TR202014524A2 - APPLICATION OF REDUCED COOKING LUSTER PIGMENTS - Google Patents

APPLICATION OF REDUCED COOKING LUSTER PIGMENTS Download PDF

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TR202014524A2
TR202014524A2 TR2020/14524A TR202014524A TR202014524A2 TR 202014524 A2 TR202014524 A2 TR 202014524A2 TR 2020/14524 A TR2020/14524 A TR 2020/14524A TR 202014524 A TR202014524 A TR 202014524A TR 202014524 A2 TR202014524 A2 TR 202014524A2
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luster
glaze
firing
technique
clay
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TR2020/14524A
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Turkish (tr)
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Pala İrem
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18 Mart Üni̇versi̇tesi̇rektörlüğü
Canakkale Onsekiz Mart Ueniversitesi Rektoerluegue
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Priority to TR2020/14524A priority Critical patent/TR202014524A2/en
Publication of TR202014524A2 publication Critical patent/TR202014524A2/en

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Abstract

Buluş, örtücü sır sağlayıcı kalay bileşiğinin sırın içine ya da sırüstüne değil de sırın altına renk veren, lüster efekti veren pigmentlerle beraber uygulanmasını içeren indirgen pişirim lüster pigmentlerinin sıraltına uygulanması yöntemi ile ilgilidir.The invention relates to the method of applying reducing firing luster pigments to the underglaze, which involves applying the covering glaze tin compound together with the pigments that give color and luster effect, but not inside the glaze or on the glaze.

Description

TARIFNAME INDIRGEN PISIRIM LÜSTER PIGMENTLERININ SIRALTINA UYGU LAN MASI Teknik Alan Bulus, örtücü sir saglayici kalay bilesiginin sirin içine ya da sirin üstüne degil de sirin altina, renk veren, lüster efekti veren pigmentlerle beraber uygulanmasini içeren indirgen pisirim lüster pigmentlerinin siraltina uygulanmasi yöntemi ile ilgilidir. Önceki Teknik Pismis toprak, yaygin adi ile seramik olarak bilinmektedir. Bu adlandirma günümüzde, topragin sekillendirilmesinden sonra dayaniklilik kazanincaya kadar pisirilmesi ile elde edilen bütün ürünleri kapsamaktadir. Pismis toprak ürünlerin siniflandirmasi çesitli özelliklerine göre birden çoktur; seramik, çini, porselen, yumusak porselen, sert porselen, teknik porselen, iletken, yalitkan vb. olarak hem farkli pisirim derecelerine hem de farkli hammaddelere dolayisi ile amaçlarina göre çesitlenebilen yapilari ile siniflandirilabilmektedir. Teknik porselenler, uzay mekigi, tekstil makinesi parçasi vb. alanlar için yapilan üretimler mühendislik bilimi kapsamindadir. Yine piyasada satilmasi üzere çamur ve sir hazirlayanlar da seramik mühendisligi alanindadir. Piyasadan satin alinabilen hazir çamur ve sir kullanarak kisisel firinlarda ya da firin kiralayan atölye sahipleri araciligi ile sekillendirdikleri topragi pisirebilen herkes genel olarak seramikçi olarak isimlendirilmektedir. Geleneksel seramik üretim bilgilerini kullanarak üretim yapanlar ise sekillendirecekleri topragi geleneksel yöntemlerle dogadan çikarip, hazirlayip, sekillendirip yine geleneksel yöntemlerle yaptiklari firinlarda pisiren ustalar, genel olarak çömlekçi, bardakçi diye anilmaktadirlar. Sadece islevsel günlük kullanim esyalari ürettikleri için sayilari gün geçtikçe azalmaktadir. Günümüz hazir malzemelerini kullandikça, yeni formlar ürettikçe seramikçi olarak adlandirilmaktadir. Fakat çamurlarini geleneksel yöntemlerle hazirladiklari Bir de hazir Kütahya malzemesini kullanarak ya da saray seramigi benzerlerini üreten çiniciler bulunmaktadir. Çiniciler özellikle Iznik ve Kütahya7da kisisel atölyelerinde fabrikasyon üretimi olarak tanimlanainayan fakat yine seri olarak, tamamen el isçiligine dayanan üretim yapmaktadirlar. Bazi atölyeler kisisel fritli çamur, tas çini, pat pat çini olarak adlandirilan çamurlarini, kendi kisisel reçeteleri ile üretmektedir. Ayrica reçetelerine uygun sir, boya, astar gelistirmektedirler. Sekillendirilen topragin pisirim derecesi genel olarak 573 °C"den baslamaktadir. Piyasada sekillendirilmeye hazir olarak satilan çamur ve sir 900 ile 1070 °C derece arasinda kullaniin için uygundur ve bu malzeme ile üretim yapildiginda seramik olarak adlandirilmaktadir. Yine piyasadan kolaylikla temin edilebilen 1200 °C derece için uygun olan sir ve çamur da bulunmaktadir, bu malzeme ile üretilenlere de porselen denilmektedir. Derecelerdeki farklilik hammaddeden, hammaddenin pekisme ve erime derecelerinin farkliligindan kaynaklanmaktadir. Dünya'da ve Türkiye'de seramikçiler, genelde piyasadan edindikleri malzemeler ile ürettikleri form, doku, dekor, renk farkliliklari ile kendilerini ifade etmektedirler. Seramikçilerin çok azinligi kendi çamurunu, sirini, boyasini üretmektedir. Kisisel reçeteleri, tecrübeleri, kendi farkliliklarini ayrica olusturmaktadir. Genelde artistik amaçli heykel yanisira günlük kullanim esyasi olan formlar ile dekoratif esyalar üretmektedirler. Bu üretimler fabrikalarda degil atölyelerde gerçeklesmektedir. Bu atölyeler kisisel hobi ya da ticari amaçli olabildigi gibi güzel sanatlar liseleri, meslek yüksekokullari, fakültelera kurslar bünyelerindedir. Indirgen pisirim Siralti lüster teknigi ile iliskili 4 teknik bulunmaktadir: Indirgen pisirim kil macun lüsteri (Firça dekoru) Indirgen pisirim raku Bu dört teknikle ilgili gerek fen bilimleri gerekse sosyal bilimler alaninda birçok yayin bulunmaktadir ve bu yayinlarda reçeteler belirtilmistir. 1. Indirgen pisirim kil macun lüsteri (Firça dekoru) 18. yüzyila gelininceye kadar lüster efektleri indirgen pisirim ortaininda örtücü sir üzerine uygulanan dekorlama teknigi olan Indirgen Pisirim Kil Macun Lüsteri teknigi ile elde edilmistir. Literatürde genel olarak lüster- Iustre- luster olarak adlandirilmaktadir. Yaklasik 1000 yil önce cam ustalari sonrasinda, Islam seramikçileri tarafindan gelistirilmis bir dekorlama teknigidir. Ilk uygulandigi yillar simyanin (çesitli yöntemlerle altin elde etmenin) popüler oldugu zamana denk gelmektedir1 ve topragin (hammaddenin) indirgendikten sonra altin gibi parlamasinin basarisidir. Islam inancinda degerli kaptan yemek yemenin (genel olarak) yasak olmasi, teknigi ayrica degerli kilmistir.2 Bazi Türk sanat tarihçiler, 20- 30 yil öncesine kadar sadece Selçuklular Dönemi dekorlama teknigi olan lüsteri, "Perdah teknigi" olarak adlandirrnistir. Lüster bir sirüstü dekorlama teknigidir. Lüster efektleri, örtücü sir ile sirlanan ürünün, indirgenebilir pigmentler ve kil ile hazirlanan kil macunu ile dekorlanmasi ve sonra indirgenmesi, soguduktan sonra üzerindeki kil tabakasinin temizlenmesi ile elde edilmektedir. Belirtilen indirgen ortam kil macun lüsteri üretim teknigi genel olarak söyledir: forin sekillendirilir. Ilk pisirimi yapilir. Genellikle alkali ve kalayla örtücülestirilmis 900 CC derecelerde gelisebilen sir ile sirlanir. Sir pisirimi yapilir. Sirlanmis parlak yüzey üzerine farkli oranlarda ve kombinasyonlarda kalay, civa, kil, demir, gümüs, bizmut, bakir gibi indirgenebilir bilesiklerden hazirlanmis macun ile firça dekoru yapilir ve yaklasik 600 °C dereceye kadar firin isitilir ve firinin içerisine çira, yag, odun gibi alev ve duman yapici malzeme atilir. Firin hava almayacak sekilde her tarafi kapatilir. Firin içerisinde bulunan CO, COz olmak isterken seramiklerde bulunan, alabilecegi Oksijeni alir. Bu oksijen kaybi seramik yüzeyde lüster etkisinin olusmasini saglar. Sirlarin üzerini kaplayan metal bazli, saydam film tabakasidir. Günümüzde indirgen pisirim kil macun lüsteri özellikle "Iran lüsteri" olarak hala kullanilmaktadir. 2. Indirgen pisirim siriçi lüster Indirgenebilir elementler sirin içine eklenir. Form sirlanir. Sir gelistirilir ve istege bagli gelistigi derecede veya sogurken, firin içerisine duman yapici atilarak firinin hava almamasi saglanir, indirgenir. Bazi sanatçilar renk veren oksitleri renkli astar olarak siraltina uygulamaktadir. Fakat lüster pigmentini yani özellikle gümüsü sirin içine eklemektedirler. Ayni sir raku teknigi ile de indirgenebilmektedir. 3. Rezinat lüsteri (Firça dekoru) Rezinant lüsteri ise Sivi yaldizlar gibi yine sir üstü dekorlama teknigidir fakat indirgeme pisirimi yapilmadan genelde 600 0C derece civarinda 3. Pisirim ile elde edilmektedir. olarak indirgenip, çesitli renklerde sir yüzeyine yapismalaridir. Elde edilen sonuç, kullanilan yöntemler geregi, kimyasal etkilesim ve degismelerle ya da radikal bir etkilesim olmadan, yüzeylerin birbirleriyle uyumlu birliktelikleridir. Yüzyillardir kullanilan, oksijensiz ortamdaki indirgen pisirim sonucu, albenisi yüksek, gösterisli, üzerlerindeki sir ile kimyasal reaksiyonlara giren lüster isleri elde edilmistir. 18. yüzyildan itibaren lüster islerinin yöntemleri farklilasmis olup, sir üzeri pisirim teknigi özellikle oksijenli ortamlara tasinmistir. Bu teknikte metal tuzlari tasiyici reçine ve inceltici yag içinde bir bilesim seklinde bulundugundan bunlara "organo-metalik bilesikler" de denilmektedir. Bu yöntem uygulama açisindan digerine göre daha kolay olmakla birlikte, indirgen ortam lüsterlerinin canliligi ve çekiciligi bunlarda bulunmamaktadir. Sivi altin ve metal rezinat yöntemleriyle yapilan lüster isleri, indirgen ortam isleriyle kiyaslandiginda daha az cazip olmalarina karsin, günümüzde çagdas islerin çogunlugunda kullanilarak kabul görmektedirler. 3 Endüstriyel pismis toprak üreten fabrikalar, rezinat lüsteri kullanmaktadir. 4. Indirgen pisirim raku Siriçi lüster siri ile raku sirlari benzerdir. Ikisi de indirgenerek elde edilmektedir. Farklari, indirgenme yöntemleridir. Lüsterde firin içerisine duman yapici verilir. Raku da ise pismis toprak form firindan çikartilarak duman yapicinin içerisine gömülür. Yani, siriçi lüster, sirin yumusama derecesinde, firinin içerisine yanici organik malzemenin atilmasi sonrasinda, firinin hava almayacak ve vermeyecek sekilde kapatilmasi, raku ise sirin erime, yumusama derecesinde, seramigin firindan çikartilarak, yanici, duman verici organiklerle indirgenmesidir. Bu iki teknikte de firça dekoru uygulanmamaktadir. Ikisinde de güinüs, bizmut ve renk verenler gibi lüster pigmentleri sirin içine eklenmektedir. Bazi sanatçilar, sadece renk verenleri siraltina uygulamaktadir. Günümüzde, artistik amaçli kullanilan pismis toprak indirgen pisirim teknikleri geçmiste farkli amaçlar için kullanilan tekniklerdi. Bunlar, sirli ürünün direkt atesten korunmasi, hizli pisirim, ilk pisirim (sekillendirilmis çamurun sertlik kazanincaya kadar isitilmasi) gibi amaçlar için kullanilmaktaydi. Günümüzde raku, sagar, çukur, sepet pisirimi, kagit firin gibi adlarla anilan, firinlama ve firin türlerinin ortakligi, seramikçilerin farkli efekt elde etmek iste gidir. Teknigin bilinen durumunda yer alan bu yöntemlerin dezavantajlari asagida detayli olarak siralanmistir. - Indirgen pisirim, geleneksel Kil Macun lüsteri kullaniminda hatali bir indirgemede geri dönüs bulunmamaktadir. Kil altinda olusan lüster efekti ancak üzerinde bulunan kil tabakasinin temizlenmesi sonrasinda ortaya çikarilabilmektedir. Dolayisi ile tekrar nötr ortamda pisirildiginde, ilk uygulanan reçetedeki kil, ortamdan uzaklastirildigi için sirli yüzeyde kalan reçete degismis olmaktadir. Ayrica derece veya dumanlama miktari olarak hatali yapilan pisiriinde kil yüzeye çiktigi için sira gömülebilmektedir. Sira gömülen kil, altinda lüster efekti olsa dahi ortaya çikarilamamaktadir. - Geleneksel Kil macun lüsteri uygulandiktan sonra firinlama öncesinde tasima sirasinda deforme olabilmektedir. - Sirçi lüster ve raku teknigi uygulamalarinda da tekrar tekrar pisirmek mümkündür fakat bu iki teknikte de firça dekoru uygulanmamaktadir. - Rezinat lüsterinde, hazir lüsteri kullanan herkesin zemin sirlarindaki farkliliklar dahil benzer efektleri elde edebilmekte ve isikta lüster efekti oldukça zayiftir. - Indirgen pisirim, öncelikle meydana gelen çesitli gazlardan olusan yogun dumani insan sagligi için zararli olmayacagi bir alan gerektirmektedir. - Rezinat lüsteri ile elde edilen bazi efektler bulasik makinesinde çikabilmektedir. Kimyasal reçeteleri farkli olabildigi için düsük derecelerde elde edilen efektler için geçerli oldugu düsünülmektedir. - Indirgen pisirim Siriçi lüster ve raku tekniklerinde pismis toprak formun bütünü gümüslü sir ile kaplanmaktadir. Dolayisi ile kullanilan indirgenebilir pigmentler yani gümüs nitrat v.b. miktari dolayisi ile maliyeti, siralti lüster teknigi uygulamasina göre daha fazladir. Teknigin bilinen durumunda yer alan CN1480424 sayili Çin patent dokümaninda, yüksek sicaklikta seramik siralti renk isleminin gerçeklestirilmesi için gelistirilen bir yöntemden bahsedilmektedir. Bu bulusta amaç sadece yapilan dekorun bozulmamasina yöneliktir. Yöntem perdahlama gerektirmektedir. Dekorlandiktan sonra sirlamadan önce 700 derecede pisirilerek boyalar sabitlenmektedir. Indirgeme sir gelisimi sirasinda yüksek derecede gerçeklestirilmektedir. indirgen pisirim için formun sogutulmasi gerektigi ve tekrar isitilarak indirgenmesinden bahsedilmemistir. Kalay, gümüs, bizmut gibi indirgenebilir elementler patent kapsaminda ele alinmamistir. Tamamen sirüstü teknigi olarak uygulanan geleneksel kil macun lüster teknigi uygulamasina alternatif olusturmamaktadir. Siriçi renklendirmeye alternatif olusturmaktadir. Teknigin bilinen durumunda yer alan CN103524112 sayili Çin patent dokümaninda çift tarafli siralti islemi uygulanan bes renkli porselen plakanin elde dilmesi yönteminden bahSedilmemektedir. Yöntemde kullanilan sir malzemesi; feldispat tozu, kuvars, talk pudrasi, kaolin, çinko oksit ve bir seramik karo içermektedir. Gelistirilen bulus, siralti uygulanan fakat tek yüzeye yapilmasina alternatif olarak iki yüzeye uygulanmasina yöneliktir. Yöntem macunla ilgili degil, sir ile ilgilidir. Sir olarak ele alinan astar gibi tutunmaya yardimci bir bilesige aittir. El dekoru, reçetesi verilen sirin yüzeye püskürtülmesinden sonra yapilmakta ve sonra tekrar sirlanmaktadir. Basvuru dokümaninin ilk paragrafinda yer alan lüster ifadesinin indirgen pisirimle degil, finalde elde edilen sirin, genel görünümünün bir parçasidir. Teknigin bilinen durumunda yer alan CN1020605 70 sayili Çin patent dokümaninda yüksek sicakliktaki siralti altin kirmizisi pigmentin hazirlama yönteminden bahsedilmektedir. Gelistirilen yöntem sadece tek bir reçete ile tek bir renk ve bu rengin üretim metodu ile sinirlidir. Bulus, 1400 °C derece ile sinirlidir ve amaçlari bu derecede kullanilabilecek siralti altin kirmizi rengin elde edilmesinde yeni bir yöntem sunmaktadir. Yöntemde kizdirma yer almaktadir. B u teknikle elde edilen rengin üzerine ayrica sir uygulanmamaktadir. Örnek gösterilen patent dokümanlarin gelistirilen yöntemlerde yüksek dereceler kullanilmistir. Yöntemler Sadece porselen bünyeler içindir. Hiçbiri öncesinde sirüstüne uygulanan bir teknigin siraltina uygulanmasi ile ilgili degildir. Teknigin bilinen durumunda yer alan yöntemlerde karlilasilan sorunlar yukarida detayli olarak bahsedilmistir. Bu somnlari çözmek için bulus konusu indirgen pisirim lüster pigmentlerinin siraltina uygulanmasi yönteminin gelistirilmesi ihtiyaci duyulmustur. Bulusuii Amaçlari B u bulusun amaci, örtücü sir saglayici kalay bilesiginin sirin içine degil de sirin altina renk veren, lüster efekti veren pigmentlerle beraber uygulanmasini içeren indirgen pisirim lüster pigmentlerinin siraltina uygulanmasi yönteminin gerçeklestirilmesidir. Bulusun Ayrintili Açiklamasi Bulus, indirgen pisirim lüster pigmentlerinin siraltina uygulanmasi yöntemi olup; - Çömlekçi çamurlari, fritli çamur ve piyasada bulunan samotlu çamur, ESÇ 1, ESÇ 3 ile istenilen formun istenilen yöntemle elde edilmesi, - Formun üzerine istenilirse çesitli içeriklerde astar uygulanmasi, - Sekillendirilen çamura göre bisküvi pisiriminin yapilmasi - Ince bir zimpara ile yüzeyin pürüzsüzlestirilmesi, yikanarak tozlarindan arindirilmasi, - Siralti lüster macununu olusturacak olan kalay, gümüs, bakir, demir, bizmut gibi indirgenebilir bilesiklerin, istenilen renk ve efekte göre istenilirse titan, kursun, çinko, kursun silikat, üleksit gibi çesitli hammadde ve bilesikler de eklenerek farkli kombinasyonlarda çesitli oranlarda, porselen havanda su ile kismen ögütülmesi- karistirilmasi veya porselen tabak gibi su emmeyen bir düzlem üzerine piyasada bulunan hazir boyalarin aktarilip gümüs ve/veya kalay ve/veya bizmut eklenerek dekor firçasi ile karistirilmasi, su ile istenilen macun kivaminin elde edilmesi veya daha önce hazirlanmis olan macunun tekrar kullanilmak üzere su ve bekleme süresine göre gümüs nitrat eklenerek istenilen macun kivaminin elde edilmesi, - Istenilen sayida indirgenebilir lüster maeununun istenilen alanlara ve istenilirse piyasada hazir bulunan indirgenmeyen diger boyalar da kullanilarak firça veya benzeri ile istenilen efekte göre çesitli kalinliklarda dekor yapilmasi, - Sekillendirilen çamura, istenilen renge, efekte göre piyasada bulunan seffaf sirlar ile veya seffaf ham sirlar ile sirlanmasi, - Kullanilan sir gelisinceye kadar pisirilmesi (900- , - Lüster firininda, istenilen efekte göre en az 573 °C dereceye kadar isitilip firin sicakken içerisine çira, yag gibi duman vericilerin atilip firinin her tarafi hava alamayacak sekilde kapatilmasi, sogurken gerekirse kapaktan birkaç kez daha duman yapici atilip yine firinin her tarafinin kapatilmasi ve çamur yapisina göre sogumasinin beklenmesi; ya da raku firininda, kullanilan sir yumusayincaya kadar yaklasik 700 0C dereceden sonrasina kadar firinin isitilmasi, bir masa ile formun firindan alinip, talas gibi kolay yanici malzemenin bulundugu bir toprak çukur, tencere gibi kapakli metal bir kovaya konulmasi ve üzerinin kapatilmasi ve sogumasinin beklenmesi adimlarini içerrnektedir. Bulusta, çömlekçi çarkinda sekillendirilen form üzerine, bazi yerlerine bakir oksit içerikli astar uygulanmis, hazir Kütahya siri ile sirlanmistir. Sirin üstüne kil orani düsük, gümüs orani arttirilmis macun reçetesi hazirlanip uygulanmistir. Ardindan raku tekniginde indirgenmistir. Fakat geleneksel çömlekçi çamuru ile üretilen formlar raku teknigi ile indirgeme uygulamasi sirasinda çatlamistir. Raku siri olarak ise basarili sonuç alinmistir. Sirüstüne uygulanan macun reçetesinden de lüster efekti alinmis ancak duman miktari çok, derece de yüksek geldigi için köpürme meydana gelmistir. Bunun üzerine sagar tekniginde indirgemek üzere kil orani düsük, gümüs orani arttiriliriis macun reçetesi hazirlanip sirin altina uygulanmistir, Sir ikinci pisirimde gelistirilmistir. Üçüncü pisirimde form, sagar kutusu içerisinde nötr firinda Indirgenmistir ancak sagarda formlarin saglam çikmasina ragmen duman verici olarak koyulan malzemeler sira yapismistir. Lüster efekti kismen elde edilmistir. Bunun üzerine denenmis olan kil orani düsük, gümüs orani arttirilmis macun reçetesinden yola çikarak lüster firininda indirgemek üzere hem hazir boyalarin içerisine gümüs nitrat, bizmut. kalay eklenmis hem de sadece gümüs nitrat, bizmut, kalay, demir, bakir bilesikleri karistirarak hazirlanan indirgenebilir siralti lüster macun reçeteleri siraltina uygulanmistir. Uygulama sirasinda firça dekoru için kullanilan düz tabagin üzerine gümüs nitrat, bakir ve kalay karisimi, yanina indirgenemeyen kobalt boya koyarak her firçayi alis Sirasinda kobalt boyadaki indirgenebilir malzeme karisimini çogaltarak efektte geçis denenmistir. Ikinci pisirimde Kütahya siri gelistirilmistir. Gazli firindaki Üçüncü pisiriinimde kil macun lüsterinde oldugu gibi firin içerisine duman yapici çira atarak ve sonra firinin her tarafini kapatarak bazen ikinci üçüncü dumanlama daha yaparak formlar indirgenmistir. Indirgeme dereceleri zemin sirina göre 600- 750 °C derece arasinda degisinektedir. Kursun alkali hazir Kütahya friti ile Bor Alkali hazir endüstriyel sir kullanilmistir. Ayrica ESÇ 3 çamuru ile uyumlu 1200 0C derecelik sir ile yani porselen bünyede de siralti lüster teknigi ile lüster efekti elde edilmistir. Geleneksel sirüstü kil macun reçetelerini siraltina uygulamak için kalay, bizmut ve gümüs gibi indirgenebilir pigmentlerin miktarini arttirilmis dolayisi ile kil orani azaltilmistir. Böylece yine siralti indirgenebilir lüster macunu kullanmistir. Gelistirilen indirgen pisirim siralti lüsteri yönteminin temel özelligi, örtücü sir saglayici kalay bilesiginin sirin içine degil de sirin altina renk veren, lüster efekti veren pigmentlerle beraber uygulanmasidir. Böylece lüster efekti saglayan örtücülük özelligi formun istenilen yerlerine uygulanir. indirgen pisirim kil macun lüsteri macun reçetesinden en önemli farki, kalay oraninin yüksek kil oraninin ise oldukça düsük olmasidir. Kalay macun yanisira astarla beraber, astarin içine eklenerek de uygulanabilir fakat maliyet daha yüksek olacaktir. Gelistirilen yöntemin avantajlari asagida detayli olarak açiklanmistir. siralti lüster macunu, sirin altina uygulandigi için sirüstü kil macun- lüsterinden farkli olarak bozulmadan birden çok kez 4. Pisiriin olarak nötr ortamda pisirdikten sonra 5. Pisirim olarak veya direkt 4. Pisirim olarak tekrar indirgenebilmektedir. Kil macun lüsterinden en önemli farki budur. Çünkü kil macun lüsteri, indirgeme pisirimi sonlanmis olan formun üzerindeki kilin temizlenmesinden sonra lüster efekti görülebildigi için 4. Pisirimde dekorda kullanilan kimya, bilesim degismektedir. Dolayisi ile hatali pisirimden geri dönüs yoktur. Indirgen pisirim siralti lüster teknigi için üretilecek olan hazir macunlar ve kullanim kilavuzu ile çalisildiginda, indirgen pisirim efekti elde etmek isteyen fakat acemi, ise hakim olmayan, seramik kimya bilgisi yetersiz, laboratuar ortami olmayan pismis toprak üreticilerine uygun bir tekniktir. Siriçi lüster tekniginde de tekrar tekrar indirgemek mümkündür fakat siriçi teknigi ile firça dekoru yapmak mümkün degildir söyle ki: uygulanacak çesitli derecelerdeki kimyasal bilesim ve yapidaki sirlar eriyip gelisirken sirlar birbirlerine karisabilmektedir. siraltinda kullanilmak üzere hazirlanan indirgen pisirim lüster pigmentleri ile yapilan macun, lüster pisirimi yani firin içerisine belirli bir süre duman verilmesi yerine raku tekniginde de indirgenerek lüster efekti elde edilebilmektedir. Bu yolla raku teknigine uygun olmayan firça dekoru kullanilarak efektlerin kontrolü saglanabilmektedir. Bu da günümüzde tamamen artistik amaçlar, sosyallesme, paylasma ve estetik bazen teorik aktarim gibi amaçlar için kullanilan raku teknigine alternatif bezeme, uygulama teknigi sunmaktadir. Lüster teknigi, raku teknigine göre daha sakin uygulanmaktadir. Rakuda 700- 1100 0C derecelere isitilmis bir ürün firindan çikartildiginda oldukça heyecan vericidir, dikkat çekicidir ve tehlikelidir; lüster tekniginde ürün, güvenli firinin içindedir. Ayrica raku tekniginde sonuç yaklasik yarim saat içerisinde elde Edil irken lüster de firinin sogumasi için bekleinek gerekmektedir. Bu nedenlerle workshop, çalistay olarak adlandirilan paylasim ortamlarinda indirgen pisirim teknigi olarak raku tercih edilmektedir. Indirgen pisirim yapilacak üründe sirin altina örtücülügü saglayan özellikle kalay oksit katkisi ile hazirlanmis lüster pigmentleri alkali, kursunlu, kursun alkali, alkali bor, kursun bor, karisimi sirlarla kullanilabilir. Kil macun lüsterinin özelligi olan örtücü sir saglayici kalay, sirin altina renk veren, lüster efekti veren pigmentlerle beraber uygulanir. Böylece lüster efekti saglayan örtücülük özelligi formun istenilen yerlerine uygulanabilir. Ayrica kalay ile örtücülük saglanmayan boyalarla veya indirgenmeyen renk veren pigmentlerle ayni üründe hem indirgenebilen hem de indirgenemeyen efektler, renkler bir arada kullanilabilir. Reziant lüsterinde elde edilen efektlerden, isiklardan daha güçlüdür, degiskendir, artistik oynamalara ve kisisel farkliliklar yapmaya oldukça uygundur. Rezinat lüsteri standarttir, efekti zayiftir. Siralti lüster tekniginde kullanilan pigmentler firça ile uygulanip, seffaf sir ile sirlanarak elde edildigi için raku tekniginde de uygulanabilinektedir. Ve farkli efektlerin, istenilen alanlarda elde edilmesi saglanmaktadir. Raku yapan pismis toprak üreticileri hazir Siriçi lüsterler ve raku sirlarinda efekt vericiler yani basta gümüs nitrat ya da diger bilesikleri daha çok kullanilmaktadir. Dolayisi ile sirin altina uygulanmasindan daha pahalidir. Bünye, astar, sir reçetelerinin çesitlenmesi, indirgeme pisirim dereceleri, dumanlama miktari, denenmemis elementin denenmesi ile elde edilebilecek oldukça çok çesitlenebilecek yeni efektler elde edilebilir. Siralti lüster- raku teknigi, kalay kullanilmayan macun reçetesi, platin, altin bilesikleri, Sirüstüne uygulanan kil macun lüsteri macunu reçetesi hiç degistirilmeden siraltinda, özellikle kalay ile örtücülestirilmis sirin altinda, piyasada satilan endüstriyel diger sirlarla denenmemistir. Cuerda seca tekniginde de denenebilir. Desenli, sirli ve indirgenmis ürün elde edilebilir fakat bu da siriçi lüster teknigi kapsaminda degerlendirilmedir. Çünkü cuerda seca tekniginde yani motiflerin sekerli su, parafin gibi su emmeyi engelleyen bir madde ile desenlerin belirlendigi, sinirlarin çizildigi daha sonra bu sinirlarin içerisine farkli renkli sirlarin doldurulmasi teknigi ile bezenen bir ürün ile firça dekoru ile bezenen bir üründeki motif detaylari oldukça farklidir. TR TR TR DESCRIPTION UNDERGLASS APPLICATION OF REDUCED FIRING LUSTERS PIGMENTS Technical Field The invention is related to the underglaze application method of reducing firing luster pigments, which involves applying the covering glaze providing tin compound under the glaze, rather than in or on the glaze, together with pigments that give color and luster effect. Prior Art Terracotta is commonly known as ceramics. This nomenclature today covers all products obtained by shaping the soil and then cooking it until it gains durability. There are multiple classifications of terracotta products according to their various characteristics; ceramics, tiles, porcelain, soft porcelain, hard porcelain, technical porcelain, conductor, insulator, etc. They can be classified according to their structures, which can vary according to both different firing degrees and different raw materials, and therefore their purposes. Technical porcelains, space shuttle, textile machine parts, etc. Productions made for these fields are within the scope of engineering science. Those who prepare mud and glaze to be sold in the market are also in the field of ceramic engineering. Anyone who can bake the soil they shape in personal kilns or through workshop owners who rent kilns, using ready-made clay and glaze that can be purchased from the market, is generally called a ceramicist. Those who produce using traditional ceramic production knowledge are generally referred to as potters and cupmakers, who extract the soil they will shape from nature, prepare it, shape it, and bake it in kilns using traditional methods. Their numbers are decreasing day by day because they only produce functional daily use items. As they use today's ready-made materials and produce new forms, they are called ceramists. However, there are also tile makers who prepare their clay using traditional methods, using ready-made Kütahya materials or producing palace ceramics. Tile makers, especially in Iznik and Kütahya, make mass production in their personal workshops, which cannot be defined as fabrication production, but is based entirely on hand workmanship. Some workshops produce clays called personal fritted clay, stone tile, pat pat tile, with their own personal recipes. They also develop glazes, paints and primers in accordance with their recipes. The firing temperature of the shaped soil generally starts from 573 °C. The mud and glaze sold ready to be shaped in the market are suitable for use between 900 and 1070 °C and are called ceramics when produced with this material. The temperature of 1200 °C, which is also easily available from the market. There are also glazes and clays that are suitable for porcelain, and the ones produced with this material are called porcelain. The difference in the grades is due to the difference in the raw material and the hardening and melting degrees of the raw material. Ceramics in the world and in Turkey generally produce the forms, textures, decorations and materials they produce with the materials they obtain from the market. They express themselves with differences in color. A minority of ceramicists produce their own clay, glaze and paint. Their personal recipes and experiences also create their own differences. In addition to artistic sculptures, they produce forms and decorative items for daily use. These productions take place in workshops, not in factories. These workshops can be for personal hobby or commercial purposes, as well as courses in fine arts high schools, vocational schools, faculties. There are four techniques related to the underglaze luster technique: Reductive firing clay paste luster (Brush decoration) Reductive firing raku. There are many publications regarding these four techniques in both physical and social sciences, and prescriptions are stated in these publications. 1. Reductive firing clay paste luster (Brush decoration) Until the 18th century, luster effects were achieved with the Reductive Firing Clay Paste Luster technique, which is a decoration technique applied to the covering glaze in the middle of the reducing firing. In the literature, it is generally called luster-lustre-luster. It is a decoration technique developed approximately 1000 years ago by glass masters and then by Islamic ceramicists. The years when it was first applied coincided with the time when alchemy (obtaining gold by various methods) became popular1 and the success of the soil (raw material) shining like gold after being reduced. The fact that it is (generally) forbidden to eat from a precious vessel in Islamic belief has made the technique additionally valuable.2 Some Turkish art historians have called luster, which was a decoration technique only in the Seljuk Period until 20-30 years ago, as "Polishing technique". Luster is a surface decoration technique. Luster effects are achieved by decorating the product glazed with covering glaze with a clay paste prepared with reducible pigments and clay, and then reducing it and cleaning the clay layer on it after it has cooled. The specified reducing medium clay paste luster production technique is generally as follows: forin is shaped. The first cooking is done. It is usually glazed with glaze, which can be developed at 900 CC degrees, covered with alkali and tin. The glaze is cooked. Brush decoration is made on the glazed shiny surface with a paste prepared from reducible compounds such as tin, mercury, clay, iron, silver, bismuth, and copper in different proportions and combinations, and the oven is heated to approximately 600 °C and flames such as kindling, oil, and wood are placed inside the oven. smoke producing material is thrown away. The oven is closed on all sides so that no air gets in. While the CO in the kiln wants to become CO2, the one in the ceramics takes the Oxygen it can get. This loss of oxygen causes the luster effect to occur on the ceramic surface. It is a metal-based, transparent film layer that covers the glazes. Today, reductive firing clay paste luster is still used, especially as "Iranian luster". 2. Luster in reductive firing siren. Reduceable elements are added into the siren. The form is hidden. The glaze is developed and reduced to the desired degree by adding smoke agent into the kiln as it develops or while it cools, preventing the kiln from getting any air. Some artists apply color-giving oxides under glaze as a colored primer. However, they add luster pigment, especially silver, into the sirin. The same secret can also be reduced with the raku technique. 3. Resinate luster (Brush decoration) Resinant luster is an overglaze decoration technique like liquid gilding, but it is obtained by a third firing, usually around 600 0C, without reduction firing. They are reduced and adhere to the glaze surface in various colors. The result obtained is the harmonious combination of surfaces with each other, without chemical interactions and changes or a radical interaction, depending on the methods used. As a result of reductive firing in an oxygen-free environment, which has been used for centuries, luster works that are attractive and showy and enter into chemical reactions with the glaze on them are obtained. Since the 18th century, the methods of luster work have changed and the over-glaze firing technique has been carried especially to oxygenated environments. In this technique, metal salts are found as a composition in the carrier resin and thinning oil, so they are also called "organo-metallic compounds". Although this method is easier than the other in terms of application, it does not have the liveliness and attractiveness of reducing media lusters. Although luster works made with liquid gold and metal resinate methods are less attractive compared to reducing medium works, they are accepted today by being used in the majority of contemporary works. 3 Factories producing industrial terracotta use resinate luster. 4. Reduced firing raku glazes are similar to luster glazes and raku glazes. Both are obtained by reduction. Their difference is their method of reduction. In the luster, smoke generator is introduced into the oven. In raku, the baked clay form is removed from the oven and buried in the smoke generator. In other words, luster in glaze is the process of closing the kiln in a way that does not allow air in or out after throwing flammable organic material into the kiln at the softening level of the glaze, while raku is removing the ceramic from the kiln at the melting and softening level of the glaze and reducing it with flammable, smoke-producing organics. Brush decoration is not applied in these two techniques. In both of them, luster pigments such as silver, bismuth and colorants are added to the sirin. Some artists only apply colorants under glaze. Today, terra cotta reductive firing techniques used for artistic purposes were techniques used for different purposes in the past. These were used for purposes such as protecting the glazed product from direct fire, fast firing, and first firing (heating the shaped clay until it gains hardness). The commonality of firing and kiln types, which are today known as raku, sagar, pit, basket firing, paper kiln, is the aim of ceramicists to achieve different effects. The disadvantages of these methods, which are in the known state of the art, are listed in detail below. - Reductive firing, in the use of traditional Clay Paste luster, there is no reversal in case of an incorrect reduction. The luster effect that occurs under the clay can only be revealed after the clay layer on it is cleaned. Therefore, when it is fired again in a neutral environment, the clay in the first recipe is removed from the environment and the recipe remaining on the glazed surface changes. In addition, if the cooking is done incorrectly regarding the temperature or amount of smoke, the row may become buried as the clay floats to the surface. Clay buried in rows cannot be revealed even if there is a luster effect underneath. - After the traditional clay paste luster is applied, it may be deformed during transportation before baking. - It is possible to fire repeatedly in glaze luster and raku techniques, but brush decoration is not applied in these two techniques. - In Resinate luster, everyone who uses ready-made luster can achieve similar effects, including differences in the ground glaze, and the luster effect is quite weak in the light. - Reductive firing requires an area where the dense smoke consisting of various gases will not be harmful to human health. - Some effects obtained with Resinate luster may appear in the dishwasher. It is thought to be valid for effects obtained at low degrees, as their chemical recipes may differ. - In reduction firing, in-glaze luster and raku techniques, the entire fired earthen form is covered with silver glaze. Therefore, the reducible pigments used, i.e. silver nitrate, etc. Due to its quantity, its cost is higher than the underglaze luster technique application. In the Chinese patent document numbered CN1480424, which is in the state of the art, a method developed for performing ceramic underglaze color processing at high temperature is mentioned. The purpose of this invention is only to prevent the decoration from being damaged. The method requires polishing. After decorating, the paints are fixed by baking at 700 degrees before glazing. Reduction is carried out to a high degree during glaze development. It is not mentioned that the form must be cooled for reducing firing and that it can be reduced by heating again. Reducible elements such as tin, silver and bismuth are not covered within the scope of the patent. It does not constitute an alternative to the traditional clay paste luster technique, which is applied as a completely supine technique. It provides an alternative to infused coloring. In the Chinese patent document numbered CN103524112, which is in the state of the art, there is no mention of the method of obtaining five-color porcelain plate with double-sided underglaze process. Glaze material used in the method; It contains feldspar powder, quartz, talcum powder, kaolin, zinc oxide and a ceramic tile. The invention developed is for the application of underglaze on two surfaces as an alternative to applying it on a single surface. The method is not about the paste, it is about the glaze. It belongs to a compound that helps adhesion like a primer, which is considered as a glaze. Hand decoration is made after the prescribed glaze is sprayed on the surface and then glazed again. The term luster in the first paragraph of the application document is not a result of reductive firing, but is a part of the general appearance of the final result. In the Chinese patent document numbered CN1020605 70, which is in the state of the art, the preparation method of underglaze gold red pigment at high temperature is mentioned. The developed method is limited to a single recipe, a single color and the production method of this color. The invention is limited to 1400 °C and offers a new method for obtaining the underglaze golden red color that can be used at this temperature. The method includes irritation. No additional glaze is applied on the color obtained with this technique. High grades were used in the methods developed in the patent documents shown as examples. Methods Only for porcelain bodies. None of them are related to applying a technique that was previously applied on the back to the underside. The problems encountered in the methods in the known state of the technique are mentioned in detail above. In order to solve these problems, there was a need to develop the underglaze application method of the reductive firing luster pigments of the invention. Purposes of the Invention The purpose of this invention is to realize the method of applying reductive firing luster pigments under the glaze, which involves applying the covering glaze-providing tin compound together with the pigments that give color and luster effect under the glaze, rather than into the glaze. Detailed Description of the Invention The invention is a method of applying reductive firing luster pigments under secret; - Obtaining the desired form with the desired method using potter's clay, frit clay and samot clay available in the market, ESÇ 1, ESÇ 3, - Applying primer with various contents on the form if desired, - Baking biscuits according to the shaped clay - Smoothing the surface with a fine sandpaper, washing. - Removing reducible compounds such as tin, silver, copper, iron and bismuth, which will form the underglaze luster paste, in various ratios in different combinations, depending on the desired color and effect, by adding various raw materials and compounds such as titanium, lead, zinc, lead silicate and ulexite, Partially grinding and mixing with water in a porcelain mortar, or transferring commercially available ready-made paints onto a non-water-absorbing surface such as a porcelain plate, adding silver and/or tin and/or bismuth and mixing with a decor brush, obtaining the desired paste consistency with water, or using a previously prepared paste. Obtaining the desired paste consistency by adding water for reuse and silver nitrate according to the waiting time, - Applying the desired number of reducible luster wax to the desired areas and, if desired, using other non-reducing paints available in the market to decorate in various thicknesses according to the desired effect with a brush or similar, - Applying the shaped mud to the desired effect. , glazing with transparent glazes available on the market or with transparent raw glazes depending on the desired color and effect, - Baking until the glaze used develops (900- , - In the luster kiln, heated to at least 573 °C depending on the desired effect and adding kindling, oil etc. into the kiln while it is hot. Throwing out the smoke generators and closing the oven on all sides so that no air can get in. While it is cooling, if necessary, throw the smoke generator through the lid a few more times and closing the oven on all sides and waiting for it to cool down according to the sludge structure; or in the raku kiln, heating the kiln to approximately 700 0C until the glaze used softens, taking the form from the kiln on a table, placing it in an earthen pit containing easily flammable material such as sawdust, or a metal bucket with a lid such as a pot, and covering it and waiting for it to cool. . In the invention, a copper oxide-containing primer was applied to some parts of the form shaped on the potter's wheel and it was glazed with ready-made Kütahya glaze. A paste recipe with low clay content and increased silver content was prepared and applied on the glaze. Then it was reduced in the raku technique. However, the forms produced with traditional potter's clay cracked during the reduction application with the raku technique. Successful results were obtained as Raku Siri. The luster effect was obtained from the paste recipe applied on top, but as the amount of smoke was too high, foaming occurred. Thereupon, a paste recipe with low clay content and increased silver content was prepared and applied under the glaze using the sagar technique, and the glaze was developed in the second firing. In the third firing, the form was lowered into the neutral oven in the sagar box, but although the forms came out intact in the sagar, the materials placed as smokers stuck to the row. The luster effect has been partially achieved. Thereupon, based on the tried paste recipe with low clay content and increased silver content, silver nitrate and bismuth were added to the ready-made paints to reduce them in the luster furnace. Tin was added and reducible underglaze luster paste recipes prepared by mixing only silver nitrate, bismuth, tin, iron and copper compounds were applied under the underglaze. During the application, a mixture of silver nitrate, copper and tin was placed on the flat plate used for brush decoration, and irreducible cobalt paint next to it, and a transition in the effect was tried by increasing the reducible material mixture in the cobalt paint during the application of each brush. In the second cooking, Kütahya siri was developed. In the third firing in the gas oven, the forms were reduced by throwing smoke-making kindling into the oven, as in the clay paste luster, and then covering all sides of the oven and sometimes doing a second or third smoke. Reduction degrees vary between 600 and 750 °C depending on the soil temperature. Lead alkali ready Kütahya frit and Boron Alkali ready industrial glaze were used. In addition, a luster effect was achieved with a 1200 0C glaze compatible with ESÇ 3 clay, that is, with the underglaze luster technique on the porcelain body. In order to apply traditional over-glazed clay paste recipes under-glaze, the amount of reducible pigments such as tin, bismuth and silver has been increased, thus the clay ratio has been reduced. Thus, he again used underglaze reducible luster paste. The main feature of the developed reductive firing underglaze luster method is that the covering glaze providing tin compound is applied together with the pigments that give color and luster effect under the glaze, rather than into the glaze. Thus, the covering feature that provides a luster effect is applied to the desired parts of the form. The most important difference between reducing firing clay paste and luster paste recipe is that the tin ratio is high and the clay ratio is quite low. In addition to tin putty, it can also be applied with the primer or by adding it into the primer, but the cost will be higher. The advantages of the developed method are explained in detail below. Since underglaze luster paste is applied under the glaze, unlike overglaze clay paste-luster, it can be reduced again as the 5th firing or directly as the 4th firing after being fired in a neutral environment as the 4th firing multiple times without deterioration. This is the most important difference from clay paste luster. Because the luster effect of clay paste can be seen after the clay on the form whose reduction firing has been completed is removed, the chemistry and composition used in the decoration changes during the 4th firing. Therefore, there is no turning back from incorrect cooking. When working with the ready-made pastes and user manual to be produced for the reductive firing underglaze luster technique, it is a technique suitable for terracotta producers who want to achieve the reductive firing effect but are novices, have insufficient knowledge of ceramic chemistry, and do not have a laboratory environment. It is possible to reduce the glaze repeatedly in the luster technique, but it is not possible to make brush decoration with the glaze technique. That is to say: the glazes of various chemical composition and structure to be applied can mix with each other as they melt and develop. The paste made with reductive firing luster pigments prepared to be used under glaze can be reduced in the raku technique to obtain a luster effect, instead of luster firing, that is, introducing smoke into the oven for a certain period of time. In this way, effects can be controlled by using brush decor that is not suitable for the raku technique. This offers an alternative decoration and application technique to the raku technique, which is used today for purely artistic purposes, socialization, sharing and aesthetic and sometimes theoretical transfer. The luster technique is applied more calmly than the raku technique. Rakuda, a product heated to 700-1100 0C degrees, is quite exciting, eye-catching and dangerous when taken out of the oven; In the luster technique, the product is in the safe oven. In addition, in the raku technique, the result is obtained in about half an hour, while in luster, it is necessary to wait for the oven to cool down. For these reasons, raku is preferred as a reducing firing technique in sharing environments called workshops. Luster pigments, especially prepared with the addition of tin oxide, which provide coverage under the glaze on the product to be reduced fired, can be used with alkali, lead, lead alkali, alkaline boron, lead boron and mixed glazes. Tin, which provides the covering glaze, which is a feature of clay paste luster, is applied together with pigments that give color to the underside of the glaze and give a luster effect. Thus, the covering feature that provides a luster effect can be applied to any desired part of the form. In addition, both reducible and non-reducible effects and colors can be used together in the same product with paints that do not provide covering with tin or pigments that give non-reducible color. It is stronger than the effects and lights obtained on reziant luster, it is variable, and it is quite suitable for artistic playing and making personal differences. Resinate luster is standard, its effect is weak. Since the pigments used in the underglaze luster technique are applied with a brush and obtained by glazing with transparent glaze, they can also be applied in the raku technique. And different effects can be achieved in the desired areas. Terracotta producers who make raku are more likely to use ready-made lusters and effect enhancers in raku glazes, namely silver nitrate or other compounds. Therefore, it is more expensive than applying it under the glaze. A wide variety of new effects can be achieved by varying the body, slip and glaze recipes, reduction firing degrees, amount of smoking, and trying untested elements. Underglaze-lusterraku technique, tin-free paste recipe, platinum, gold compounds, clay paste applied on the glaze, glaze paste recipe has not been tested with any other commercially available industrial glazes under the glaze, especially under the glaze covered with tin. It can also be tried in the cuerda seca technique. Patterned, glazed and reduced products can be obtained, but this should be evaluated within the scope of the glazed luster technique. Because in the cuerda seca technique, in which the motifs are determined with a substance that prevents water absorption such as sugar water or paraffin, the borders are drawn, the motif details in a product decorated with the technique of filling different colored glazes into these borders and a product decorated with brush decoration are quite different.TR TR TR

TR2020/14524A 2020-09-14 2020-09-14 APPLICATION OF REDUCED COOKING LUSTER PIGMENTS TR202014524A2 (en)

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