TWI495624B - Ceramic glaze having bronze metallic gloss and its preparation method - Google Patents
Ceramic glaze having bronze metallic gloss and its preparation method Download PDFInfo
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Description
本發明係與陶瓷釉料之製備技術有關，更詳而言之是指一種燒成後可令陶瓷表面具有金屬光澤之古銅色金屬光澤陶瓷釉料及其製備方法者。The invention relates to the preparation technology of the ceramic glaze, and more specifically to a bronze-colored metallic luster ceramic glaze which can make the ceramic surface have a metallic luster after firing and a preparation method thereof.
隨著瓷磚工藝的進步與消費市場多樣化的需求，瓷磚的花色和款式不斷更新替換，例如有仿木紋、仿皮革、仿天然石材、仿織物、仿金屬等圖案可供選擇，其中仿金屬圖案的瓷磚，給人豪華和富麗堂皇的感覺，用在地面和牆面上十分氣派，目前廣泛用於建築陶瓷、日用陶瓷和工藝陶瓷製品的裝飾上。2005年義大利與西班牙兩大國際陶瓷展開啟一股金屬釉磚流行的風氣，從此金屬釉磚不僅作為一種建材，且成為一種品味與時尚的象徵。With the advancement of ceramic tile technology and the diversified needs of the consumer market, the color and style of ceramic tiles are constantly updated and replaced, such as imitation wood grain, imitation leather, imitation natural stone, imitation fabric, imitation metal and other patterns, among which imitation metal The patterned tiles give a luxurious and palatial feel to the floor and walls, and are now widely used in the decoration of architectural ceramics, household ceramics and craft ceramics. In 2005, Italy and Spain's two international ceramics exhibitions opened a popular trend of metal glazed bricks. From then on, metal glazed bricks not only serve as a building material, but also become a symbol of taste and fashion.
習知於瓷磚上產生金屬光澤釉面效果之技術，主要可分為下述三種：The technique of producing a metallic luster glaze effect on a tile is mainly divided into the following three types:
(一)金屬膜(a) metal film
此機制主要以各種金屬及金屬氯化物與樹脂鹽類混合製成金屬樹脂酸鹽，並以芳香油類將其溶解生成黑褐色黏稠液體，塗裝於釉面再低溫燒成後，生成極薄的金屬膜，從而產生金屬光澤，此種產品缺點為生產成本高，釉面上的金屬膜易磨耗、風化而退色。This mechanism is mainly prepared by mixing various metals and metal chlorides with resin salts to form a metal resinate, and dissolving it as an aromatic oil to form a dark brown viscous liquid, which is applied to the glaze and then fired at a low temperature to form a very thin film. The metal film, which produces metallic luster, has the disadvantage of high production cost, and the metal film on the glaze is easy to wear, weathering and discoloring.
(二)膠態金屬(2) Colloidal metal
此機制為在鉛釉表面塗上一層物質，如：銅、銀或鐵的化合物以及黏土與其他等混合物，經還原熱處理(550℃)，持溫一段時間，金屬離子擴散進入釉層中，再經冷卻即可得帶有金屬光澤釉面，分析結果顯示，發現釉內有銅、銀金屬奈米粒子(10至50nm)，其對光線產生偶極電漿子偶合效應(dipole plasmon coupling)，因而使釉面產生金屬光澤。此釉面較前法耐風化與磨耗，但必須配合使用在低溫的鉛釉上，因此其用途受到限制。This mechanism is to apply a layer of material on the surface of the lead glaze, such as copper, silver or iron compounds and other mixtures of clay and other materials, after reduction heat treatment (550 ° C), holding the metal ions diffused into the glaze layer for a period of time, and then The metal glaze is obtained by cooling, and the analysis results show that there are copper and silver metal nanoparticles (10 to 50 nm) in the glaze, which produces dipole plasmon coupling to the light. Thus, the glaze produces a metallic luster. This glaze is resistant to weathering and wear than the previous method, but it must be used in combination with low-temperature lead glaze, so its use is limited.
(三)結晶體(3) Crystals
此機制指在基礎釉中加入一種或多種的過渡或稀土金屬氧化物，並在高溫下析出結晶，因而在釉面產生金屬光澤效果，且釉面的色澤取決於基礎釉的種類與添加過渡或稀土氧化物的種類及析出結晶相，此種釉面最耐風化與磨耗，惟此機制的釉料大部分含氧化鉛，由於其具有毒性，因此易危害人體健康。This mechanism refers to the addition of one or more transition or rare earth metal oxides to the base glaze and precipitation of crystals at high temperatures, thus producing a metallic luster effect on the glaze, and the color of the glaze depends on the type of base glaze and the transition or The type of rare earth oxides and the precipitation of crystalline phase, the glaze is most resistant to weathering and abrasion. However, most of the glazes of this mechanism contain lead oxide, which is toxic and therefore harmful to human health.
由上可知，上述現有技術中金屬膜或膠態金屬機制的釉料，其產生金屬光澤的方式分別存在有生產成本高而易退色以及用途受到限制的缺點，而結晶體機制的釉料因含有鉛而具有毒性的缺點。It can be seen from the above that the glazes of the above-mentioned prior art metal film or colloidal metal mechanism have the disadvantages of high production cost, easy fading and limited use, and the glaze of the crystal mechanism contains lead. It has the disadvantage of being toxic.
本發明之主要目的即在提供一種古銅色金屬光澤陶瓷釉料及其製備方法，其藉由添加特定的金屬氧化物，使其燒成後可穩定地呈現金屬光澤，係屬於具有耐風化與磨耗優點的結晶體機制，且組成物不含氧化鉛、無毒性，可解決前述習知技術之缺點者。The main object of the present invention is to provide a bronze-colored metallic luster ceramic glaze and a preparation method thereof, which can stably exhibit metallic luster by adding a specific metal oxide, and has the advantages of weathering resistance and wear resistance. The crystal mechanism, and the composition does not contain lead oxide, is non-toxic, and can solve the disadvantages of the prior art.
為達成上述發明目的，本發明提供一種古銅色金屬光澤陶瓷釉料，各組成物成分範圍(重量百分率)如下：In order to achieve the above object, the present invention provides a bronze-colored metallic luster ceramic glaze, and the composition range (weight percentage) of each composition is as follows:
40至60wt%之磷酸鹽化合物；15至30wt%之金屬氧化物；15至20wt%之氧化矽(SiO2 )；及5-10wt%之助熔劑，係氧化物。40 to 60% by weight of the phosphate compound; 15 to 30% by weight of the metal oxide; 15 to 20% by weight of cerium oxide (SiO 2 ); and 5 to 10% by weight of the fluxing agent, which is an oxide.
進一步地，該磷酸鹽化合物係磷酸鋁或磷酸鋁與偏磷酸鋁之混合物其中之一。Further, the phosphate compound is one of a mixture of aluminum phosphate or aluminum phosphate and aluminum metaphosphate.
進一步地，該金屬氧化物係氧化鐵或四氧化三鐵其中之一。Further, the metal oxide is one of iron oxide or triiron tetroxide.
進一步地，該氧化矽與助熔劑之重量比比值介於4至6之間。Further, the ratio of the weight ratio of the cerium oxide to the flux is between 4 and 6.
進一步地，該助熔劑包含氧化鈉、氧化鉀、氧化鈣、氧化鎂及氧化鋅。Further, the flux comprises sodium oxide, potassium oxide, calcium oxide, magnesium oxide, and zinc oxide.
進一步地，該氧化鈉與助熔劑的重量比比值介於0.5至0.55之間，氧化鉀與助熔劑的重量比比值介於0.05至0.06之間，氧化鈣與助熔劑的重量比比值介於0.35至0.40之間，氧化鎂與助熔劑的重量比比值介於0.045至0.055之間，而氧化鋅與助熔劑的重量比比值介於0.005至0.007之間。Further, the ratio of the weight ratio of the sodium oxide to the flux is between 0.5 and 0.55, the ratio of the weight ratio of the potassium oxide to the flux is between 0.05 and 0.06, and the ratio of the weight ratio of the calcium oxide to the flux is between 0.35. Between 0.40, the weight ratio of magnesium oxide to flux is between 0.045 and 0.055, and the weight ratio of zinc oxide to flux is between 0.005 and 0.007.
此外，本發明更提供前述古銅色金屬光澤陶瓷釉料的製備方法，其步驟包含有：濕式混合：將陶瓷釉料之組成物與研磨球石、水以1：2：1之體積比進行球磨、混合而形成陶瓷釉漿料；施釉：將前述陶瓷釉漿料施於一坯體表面；燒成：將該坯體置於一加熱爐中，在氧化氣氛下，於1至3小時之間升溫至1160-1210℃之間，並持溫5至10分鐘之間後爐冷而燒成。In addition, the present invention further provides a method for preparing the foregoing bronze metallic lustrous ceramic glaze, the steps comprising: wet mixing: ball-milling the composition of the ceramic glaze with the grinding ball and water at a volume ratio of 1:2:1. And mixing to form a ceramic glaze slurry; glazing: applying the ceramic glaze slurry to a surface of a blank; firing: placing the green body in a heating furnace under an oxidizing atmosphere for between 1 and 3 hours The temperature was raised to between 1,160 and 1,200 ° C, and the temperature was maintained for 5 to 10 minutes, and then the furnace was cooled and fired.
進一步地，施釉之步驟中，該坯體表面覆蓋有底釉。Further, in the step of glazing, the surface of the blank is covered with a bottom glaze.
進一步地，該坯體表面之底釉或可用化妝土取代。Further, the underglaze of the surface of the blank may be replaced with a cosmetic soil.
進一步地，施釉之步驟中，係採用噴、淋或印刷等方式之一將陶瓷釉漿料施於坯體表面。Further, in the step of glazing, the ceramic glaze slurry is applied to the surface of the green body by one of spraying, showering or printing.
以下，茲舉本發明數實施例，並配合圖式做進一步之詳細說明如後：本發明一較佳實施例之古銅色金屬光澤陶瓷釉料，係以磷酸鹽化合物、金屬氧化物及氧化矽(SiO2 )為主成分，並含有5-10wt%的助熔劑，其中，磷酸鹽化合物佔40-60wt%，係偏磷酸鋁(Al(PO3 )3 )、磷酸鋁(Al(PO3 ))或磷酸鋁與偏磷酸鋁之混合物其中之一，金屬氧化物佔15-30wt%，係氧化鐵(Fe2 O3 )或四氧化三鐵其中之一，氧化矽(SiO2 )與助熔劑的重量比的比值介於4至6之間，而該助熔劑包括有氧化鈉(Na2 O)、氧化鉀(K2 O)、氧化鈣(CaO)、氧化鎂(MgO)及氧化鋅(ZnO)，其中該氧化鈉與助熔劑的重量比的比值介於0.5至0.55之間，氧化鉀與助熔劑的重量比的比值介於0.05至0.06之間，氧化鈣與助熔劑的重量比的比值介於0.35至0.40之間，氧化鎂與助熔劑的重量比的比值介於0.045至0.055之間，而氧化鋅與助熔劑的重量比的的比值介於0.005至0.007之間。詳言之，各成份之使用原料及重量為：鈉長石22.35g，三氧化二鐵25.79g，偏磷酸鋁46.72g，石英4.23g，煅燒氧化鋅0.02g，碳酸鈣0.22g，煅燒滑石0.58g，金紅石0.08g。Hereinafter, the embodiments of the present invention will be further described in detail with reference to the accompanying drawings. The bronze-colored metallic luster ceramic glaze according to a preferred embodiment of the present invention is a phosphate compound, a metal oxide and cerium oxide ( SiO 2 ) is a main component and contains 5-10% by weight of a flux, wherein the phosphate compound accounts for 40-60% by weight, is aluminum metaphosphate (Al(PO 3 ) 3 ), aluminum phosphate (Al(PO 3 )) Or one of a mixture of aluminum phosphate and aluminum metaphosphate, the metal oxide accounts for 15-30% by weight, is one of iron oxide (Fe 2 O 3 ) or triiron tetroxide, cerium oxide (SiO 2 ) and flux The ratio of the weight ratio is between 4 and 6, and the flux includes sodium oxide (Na 2 O), potassium oxide (K 2 O), calcium oxide (CaO), magnesium oxide (MgO), and zinc oxide (ZnO). Wherein the ratio of the weight ratio of the sodium oxide to the flux is between 0.5 and 0.55, and the ratio of the weight ratio of potassium oxide to the flux is between 0.05 and 0.06, and the ratio of the weight ratio of calcium oxide to the flux Between 0.35 and 0.40, the ratio of the weight ratio of magnesium oxide to flux is between 0.045 and 0.055, and the weight ratio of zinc oxide to flux Ratio is between .005 to .007. In detail, the raw materials and weight of each component are: azusite 22.35g, ferric oxide 25.79g, aluminum metaphosphate 46.72g, quartz 4.23g, calcined zinc oxide 0.02g, calcium carbonate 0.22g, calcined talc 0.58g , rutile 0.08g.
基此，再依據以下步驟製備前述古銅色金屬光澤陶瓷釉料，如第一圖所示，其步驟包含有：濕式混合110：係將前述陶瓷釉料、研磨球石與水以1：2：1的體積比進行球磨，從而將陶瓷釉料與水混合成比重為1.4的陶瓷釉漿料，球磨時間控制於過325目篩網殘留量小於1%。前揭研磨球石可使用氧化鋁等球石。Therefore, the foregoing bronze-colored metallic luster ceramic glaze is prepared according to the following steps. As shown in the first figure, the steps include: wet mixing 110: the following ceramic glaze, grinding ball stone and water are 1:2: The volume ratio of 1 is ball-milled to mix the ceramic glaze with water to form a ceramic glaze slurry having a specific gravity of 1.4, and the ball milling time is controlled to be less than 1% of the residual amount of the 325 mesh screen. A ball such as alumina can be used for the previously disclosed grinding ball.
施釉120：係以噴、淋或印刷等方式將前述陶瓷釉漿料施於一表面覆蓋底釉之坯體上。本實施例該坯體係25×25 mm之瓷磚，底釉係化妝土，其釉漿比重1.5，施釉重約0.4g，施加陶瓷釉漿料後重約0.12g。Glazing 120: The ceramic glaze slurry is applied to a surface of the glaze by spraying, showering or printing. In the present embodiment, the billet system has a 25×25 mm ceramic tile, and the bottom glaze is a cosmetic soil. The glaze has a specific gravity of 1.5, a glaze weight of about 0.4 g, and a ceramic glaze slurry of about 0.12 g.
燒成130：係將前述坯體置於一加熱爐中，在氧化氣氛下於1至3小時之間內升溫至1160至1210℃之間(本實施例係3小時內升溫至1170℃)，並持溫5至10分鐘之間(本實施例係6分鐘)後爐冷而燒成，如附件一之照片所呈現的釉面，其結晶相為赤鐵礦(hematite)及白矽石(cristobalite)，其X光繞射圖(XRD)如第二圖所示。Firing 130: placing the green body in a heating furnace and raising the temperature to between 1160 and 1210 ° C in an oxidizing atmosphere for 1 to 3 hours (the temperature is raised to 1170 ° C in 3 hours in this embodiment). And after holding the temperature for 5 to 10 minutes (6 minutes in this embodiment), the furnace is cooled and fired. The glazed surface shown in the photo of Annex I has the crystal phase of hematite and white meteorite. Cristobalite), its X-ray diffraction pattern (XRD) is shown in the second figure.
請參閱附件二之照片所示，因析出赤鐵礦(hematite)及白矽石(cristobalite)結晶而產生古銅色金屬光澤，其X光繞射圖(XRD)如第三圖所示，係以如下之使用原料及重量透過前述製備方法進行燒成之釉面(3小時內升溫至1160℃)：鈉長石18.97 g，三氧化二鐵23.72g，偏磷酸鋁52.18g，石英4.23g，煅燒氧化鋅0.02g，碳酸鈣0.22g，煅燒滑石0.58g，金紅石0.08g。Please refer to the photo in Annex II for the appearance of bronze metal luster due to the precipitation of hematite and cristobalite crystals. The X-ray diffraction pattern (XRD) is shown in the third figure as follows. The glaze (the temperature is raised to 1160 ° C in 3 hours) using the raw materials and the weight by the above preparation method: 18.97 g of albite, 23.72 g of ferric oxide, 52.18 g of aluminum metaphosphate, 4.23 g of quartz, calcined zinc oxide 0.02 g, 0.22 g of calcium carbonate, 0.58 g of calcined talc, and 0.08 g of rutile.
基此，本發明藉由前述釉料與製備方法，可使得釉層表面燒成後析出赤鐵礦(hematite)及白矽石(cristobalite)結晶體，從而令釉面可穩定地呈現金屬光澤，且於釉料中不含氧化鉛，因此具有無毒性的優點。Therefore, according to the foregoing glaze and preparation method, the surface of the glaze layer can be burned to precipitate hematite and cristobalite crystals, so that the glaze can stably exhibit metallic luster, and It does not contain lead oxide in the glaze and therefore has the advantage of being non-toxic.
綜上所述，本發明古銅色金屬光澤陶瓷釉料及其製備方法，其藉由添加金屬氧化物並配合前述製備方法，可獲得具有耐風化、耐磨耗與無毒性優點之釉面，且釉面可穩定地呈現金屬光澤，乃前所未見之技術；緣是，本發明確實符合發明專利之規定，爰依法提出申請。In summary, the bronze-colored metallic luster ceramic glaze of the present invention and the preparation method thereof can be obtained by adding a metal oxide and the foregoing preparation method, thereby obtaining a glaze having the advantages of weather resistance, wear resistance and non-toxicity, and glazing It can stably present metallic luster, which is a technology that has never been seen before. The reason is that the present invention does meet the requirements of the invention patent and submits an application according to law.
110．．．濕式混合110. . . Wet mixing
120．．．施釉120. . . Glazing
130．．．燒成130. . . Burning
第一圖係本發明一較佳實施例之製備方法流程圖。The first figure is a flow chart of a preparation method of a preferred embodiment of the present invention.
第二圖係本發明一較佳實施例所製成釉面之X光繞射圖。The second drawing is an X-ray diffraction pattern of a glazed surface produced by a preferred embodiment of the present invention.
第三圖係本發明另一較佳實施例所製成釉面之X光繞射圖。The third figure is an X-ray diffraction pattern of a glaze formed by another preferred embodiment of the present invention.
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| US5993974A (en) * | 1997-11-11 | 1999-11-30 | Kawasaki Steel Corporation | Porcelain-enameled steel sheets and frits for enameling |
| US20110049122A1 (en) * | 2009-08-28 | 2011-03-03 | Chae Hyun Baek | Cooking Appliance |
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| US5993974A (en) * | 1997-11-11 | 1999-11-30 | Kawasaki Steel Corporation | Porcelain-enameled steel sheets and frits for enameling |
| US20110049122A1 (en) * | 2009-08-28 | 2011-03-03 | Chae Hyun Baek | Cooking Appliance |
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