CN105777066B - 一种以稀土尾砂为原料制备的龙泉青瓷及其制造方法 - Google Patents
一种以稀土尾砂为原料制备的龙泉青瓷及其制造方法 Download PDFInfo
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- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明公开了一种以稀土尾砂为原料制备的龙泉青瓷及其制造方法。包括龙泉青瓷坯用原料、水和添加剂，重量百分比为50～65：35～40：1～5。所述龙泉青瓷坯料氧化物中的原料重量百分比分别为：稀土尾砂15～75％，石英30～65％，煅烧氧化铝粉10～30％，煅烧高岭土粉15～30％，高岭土粉30～50％，钾长石粉2～10％，氧化钙1～3％，紫金土1～8％；以龙泉青瓷坯料计，所述添加剂的组成为粘结剂2～7％，増塑剂5～15％，润滑剂21～25％，分散剂1～5％。该发明使废弃的稀土资源得到了充分利用，有效促进稀土尾砂资源化利用和龙泉青瓷制瓷技术的应用和发展，大幅降低了龙泉青瓷规划化生产的成本。
Description
技术领域
本发明涉及一种龙泉青瓷技术领域，特别是涉及一种以稀土尾砂为原料制备的龙泉青瓷及其制造方法。
背景技术
我国稀土资源储量丰富，稀土尾砂是提取稀土后剩余的尾矿，但由于稀土矿品味较低，稀土的开采带来大量的稀土尾砂。目前，稀土尾砂的处理方式主要是堆积或填埋，这种处理方式占地面积较大，浪费大量土地资源；并且该处理方式将对水土资源造成严重污染，破坏生态平衡，阻碍了经济的可持续发展。因此，对稀土尾砂的资源再生利用，是实现矿产资源可持续发展的重要途径，不仅是我国稀土产业发展的战略需求，也是我国建立资源、能源节约型社会的迫切需求。
龙泉青瓷一直以造型端庄浑朴、色泽纯洁斑斓闻名于世，有较大的市场需求。然而，原料成本高、青瓷强度和呈色强度不足等方面的因素阻碍了龙泉青瓷的推广应用。以稀土尾砂为原料制造的龙泉青瓷可克服青瓷强度和呈色强度的不足，而且将废弃的稀土尾砂作为制造青瓷的原料，降低了原料成本，减轻了环境危害，具有显著的社会效益和经济效益。为此，一种以稀土尾砂为原料制备的龙泉青瓷及其制造方法亟待研发。
发明内容
本发明要解决的技术问题是提供一种以稀土尾砂为原料制备的龙泉青瓷及其制造方法，提高稀土尾砂的利用率。
为解决以上技术问题，本发明的技术方案是：一种以稀土尾砂为原料制备的龙泉青瓷。其包括龙泉青瓷坯用原料、水和添加剂，重量百分比为50～65：35～40：1～5。
进一步的，所述龙泉青瓷坯用原料中坯料氧化物的原料重量百分比分别为稀土尾砂15～75％，石英30～65％，煅烧氧化铝粉10～30％，煅烧高岭土粉15～30％，高岭土粉30～50％，钾长石粉2～10％，氧化钙1～3％，紫金土1～8％；以龙泉青瓷坯料计，添加剂的组成为粘结剂2～7％，増塑剂5～15％，润滑剂21～25％，分散剂1～5％。
进一步的，所述稀土尾砂化学组成含有SiO2 50～85％，Al2O3 5～20％，Fe2O3 1.5～3.5％，K2O 0.6～2.5％，Na2O 0.2～2.0％，CaO 0.1～0.3％，MgO 0.1～1.0％，TiO2 0.1～0.5％，I.L 2.0～5.0％，K2O+Na2O 2～10％。
进一步的，所述粘结剂为羧甲基纤维素、聚乙烯醇、淀粉、甘油中一种或多种；增塑剂为甘油、乙酸三甘醇、硬脂酸丁酯、松香酸甲酯中的一种或多种；润滑剂为醋酸纤维素、硬脂酸、煤油、微晶石蜡、油酸中的一种或多种；分散剂为为聚甲基丙稀酰胺(PMAA-NH4)、氯化铵(NH4Cl)、聚乙二醇(平均分子量为10000)、三油酸甘油酯(GTO)、蓖麻油(CTO)中的一种或多种。上述添加剂可提高球磨混合物中固含量，保证龙泉青瓷坯料料浆的分散性和稳定性。上述添加剂使原料料浆效果佳，且添加剂不易挥发，对人体和环境都较安全。
进一步的，所述龙泉青瓷的坯用原料为黄坛泥、浦城泥、宝溪泥和竹乡泥中的一种或多种；所述龙泉青瓷坯用原料的粒度为325目筛以下。
进一步的，一种以稀土尾砂为原料制备的龙泉青瓷制造方法，包括以下步骤：
S1将坯用原料和水按混合细磨至全部通过万孔筛，并在混料机中搅拌混合1～4h；按比例称取坯用原料、水玻璃、腐植酸钠5～8：0.3～1.0：0.45～0.65进行化浆搅拌混合3～4h，然后加入添加剂进行搅拌均匀而形成泥浆；
S2经真空练泥后进行陈腐，然后重复进行真空练泥，再进行成型；
S3将成型的龙泉青瓷坯体进行干燥，经微波干燥和热风干燥后，在500～700℃温度下进行素烧，保温1～2h；
S4待冷却后，再施传统龙泉青瓷青釉层1～2mm，在还原气氛下热处理温度1150～1300℃下烧成，热处理升温速度为2～5℃/min，保温2～3h，获得一种以稀土尾砂为原料的龙泉青瓷。
进一步的，所述步骤S1中：稀土尾砂的加入量为青瓷坯料的1～5倍；添加剂的加入量为青瓷坯料的1～3倍。
进一步的，所述步骤S1中：所述青瓷坯料混合物球磨到细度为D10＞0.06μm，D90为0.35±0.05μm，D100＜3μm，并使用孔径≤1μm的筛网进行过筛除杂，从而得到了龙泉青瓷坯料料浆。龙泉青瓷坯料料浆达到该微纳米级细度后，龙泉青瓷坯体成瓷强度更佳，致密性更佳。
进一步的，所述步骤S2中：料浆陈腐中的料浆细度325目；筛余0.3～0.6％；料浆含水率24～28％；料浆比重1.65～1.95％；料浆流速25～40秒。
进一步的，所述步骤S4中：所述龙泉青瓷青釉着色用原料为紫金土、Fe2O3、FeO中的一种或多种。
本发明采用稀土尾砂代替或替换部分现有技术中一般采用的普通石英粉和长石，配合优化的青瓷坯用原料粉体改性处理，主要是利用稀土尾砂中游离石英和由长石风化的高岭石，能够与青瓷坯用原料充分反应的特性，使固相反应进行更为完全，有助于提高青瓷成瓷强度。
本发明以稀土尾砂为原料制备龙泉青瓷，其坯用料浆具有良好的悬浮性和分散性，化学稳定性高、流变性能良好，环保无污染。而且，素烧过的坯体施釉后再经还原热处理，坯釉的结合性好、成瓷强度高、立体感强，色调细腻无色差。
本发明制造龙泉青瓷工艺简单，并且能大幅降低生产成本，充分提高稀土尾砂资源利用率。
具体实施方式
实施例1
S1按重量份计，配制龙泉青瓷坯料氧化物组分如下：稀土尾砂45％，石英55％，煅烧氧化铝粉10％，煅烧高岭土粉25％，高岭土粉15％，钾长石粉3％，氧化钙0.4％，紫金土4％。其中稀土尾砂化学组分含量为：SiO2 65.56％，Al2O3 24.57％，Fe2O3 1.7％，K2O1.0％，Na2O 0.3％，CaO 0.1％，MgO 1.2％，TiO2 0.2％，I.L 3.0％。
S2按重量百分比，龙泉青瓷坯用原料、水和添加剂的重量百分比为54：41：5。其中，以坯体坯料配方计，所述粘结剂羧甲基纤维素为12％，增塑剂甘油为15％，润滑剂醋酸纤维素为25％，分散剂PMAA-NH4为1％。将坯用原料、水和添加剂混合均匀后，置于球磨机中球磨至D10＞0.06μm，D90为0.35±0.05μm，D100＜3μm的细度后，使用孔径325目的筛网进行过筛除杂、陈腐，形成高性能龙泉青瓷坯用料浆。
S3将料浆压滤形成泥状，经真空练泥陈腐后脱泡，然后重复进行真空练泥，再将成型的龙泉青瓷坯体进行干燥，经微波干燥和热风干燥后，在650℃温度下进行素烧，保温1h。
S4待冷却后，再施传统龙泉青瓷粉青釉，在还原气氛1200℃温度下烧成，保温2h，热处理的升温速率为2℃/min，获得成瓷强度高、抗折抗压强度佳、色彩鲜艳、纹理自然、质感柔和、立体感强、具有天然粉青纹理和色彩，表面较平整和光滑的龙泉青瓷产品。
实施例2
S1按重量份计，配制龙泉青瓷坯料氧化物组分如下：稀土尾砂50％，石英50％，煅烧氧化铝粉20％，煅烧高岭土粉30％，高岭土粉10％，钾长石粉4％，氧化钙0.5％，紫金土5％。其中稀土尾砂化学组分含量为：SiO2 67.89％，Al2O3 27.78％，Fe2O3 1.5％，K2O1.1％，Na2O 0.4％，CaO 0.2％，MgO 1.0％，TiO2 0.2％，I.L 3.5％。
S2按重量百分比，龙泉青瓷坯用原料、水和添加剂的重量百分比为62：35：3。其中，以坯体坯料配方计，所述添加剂的组成粘结剂聚乙烯醇为10％，增塑剂乙酸三甘醇为13％，润滑剂醋酸纤维素为21％，分散剂聚乙二醇为1％。将坯用原料、水和添加剂混合均匀后，置于球磨机中球磨至D10＞0.06μm，D90为0.35±0.05μm，D100＜3μm的细度后，使用孔径325目的筛网进行过筛除杂、陈腐，形成高性能龙泉青瓷坯用料浆。
S3将料浆压滤形成泥状，经真空练泥陈腐后脱泡，然后重复进行真空练泥，再将成型的龙泉青瓷坯体进行干燥，经微波干燥和热风干燥后，在600℃温度下进行素烧，保温1h。
S4待冷却后，再施传统龙泉青瓷豆青釉，在还原气氛1200℃温度下烧成，保温2.5h，热处理的升温速率为2℃/min，获得成瓷强度高、抗折抗压强度佳、纹理自然、质感柔和、立体感强、具有天然豆青般纹理，表面较平整、光滑的龙泉青瓷产品。
实施例3
S1按重量份计，配制龙泉青瓷坯料氧化物组分如下：稀土尾砂52％，石英56％，煅烧氧化铝粉25％，煅烧高岭土粉34％，高岭土粉16％，钾长石粉5％，氧化钙0.7％，紫金土4％。其中稀土尾砂化学组分含量为：SiO2 68.97％，Al2O3 29.39％，Fe2O3 2.3％，K2O1.4％，Na2O 0.2％，CaO 0.3％，MgO 1.0％，TiO2 0.1％，I.L 4.5％。
S2按重量百分比，龙泉青瓷坯用原料、水和添加剂的重量百分比为61：35：4。其中，以坯体坯料配方计，所述添加剂的组成粘结剂淀粉为6.5％，增塑剂甘油为11％，润滑剂醋酸纤维素为23％，分散剂GTO为2％。将坯用原料、水和添加剂混合均匀后，置于球磨机中球磨至D10＞0.06μm，D90为0.35±0.05μm，D100＜3μm的细度后，使用孔径325目的筛网进行过筛除杂、陈腐，形成高性能龙泉青瓷坯用料浆。
S3将料浆压滤形成泥状，经真空练泥陈腐后脱泡，然后重复进行真空练泥，再将成型的龙泉青瓷坯体进行干燥，经微波干燥和热风干燥后，在600℃温度下进行素烧，保温2h。
S4待冷却后，再施传统龙泉青瓷梅子青釉，在还原气氛1250℃温度下烧成，保温1.5h，热处理的升温速率为2℃/min，获得成瓷强度高、抗折抗压强度佳、纹理自然、质感柔和、立体感强，具有天然梅子青纹理，表面较平整、光滑的龙泉青瓷产品。
实施例4
S1按重量份计，配制龙泉青瓷坯料氧化物组分如下：稀土尾砂51％，石英54％，煅烧氧化铝粉27％，煅烧高岭土粉32％，高岭土粉14％，钾长石粉6％，氧化钙1.0％，紫金土5％。其中稀土尾砂化学组分含量为：SiO2 65.28％，Al2O3 24.98％，Fe2O3 3.58％，K2O4.29％，Na2O 0.26％，CaO 0.33％，MgO 0.53％，TiO2 0.09％，I.L 4.0％。
S2按重量百分比，龙泉青瓷坯用原料、水和添加剂的重量百分比为58：37：5。其中，以坯体坯料配方计，所述添加剂的组成粘结剂聚乙烯醇为5％，增塑剂乙酸三甘醇为8％，润滑剂硬脂酸为22％，分散剂PMAA-NH4为3.5％。将坯用原料、水和添加剂混合均匀后，置于球磨机中球磨至D10＞0.06μm，D90为0.35±0.05μm，D100＜3μm的细度后，使用孔径325目的筛网，并进行过筛除杂、陈腐，形成高性能龙泉青瓷坯用料浆。
S3将料浆压滤形成泥状，经真空练泥陈腐后脱泡，然后重复进行真空练泥，再将成型的龙泉青瓷坯体进行干燥，经微波干燥和热风干燥后，在550℃温度下进行素烧，保温1h。
S4待冷却后，再施传统龙泉青瓷豆青釉，在还原气氛1200℃温度下烧成，保温1.5h，热处理的升温速率为2℃/min，获得成瓷强度高、抗折抗压强度佳，且纹理自然、质感柔和、立体感强、具有天然豆青纹理，表面较平整、光滑的龙泉青瓷产品。
实施例5
S1按重量份计，配制龙泉青瓷坯料氧化物组分如下：稀土尾砂56％，石英58％，煅烧氧化铝粉24％，煅烧高岭土粉32％，高岭土粉18％，钾长石粉6％，氧化钙0.9％，紫金土5％。其中稀土尾砂化学组分含量为：SiO2 63.07％，Al2O3 26.06％，Fe2O3 3.9％，K2O2.4％，Na2O 0.1％，CaO 0.5％，MgO 0.6％，TiO2 0.2％，I.L 3.9％。
S2按重量百分比，龙泉青瓷坯用原料、水和添加剂的重量百分比为60：37：3。其中，以坯体坯料配方计，所述添加剂的组成粘结剂淀粉为6％，增塑剂硬脂酸丁酯为10％，润滑剂醋酸纤维素为22％，分散剂聚乙二醇为2.5％。将坯用原料、水和添加剂混合均匀后，置于球磨机中球磨至D10＞0.06μm，D90为0.35±0.05μm，D100＜3μm的细度后，使用孔径325目的筛网，并进行过筛除杂、陈腐，形成高性能龙泉青瓷坯用料浆。
S3将料浆压滤形成泥状，经真空练泥陈腐后脱泡，然后重复进行真空练泥，再将成型的龙泉青瓷坯体进行干燥，经微波干燥和热风干燥后，在650℃温度下进行素烧，保温2h。
S4待冷却后，再施传统龙泉青瓷豆青釉，在还原气氛1250℃温度下烧成，保温2.5h，热处理的升温速率为2℃/min，获得成瓷强度高、抗折抗压强度佳，且纹理自然、质感柔和、立体感强，具天然豆青纹理，表面较平整、光滑的龙泉青瓷产品。
实施例6
S1按重量份计，配制龙泉青瓷坯料氧化物组分如下：稀土尾砂50％，石英46％，煅烧氧化铝粉18％，煅烧高岭土粉31％，高岭土粉12％，钾长石粉6％，氧化钙0.8％，紫金土5％。其中稀土尾砂化学组分含量为：SiO2 64.12％，Al2O3 25.63％，Fe2O3 3.9％，K2O3.4％，Na2O 0.3％，CaO 0.5％，MgO 1.0％，TiO2 0.09％，I.L 5.5％。
S2按重量百分比，龙泉青瓷坯用原料、水和添加剂的重量百分比为59：36：4。其中，所述添加剂的组成粘结剂淀粉为7％，增塑剂硬脂酸丁酯为13％，润滑剂油酸为24％，分散剂聚乙二醇为4％。将坯用原料、水和添加剂混合均匀后，置于球磨机中球磨到D10＞0.06μm，D90为0.35±0.05μm，D100＜3μm的细度后，使用孔径325目的筛网，并进行过筛除杂、陈腐，形成高性能龙泉青瓷坯用料浆。
S3将料浆压滤形成泥状，经真空练泥陈腐后脱泡，然后重复进行真空练泥，再将成型的龙泉青瓷坯体进行干燥，经微波干燥和热风干燥后，在700℃温度下进行素烧，保温1.5h。
S4待冷却后，再施传统龙泉青瓷梅子青釉，在还原气氛1280℃温度下烧成，保温3h，热处理的升温速率为2℃/min，获得成瓷强度高、抗折抗压强度佳，且纹理自然、质感柔和、立体感强、具天然豆青纹理，表面较平整、光滑的龙泉青瓷产品。
本发明技术优势：
1、本发明以稀土尾砂为原料制造龙泉青瓷，不仅大大降低龙泉青瓷的生产成本，且充分利用资源，减少稀土尾砂对环境的危害，迅速传承世界“非遗”龙泉青瓷文化，传播民族文化精神，具有重大的经济和社会效益。不仅符合我国资源再生利用的战略需求，而且符合未来我国建设能源集约化、绿色环保社会的发展要求。
2、本发明制备的龙泉青瓷成瓷强度高、致密度高(抗冲击强度达到4.00KJ/m2，抗折强度达到120Mpa以上，热稳定性可保证200～20℃水冷热交换一次不裂)，可满足各种型号手机对材料性能要求。
3、本发明制造工艺简单，原料成本低(可节约35％以上)，有利于节能减排和产业化的生产。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将权利要求等同要件含义和范围内的所有变化囊括在本发明内。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (3)
1.一种以稀土尾砂为原料制备的龙泉青瓷制造方法，其特征在于，包括以下步骤：
S1将青瓷坯料和水按混合细磨至全部通过万孔筛，并在混料机中搅拌混合1～4h；按重量比例称取青瓷坯料、水玻璃、腐植酸钠5～8：0.3～1.0：0.45～0.65进行化浆搅拌混合3～4h，然后加入添加剂进行搅拌均匀而形成泥浆；所述龙泉青瓷的坯用原料为黄坛泥、浦城泥、宝溪泥中的一种或多种；所述青瓷坯料的粒度为325目筛以下；步骤S1中：稀土尾砂的加入量为青瓷坯料的1～5倍；添加剂的加入量为青瓷坯料的1～3倍；
S2经真空练泥后进行陈腐，然后重复进行真空练泥，再进行成型；
S3将成型的龙泉青瓷坯体进行干燥，经微波干燥和热风干燥后，在500～700℃温度下进行素烧，保温1～2h；
S4待冷却后，再施传统龙泉青瓷青釉层1～2mm，在还原气氛下热处理温度1150～1300℃下烧成，热处理升温速度为2～5℃/min，保温2～3h，获得一种以稀土尾砂为原料的龙泉青瓷。
2.根据权利要求1所述一种以稀土尾砂为原料制备的龙泉青瓷制造方法，其特征在于，步骤S1中：所述青瓷坯料混合物球磨到细度为D10＞0.06μm，D90为0.35±0.05μm，D100＜3μm，并使用孔径≤1μm的筛网进行过筛除杂，从而得到了龙泉青瓷坯料料浆。
3.根据权利要求1所述一种以稀土尾砂为原料制备的龙泉青瓷制造方法，其特征在于，步骤S4中：所述龙泉青瓷青釉着色用原料为紫金土、Fe2O3、FeO中的一种或多种。
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