlari) Granül frit Na20, KZO, CaO, MgO, 20-40 BaO, SrO, SiOz, Ai203 Kassiterit SnOz 0-20 Kalay Sn 0-20 Kuvars SiOz 0-10 Kaolen AI203, SiOz, HZO 0-10 Bulus kapsaminda gelistirilen kompozisyon agirlikça % 5-35 oraninda erime noktasi 1200 °C'den yüksek en az bir metal veya metal alasimini, agirlikça % 20-40 oraninda granül friti, agirlikça % 0-20 oraninda kassiterit, agirlikça % 0-20 oraninda kalay, agirlikça % 0-10 oraninda kuvars ve agirlikça % 0-10 oraninda kaolen içermektedir. Table 1. Composition of metal added glass-ceramic glaze (MCS) Composition Components Composition Percent weight Cobalt-based alloy (melting C0, Cr, Ni, C, Si, W, Mn, 5-35 Mo point higher than 1200 °C other metals and metal alloys) Granular frit Na20, KZO, CaO, MgO, 20-40 BaO, SrO, SiOz, Al2O3 Cassiterite SnOz 0-20 Tin Sec 0-20 Quartz SiOz 0-10 Kaolin AI203, SiOz, HZO 0-10 The composition developed within the scope of the invention has a melting point of 1200 at a rate of 5-35% by weight. At least one metal or metal alloy above °C, 20-40% by weight granular frit, 0-20% by weight cassiterite, 0-20% by weight tin, 0-10% by weight It contains quartz and 0-10% kaolin by weight.
Tablo 1'de belirtilen metal ve metal alasimlarinin porselen karo sicakliklarinda (” erimeden ve yapisini degistirmeden sir kompozisyonu içerisinde kalabilmesi ve sir yüzeyinde metalik etkiyi olusturabilmesi için bulus kapsaminda ergime noktasi minimum 1200 °C olan metal alasimlari kullanilmistir. Bulus kapsaminda tercihen kullanilan kobalt bazli alasim içeriginde agirlikça kobalt orani %60'tan fazla, agirlikça krom orani %28'den fazla, agirlikça nikel orani %1,5'ten fazla, agirlikça karbon orani %l'den az, agirlikça silikon orani %1,5'ten az, agirlikça W (tungsten) orani % 3'ten fazla ve Mn (mangan) ile M0 (molibden) orani agirlikça %O,75'ten azdir. Aplikasyon sirasinda kolay akis saglamasi ve inorganik partiküllerin sinterlenmesi sirasinda amorf fazin metal partikülün etrafini kolaylikla doldurabilmesi için tanelerin Sekil 1'de gösterildigi gibi küresel yapida olmasi istenmektedir. At porcelain tile temperatures of metal and metal alloys specified in Table 1 (” It can stay in the glaze composition without melting and changing its structure and on the glaze surface. It has a minimum melting point of 1200 °C within the scope of the invention in order to create the metallic effect. metal alloys are used. Cobalt-based alloy preferably used in the scope of the invention content by weight of cobalt more than 60%, by weight of chromium more than 28%, by weight More than 1.5% nickel, less than 1% carbon by weight, more than 1.5% silicon by weight less, W (tungsten) content more than 3% and Mn (manganese) to M0 (molybdenum) content by weight less than 0.75% by weight. Easy flow during application and inorganic particles so that the amorphous phase can easily fill around the metal particle during sintering. The grains are desired to be spherical as shown in Figure 1.
Tablo 2. Kullanilan kobalt bazli alasim tanelerinin tane boyut dagilimi Tane Boyut Dagilimi Agirlikça Orani 75-63 ii 5 63-45 M 50 45-38 p 20 38 u'dan küçük 25 Bulus kapsaminda gelistirilen sir kompozisyonunun diger bileseni ergime noktasi metal alasimina göre oldukça düsük olan ( kalay tozudur. lsiI islem sirasinda sir bilesenine eklenen kalay erimekte sonrasinda tamami oksijen ile birlikte SnOz yapisina dönüsmektedir. Table 2. Grain size distribution of used cobalt-based alloy grains Grain Size Distribution by Weight Ratio 75-63 ii 5 63-45M 50 45-38 p 20 25 less than 38 u The other component of the glaze composition developed within the scope of the invention is the melting point metal. (it is tin powder, which is quite low compared to the alloy. It is transferred to the glaze component during heat treatment. The added tin melts and then completely turns into SnOz with oxygen.
Nihai yapida hem sir harmaninda bulunan kassiterit (SnOz) hem de kalayin oksitlenmesi ile olusan SnOz bulunmaktadir. Kalayin oksitlenmesi, isil isleme ugrayan sir katmaninda oksijen miktarini azaltmakta ve dolayisi ile kobalt bazli alasimda olusabilecek oksitlenmeleri azaltmaktadir. In the final structure, both cassiterite (SnOz) in the glaze blend and tin are oxidized. There is SnOz formed. Oxidation of tin, oxygen in the heat-treated glaze layer reduces the amount of oxidation that may occur in cobalt-based alloys. decreases.
Bulus konusu kompozisyona eklenen kassiterit tane boyutu tercihen 75 u veya altinda olarak seçilmektedir. Cassiterite grain size added to the composition of the invention should preferably be 75 u or less. is selected.
Cam-seramik yapinin olusmasini saglayan temel bilesen ise yapiya eklenen baryum içerigi yüksek granül frittir. Bulus kapsaminda kullanilan granül frit tane boyutu 150 ;1 veya altinda olarak tercih edilmektedir. Granül fritler baslangiçta amorf yapidadir, tek baslarina porselen karo yüzeylerine uygulanarak porselen karo pisirim sartlarinda (1205-1215 °C tepe sicakligi olacak sekilde toplam 40-60 dk) isil isleme tabii tutulduklarinda amorf yapi içerisinde homojen dagilan baryum stronsiyum alüminyum silikat kristallerini olustururlar. Baslangiç durumda ve isil islem sonrasi yapilan mineralojik analiz sonuçlari Sekil 2'de gösterilmistir, bahsi geçen fazlar görülmektedir. Sekil 3'te nihai yapinin elektron mikroskop görüntüsü görülmektedir. Baryum stronsiyum alüminyum silikat kristallerinin amorf yapi içerisinde homojen ve çubuk seklinde dagildigi görülmektedir. Metal ve metal alasimlari teknigin bilinen durumunda belirtilen patentlerde oldugu gibi mevcut seramik formülasyonuna ya da sir formülasyonuna direk ilave edilirse sahip olduklari yüksek termal genlesme katsayilari dolayisi ile bünye-sir uyumunu bozarak çatlaklara neden olacaktir. Bu nedenle Ilave edilen metal ya da metal alasiminin yüksek genlesme katsayisini sönümleyerek bünyeye yaklastirabilecek daha düsük genlesmeli sir olusturabilmek için bulus kapsaminda baryum içerigi yüksek fritler sir kompozisyonuna ilave edilmistir. Baryum içerigi yüksek fritler alkali içerigi yüksek fritlerden daha düsük termal genlesme katsayisina sahiplerdir. Metal ve metal alasimlari ilave edilen sirin termal genlesme katsayisi arttigindan düsük termal genlesme katsayisina sahip frit ilavesi ile ortalama sir genlesmesi dengelenmekte ve porselen karonun bünyesi ile metal katkili cam-seramik sir arasinda olusabilecek termal genlesme uyumsuzluklari giderilmektedir. The basic component that provides the formation of the glass-ceramic structure is the barium content added to the structure. high granular frit. Granular frit grain size used within the scope of the invention is 150; 1 or less is preferred. Granular frits are initially amorphous, and porcelain It is applied to tile surfaces under porcelain tile firing conditions (1205-1215 °C peak temperature). in amorphous structure when subjected to heat treatment (for a total of 40-60 minutes) They form homogeneously dispersed barium strontium aluminum silicate crystals. Beginning The mineralogical analysis results in the condition and after the heat treatment are shown in Figure 2, mentioned phases. Electron microscope image of the final structure in Figure 3 is seen. Barium strontium aluminum silicate crystals in amorphous structure It is seen that it is distributed homogeneously and in the form of rods. Metal and metal alloys technique existing ceramic formulation or If added directly to the glaze formulation, they have high thermal expansion coefficients. therefore, it will cause cracks by disrupting the body-synthesis harmony. Therefore, added absorbing the high coefficient of expansion of the metal or metal alloy into the body. In the scope of the invention, barium is used to form a glaze with a lower expansion that can approximate Frits with high content are added to the glaze composition. Frits with high barium content are alkaline They have a lower coefficient of thermal expansion than frits with high content. metal and metal Low thermal expansion as the thermal expansion coefficient of the glaze alloys is increased. With the addition of frit, the average glaze expansion is balanced and the porcelain tile thermal expansion that may occur between its body and metal-added glass-ceramic glaze inconsistencies are resolved.
Bulus kapsaminda gelistirilen yöntemin tercih edilen bir uygulamasinda sir kompozisyonunu elde etmek için öncelikle Tablo 1'de belirtilen bilesenlerden kuvars, kaolen, kassiterit ve su birlikte ögütülmektedir. Ögütülmüs hammadde karisimina belirlenen kobalt bazli alasim, kalay tozu ve granül frit ilave edilmektedir. In a preferred application of the method developed within the scope of the invention, the glaze composition is used. To obtain quartz, kaolin, cassiterite and water from the components listed in Table 1, are grinded together. Cobalt-based alloy determined to the ground raw material mixture, tin powder and granular frit are added.
Sir süspansiyonunun karo yüzeylerine uygulanabilmesi Için belli bir akiskanliga sahip olmasi gerekir. Akiskanligi saglamak için geleneksel sirlarda oldugu gibi sadece su kullanilirsa metal partiküller ve granül fritler viskoz sir süspansiyonu içerisinde çökebilirler, homojen dagilima engel olabilirler. Bu nedenle akiciligi saglamak için medyum ve su birlikte kullanilmistir. In order for the glaze suspension to be applied to the tile surfaces, it must have a certain fluidity. must. If only water is used to provide fluidity, as in traditional glazes, the metal particles and granular frits can settle in the viscous glaze suspension, homogeneous distribution they can be an obstacle. For this reason, medium and water were used together to provide fluidity.
Bahsedilen medyumlar (M) "mediums for ceramics" olarak bilinen çesitli ajan ve kimyasallari içeren kompozisyonlardir. Daha önce birlestirilmis karisim (ögütülmüs hammaddeler, kobalt bazli alasim, kalay ve granül frit) su ve medyum ile birlikte mekanik karistiricida homojen hale gelene kadar karistirilmaktadir. Metal katkili sir süspansiyonunun viskozitesi 27-35 sn yogunlugu 1700-1800 gr/It araligina geldiginde angopla kaplanmis karo yüzeylerine uygulanmaktadir. Uygulama tercihen kampana yöntemi ile gerçeklestirilmektedir. Sir uygulamasindan sonra dijital baski yöntemi ile karo üzerine istenilen desen basilabilmektedir. Aplikasyonu tamamlanan ürün, pisirimden önce tamamen kurumasi için kurutucularda kurutulmaktadir. Bahsedilen kurutucularin sicakligi tercihen 100-120 °C araligindadir. Metal katkili sir kompozisyonu ile kaplanan porselen karo 1205 - 1215°C tepe sicakliklarina ulasan rulolu endüstriyel hizli pisirim firinlarinda 40 ile 60 dk arasinda degisen parlatilmaktadir. Mentioned mediums (M) contain various agents and chemicals known as "mediums for ceramics". containing compositions. Previously compounded mixture (milled raw materials, cobalt based alloy, tin and granular frit) homogeneously in a mechanical mixer with water and medium is mixed until it becomes Viscosity of metal added glaze suspension 27-35 sec When the density is in the range of 1700-1800 gr/It, it can be applied to the tile surfaces covered with angopla. is being implemented. The application is preferably carried out by the drum method. Secret After the application of the desired pattern on the tile with the digital printing method. can be printed. The product, whose application is completed, should be completely dried before firing. dried in dryers. The temperature of the said dryers is preferably 100-120 °C. is in the range. Porcelain tile coated with metal added glaze composition 1205 - 1215°C top temperature varying between 40 and 60 minutes in industrial quick-firing ovens with rolls is polished.
Bulus konusu yöntemin tercih edilen bir diger uygulamasinda öncelikle inorganik bilesenlerden olusan sir karisimi angoplanmis karo yüzeylerine uygulanmakta ve hemen arkasindan sadece metalleri içeren karisim karo yüzeyine uygulanmaktadir. Inorganik bilesenler kampana yöntemi ile metalleri içeren karisim ise spreyleme teknigi ile uygulanmaktadir. Bu uygulama için; Tablo 1'de belirtilen bilesenlerden kuvars, kaolen ve kassiterit su ile birlikte ögütülmektedir. Ögünmüs hammadde karisimina reçetede belirlenen granül frit ilave edilmekte ve mekanik karistirici ile homojen hale gelene kadar geldiginde angopla kaplanmis karo yüzeylerine kampana yöntemi ile uygulanmaktadir. In another preferred application of the inventive method, primarily inorganic The glaze mixture consisting of components is applied to the angulated tile surfaces and immediately then the mixture containing only metals is applied to the tile surface. Inorganic The components are made by drum method and the mixture containing metals is sprayed. is being implemented. For this application; Of the components listed in Table 1, quartz, kaolin and cassiterite is ground together with water. determined in the recipe for the mixture of original raw materials. Granular frit is added and mixed with a mechanical mixer until it becomes homogeneous. It is applied to the tile surfaces covered with angopla by the drum method.
Kobalt bazli alasim ve kalay medyum içerisinde dagitilarak yogunlugu 1600-1700 gr/It araliginda ayarlanmakta ve daha önce karo yüzeyine uygulanmis sir karisiminin üzerine spreyleme teknigi ile uygulanmaktadir. Cobalt-based alloy and tin are dispersed in the medium and its density is 1600-1700 gr/It It is set between It is applied by spraying technique.
Numunelerin pisirim isleminden sonra bu süreçle ortaya çikmis kristallerin morfolojisi ve kristal miktarlarinin gözlemlenmesi enerji dispersif x-isini (EDX) baglantili Zeiss EVO 50 EP ve Zeiss SUPRA 50 VP taramali elektron mikroskoplariyla 20 kV'da saglanmistir. Sirlarin mikro yapisal incelemeleri dogrudan Sirlarin üst yüzeylerinden yapilmistir. Mikroyapi çalismalarinda atom agirligina bagli olarak faz ayrisimini saglayan geri yansiyan elektronlarla (BEI) görüntü alinmistir. Ayrica, olusan kristallerin kimyasal bilesimini belirlemek için EDX analizi uygulanmistir. Morphology and morphology of the crystals that emerged with this process after the firing process of the samples. observing the amount of crystals Zeiss EVO 50 EP with energy dispersive x-ray (EDX) and Provided at 20 kV with Zeiss SUPRA 50 VP scanning electron microscopes. secrets micro structural examinations were made directly from the upper surfaces of the Glazes. In microstructure studies image with back-reflected electrons (BEI) that provide phase separation depending on atomic weight has been taken. In addition, EDX analysis was used to determine the chemical composition of the crystals formed. has been applied.
Gelistirilen sirin yüzeyinden çekilen farkli büyütmelerdeki elektron mikroskop görüntüleri Sekil 4'te görülmektedir. Sekil 4a'da küresel kobalt bazli alasim partikülleri diger sir bilesenleri ile birlikte amorf faz içerisinde sir yüzeyinde homojen dagilmistir. Sekil 4b'de mikro yapiyi daha yakindan inceleyebilmek için sirin tamamini yansitan küçük bir alan, daha büyük büyütme ile çekilmistir. Bu görüntüdeki kristaller üzerinden alinan EDX analiz sonuçlari sirasi ile Sekil 5'te verilmistir. Sekil 4b'de küresel ve diger kristallere göre daha büyük olan, agir element oldugu için elektron mikroskobunda açik tonda görülen kristal üzerinden yapilan EDX analiz sonucu Sekil Sa'da görülmektedir. Analiz sonucunda görülen elementler sir bilesimine eklenen kobalt bazli alasim ile tutarlidir. Beklenildigi gibi granül fritin isil islem sonucu yapida yine gri tonlarda çubuk seklinde kristaller olusmustur. Sekil 5b'de bu kristal üzerinden yapilan EDX sonucu görülmektedir. Analiz sonucunda elde edilen elementler granül fritin isil islem sirasinda olusturdugu baryum stronsiyum alüminyum silikat kristal içerigi ile uyumludur. Yapi içerisinde görülen bir diger kristal yine açik tonlarda diger kristallere göre daha küçük yapida olan EDX analiz sonucunda (Sekil Sc) elde edilen elementlerden ve sirin mineralojik analizine dayanarak kassiterit oldugu bilinen düzensiz sekilli tanelerdir. Electron microscope images at different magnifications taken from the surface of the developed glaze It is seen in Figure 4. Spherical cobalt-based alloy particles in Figure 4a are another secret. homogeneously distributed on the glaze surface in the amorphous phase with its components. in figure 4b A small area reflecting the full glaze, in order to examine the microstructure more closely, Taken with great magnification. EDX analysis results from the crystals in this image are given in Figure 5, respectively. Spherical in Figure 4b and larger than other crystals, Since it is a heavy element, it can be seen through the light crystal in the electron microscope. EDX analysis result is shown in Figure Sa. Elements seen as a result of the analysis It is consistent with the cobalt-based alloy added to the glaze composition. As expected, the heat treatment of the granular frit As a result, rod-shaped crystals in gray tones were formed in the structure. In Figure 5b this crystal The EDX result made over the can be seen. The elements obtained as a result of the analysis barium strontium aluminum silicate crystal formed by granular frit during heat treatment compatible with its content. Another crystal seen in the structure is still in light tones. As a result of the EDX analysis (Figure Sc), which is smaller than the crystals, the irregularities known to be cassiterite based on the elements and mineralogical analysis of the clay. are shaped grains.
Elektron mikroskobu görüntülerinden de anlasildigi üzere porselen karo üzerinde olusan nihai tabaka camsi faz içerisinde dagilan baryum stronsiyum alüminyum silikat, kassiterit ve kuvars kristallerini ve ayrica kobalt bazli alasim tanelerini içeren cam-seramik sir'dir. As can be seen from the electron microscope images, the formation on the porcelain tile The final layer is barium strontium aluminum silicate, cassiterite and dispersed in the glassy phase. It is a glass-ceramic glaze containing quartz crystals and cobalt-based alloy grains.
Bulus kapsaminda metal-katkili cam-seramik sir gelistirilmistir. Yapida küçük kristaller halinde dagilan kassiterit kristallerinden, çubuk seklinde dagilmis baryum stronsiyum alüminyum silikat kristallerinden ve kobalt bazli alasim tanelerinden yansiyan isinlar yüzeyin bazi noktalarinda parlak metalik bazi noktalarinda mat metalik bir görüntü olusturarak sir yüzeyinde zengin bir görüntü olusturmaktadir. Amorf yapi Içerisinde dagilan yogun kristaller sirin mekanik (PEI 4) ve kimyasal dayanimini artirmistir. Within the scope of the invention, metal-added glass-ceramic glaze was developed. small crystals in structure barium strontium dispersed in rod form from cassiterite crystals dispersed as Rays reflected from aluminum silicate crystals and cobalt-based alloy grains It creates a shiny metallic image at some points and a matte metallic image at some points. It creates a rich image on the surface. Dense crystals dispersed in amorphous structure It has increased its cool mechanical (PEI 4) and chemical resistance.
Sir yüzeylerine dijital baski yapilabilmesi için sir yüzeyinin dijital baski mürekkebini tamamen içine çekmemesi ve üzerine uygulanan rengi göstermesi gerekmektedir. Elde edilen sir yüzeyinde amorf faz ve kristaller homojen dagildiklarindan dijital mürekkeple uyum saglamaktadir ve sir yüzeyinde dijital teknoloji ile uygulanan dekor istenilen sekilde elde edilebilmektedir. In order to make digital printing on the glaze surfaces, the digital printing ink of the glaze surface must be completely It should not absorb it and show the color applied on it. The resulting secret Compatibility with digital ink as amorphous phase and crystals are homogeneously dispersed on its surface. and the decor applied with digital technology on the glaze surface can be achieved as desired. can be achieved.
Relative lntensity Relative Intensity
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR2016/19465A TR201619465A2 (en) | 2016-12-24 | 2016-12-24 | METAL ADDITIVE GLASS-CERAMIC Glazing COMPOSITION AND PRODUCTION OF PORCELAIN TILES WITH THIS COMPOSITION |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR2016/19465A TR201619465A2 (en) | 2016-12-24 | 2016-12-24 | METAL ADDITIVE GLASS-CERAMIC Glazing COMPOSITION AND PRODUCTION OF PORCELAIN TILES WITH THIS COMPOSITION |
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