發(fā)布時間：2018-06-14 07:43

  本文選題：分相釉 + 結(jié)構(gòu)色　； 參考：《陜西科技大學(xué)》2016年博士論文

【摘要】：釉的分相呈色及結(jié)構(gòu)呈色作為一種重要的物理裝飾技術(shù),既能豐富陶瓷釉的品種,增強呈色的穩(wěn)定性,獲得美觀多樣的色彩,還可以充分利用礦渣等廢棄資源,實現(xiàn)節(jié)能減耗、綠色環(huán)保。本論文以研究制備新型分相色釉為目標(biāo),合理設(shè)計出磷系乳濁釉和硼磷雙助劑乳濁釉,并以其作為分相基礎(chǔ)釉,再以氧化鐵、銅粉、氧化銅和鐵礦渣作為著色物質(zhì),分別添加到基礎(chǔ)釉中,制備出呈色豐富、效果各異的釉面。通過各種測試技術(shù)分析了釉料組成、燒成制度、顯微結(jié)構(gòu)變化等對釉面性能和呈色效果的影響規(guī)律,并結(jié)合物理學(xué)、光學(xué)等理論對分相呈色及結(jié)構(gòu)呈色的機理進行了研究。分相結(jié)構(gòu)呈色具有低成本、低能耗、無污染等優(yōu)勢,對于提升陶瓷產(chǎn)品附加值具有較強的理論指導(dǎo)意義和較高的實用價值。(1)在燒成溫度為1180-1230℃、850℃以上冷卻速度為25-35℃/min的工藝條件下,可以制備出白度較高的R2O-RO-Al2O3-SiO2-P2O5體系乳濁釉,在磷含量高的區(qū)域釉面白度較高,產(chǎn)生乳濁的原因是分相和熔析晶體。在硼磷雙助劑乳濁釉中,釉組成中的B2O3/P2O5質(zhì)量比對乳濁效果影響較大,在合適的B2O3/P2O5質(zhì)量比條件下,磷酸鈣含量在2.5-15%的范圍,釉面白度高、光澤度好且無裂紋；燒成溫度對孤立液滴的大小、含量、分布有較大影響,進而影響釉的乳濁程度；釉面產(chǎn)生乳濁的主要原因是多次不混溶分相。因此,合理的配方組成、分相促進劑的配比與燒成制度是制備高質(zhì)量分相乳濁釉的重要因素。(2)以少量鐵的氧化物為著色劑,分別添加到磷系基礎(chǔ)釉及硼磷雙助劑基礎(chǔ)釉中,在不同燒成溫度下,得到具有多種分相呈色效果的釉面。通過分析氧化鐵分相色釉中釉組成、燒成溫度對分相微珠及呈色效果的影響,結(jié)合物理學(xué)、色彩學(xué)對釉色變化的機理作出解釋,即分相色釉的呈色機理符合瑞利散射及米散射規(guī)律：當(dāng)分相微珠尺寸小于100 nm時,以瑞利散射為主,釉面呈淡藍(lán)色；而分相微珠較大時,以米散射為主,釉面呈乳白色。因此,通過調(diào)整基礎(chǔ)釉的組成、燒成溫度,進而控制分相微珠尺寸及分布就可以獲得呈色豐富的氧化鐵分相色釉。(3)以單質(zhì)銅粉和氧化銅為著色劑,添加到磷系基礎(chǔ)釉中,在微氧化和氧化條件下,制備出不同呈色效果的銅系色釉。固定Ca3(PO4)2含量,隨著釉組成中SiO2/Al2O3與SiO2/CaO的變化,分相液滴的大小和分布發(fā)生變化,釉面可呈現(xiàn)月白、天青、天藍(lán)、銅綠等多種釉色。當(dāng)Cu粉含量增加時,釉面由乳白色、天青色、天藍(lán)色向海藍(lán)色轉(zhuǎn)變,乳濁度逐漸提高。當(dāng)Ca3(PO4)2含量增加時,釉面由淺黃綠色、天青色向月白色轉(zhuǎn)變,光澤度由半透明-半乳濁-乳濁漸變。在不同的燒成溫度和氣氛下,釉層中Cu+和Cu2+的比例不同,分相液滴的大小和分布對釉面呈色產(chǎn)生重要影響。(4)以鐵礦渣代替?zhèn)鹘y(tǒng)陶瓷色料,添加到磷系基礎(chǔ)釉中,通過著色離子產(chǎn)生的化學(xué)色與分相結(jié)構(gòu)產(chǎn)生的結(jié)構(gòu)色耦合,制備出不同呈色效果的鐵分相花釉。結(jié)合釉層組成、顯微結(jié)構(gòu)及燒成溫度等因素的分析,得出鐵礦渣加入量為25 wt%,燒成溫度在1190-1250℃范圍時,釉面平整、光澤度好,而且釉色及釉面花紋都較豐富。燒成溫度在1160℃和1220℃時,未熔解的磷酸鈣晶體是釉面出現(xiàn)花紋的原因；燒成溫度為1280℃時,釉中的磷酸鈣晶體完全熔融,發(fā)生微相功能轉(zhuǎn)化,產(chǎn)生釉面花紋。隨著鐵礦渣加入量的增多,熔解在釉中的Fe203含量增多,釉面顏色加深；當(dāng)鐵礦渣加入量過多時,剩余的Fe203以赤鐵礦的形式析出,使釉面帶有金屬閃光。(5)分相釉中的結(jié)構(gòu)色機制包括光子晶體結(jié)構(gòu)色、瑞利散射色和分相結(jié)構(gòu)呈色等,但因分相釉中兩玻璃相折射率比值較低,釉面呈色效果不明顯。引入Fe、Cu元素于分相釉中,分相對著色元素的聚集作用與其自身多種化學(xué)呈色相耦合、各種結(jié)構(gòu)色機制也因折射率之比提高得到強化,產(chǎn)生了豐富多彩的呈色效果。進一步豐富了陶瓷色釉的呈色機理,改變了“只有氣氛才能變換色彩”的觀念。
[Abstract]:The color distribution and structural color of the glaze as an important physical decoration technology can not only enrich the variety of the ceramic glaze, enhance the stability of the color and obtain the beautiful and diverse colors, but also make full use of the waste resources such as slag to achieve energy saving and environmental protection. This paper is aimed at the research and preparation of a new phase color glaze for the purpose of rational design. Phosphorous opacification glaze and boron phosphorus double additive glaze are used as phase separation base glaze, and then iron oxide, copper powder, copper oxide and iron slag are added to the base glaze, respectively. The glaze with rich color and different effect is prepared. The glaze composition, sintering system, microstructure change and so on are analyzed by various test techniques. The influence of performance and color rendering effect is studied in combination with the theory of physics, optics and other theories. The phase separation structure has the advantages of low cost, low energy consumption, no pollution and so on. It has strong theoretical guiding significance and high practical value for enhancing the added value of ceramic products. (1) in the sintering temperature Under the conditions of 1180-1230 C and 850 centigrade cooling rate of 25-35 C /min, the opacification glaze of R2O-RO-Al2O3-SiO2-P2O5 system with higher whiteness can be prepared. The white degree of the glaze is higher in the region with high phosphorus content. The cause of the opacification is phase separation and melting crystal. The B2O3/P2O5 quality ratio in the glaze composition of the boron phosphorus double aid opaque glaze is compared. The effect of opacification is great. Under the suitable B2O3/P2O5 mass ratio, the calcium phosphate content is in the range of 2.5-15%, the white degree of glaze is high, the glossiness is good and there is no crack. The firing temperature has a great influence on the size, content and distribution of the isolated droplet, and then affects the opacification degree of the glaze, and the main reason for the opacification of the glaze is the multiple unmiscible phase separation. Therefore, the rational formulation, the proportioning of the phase separation promoter and the firing system are important factors for the preparation of high quality phase separated opaque glaze. (2) a small amount of iron oxide as the colorant is added to the base glaze of the phosphorus system and the basic glaze of the boron and phosphorus double auxiliaries. At different firing temperatures, the glaze with a variety of phase separation effects is obtained. The composition of the glaze in the phase color glaze of ferric oxide, the influence of the firing temperature on the phase separation microsphere and the color rendering effect, and the explanation of the mechanism of the color change in physics and color science, that is, the color mechanism of the phase color glaze is in accordance with the Rayleigh scattering and the rice scattering law: when the size of the phase microsphere is less than 100 nm, the Rayleigh scattering is the main and the glaze is light blue. And the glaze is milky white when the microsphere is large, and the glaze is milky white. Therefore, by adjusting the composition of the base glaze and burning the temperature, and then controlling the size and distribution of the phase microbeads, the color rich phase color glaze of iron oxide can be obtained. (3) the copper powder and copper oxide as the colorant are added to the base glaze of the phosphorus system and in the micro oxidation and oxygen. Under the conditions, the copper color glaze with different color effect was prepared. The content of Ca3 (PO4) 2 was fixed. With the change of SiO2/Al2O3 and SiO2/CaO in the composition of the glaze, the size and distribution of the phase droplet changed. The glaze could show a variety of glaze color, such as the white, the celestite, the sky blue and the copper green. When the content of the Cu powder increased, the glaze was milky white, sky blue, and sky blue to sea blue. When the content of Ca3 (PO4) 2 increases, the glaze is changed from light yellow green to yellow green, sky blue to white, and glossiness from semitransparent turbid to opacification. In different firing temperatures and atmosphere, the proportion of Cu+ and Cu2+ in the glaze layer is different. The size and distribution of the phase droplets have an important effect on the color appearance of the glaze. (4) Iron slag is added to the base glaze in the phosphorus system instead of the traditional ceramic pigment. By coupling the chemical color produced by the colored ion and the structure color of the phase separation structure, the iron separation glaze with different color effect is prepared. The composition of the glaze layer, the microstructure and the sintering temperature are analyzed. The amount of iron slag added is 25 wt%, and the sintering temperature is 1 At the range of 190-1250 C, the glaze is smooth and glossiness is good, and the glaze color and the glaze pattern are all rich. When the sintering temperature is 1160 and 1220, the amorphous calcium phosphate crystal is the cause of the glaze pattern. When the sintering temperature is 1280, the calcium phosphate crystals in the glaze are completely fused, the microphase function transformation occurs and the glaze pattern produces. With the iron, the glaze pattern is produced. With iron, with iron. With iron, with iron. With iron When the amount of Slag Added increased, the content of Fe203 in the glaze increased and the color of the glaze deepened. When the amount of iron slag added, the remaining Fe203 precipitated in the form of hematite, which made the glaze with metal flash. (5) the structure color mechanism in the phase separation glaze includes the photonic crystal structure color, the Rayleigh scattering color and the phase structure color, but the phase separation glaze. The ratio of the refractive index of the glass phase of the middle two is low, and the color effect of the glaze is not obvious. The introduction of Fe, the Cu element in the phase separation glaze, the aggregation of the relative coloring elements is coupled with its own variety of chemistry, and the color mechanism of various structures is enhanced by the ratio of the refractive index, which produces a colorful and colorful effect. Further enriching the ceramic color. The coloring mechanism of glaze changed the idea that only atmosphere can change colors.
【學(xué)位授予單位】：陜西科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TQ174.43

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