成核<strong>-</strong>生长型液<strong>-</strong>液分相对无铅低温熔剂性能的影响

doi:10.11901/1005.3093.2021.005

材料研究学报

2021, Vol. 35

Issue (9): 657-666 DOI: 10.11901/1005.3093.2021.005

研究论文

本期目录 | 过刊浏览

成核-生长型液-液分相对无铅低温熔剂性能的影响

汪鹏¹, 卢希龙¹^,²(

), 曹春娥¹(

), 陈云霞¹^,², 沈华荣¹, 张旭¹

^1.景德镇陶瓷大学材料科学与工程学院景德镇 333403
^2.景德镇市环境陶瓷材料重点实验室景德镇 333000

Influence of Nucleation-growth Liquid-liquid Phase Partition on Properties of Lead-free Low Temperature Frit

WANG Peng¹, LU Xilong¹^,²(

), CAO Chun-e¹(

), CHEN Yunxia¹^,², SHEN Huarong¹, ZHANG Xu¹

^1.College of Materials Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333403, China
^2.Jingdezhen Key Laboratory of Environmental Ceramic Materials, Jingdezhen 333000, China

引用本文:

汪鹏, 卢希龙, 曹春娥, 陈云霞, 沈华荣, 张旭. 成核-生长型液-液分相对无铅低温熔剂性能的影响[J]. 材料研究学报, 2021, 35(9): 657-666.
Peng WANG, Xilong LU, Chun-e CAO, Yunxia CHEN, Huarong SHEN, Xu ZHANG. Influence of Nucleation-growth Liquid-liquid Phase Partition on Properties of Lead-free Low Temperature Frit[J]. Chinese Journal of Materials Research, 2021, 35(9): 657-666.

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摘要:

采用高温熔制结合低温热处理制备成核-生长型液-液纳米级分相的低温熔剂，研究了分相结构对熔剂的光泽度、光泽损失、显微维氏硬度等性能的影响，用HSM和DSC研究熔剂高温变化过程中的特征点并找出了合适的热处理工艺参数，根据XRD分析了熔剂的晶相组成，用SEM和TEM观察了分相显微形貌，根据FTIR分析了分相的显微结构，根据熔剂的性能研究了分相结构改善其性能的机理。结果表明：与水淬工艺样品相比，适当的热处理可调控分散相的尺寸、体积分数和分布，使熔剂的显微硬度和耐磨性显著提高。随着热处理温度的提高熔剂的光泽损失呈“Z”字形变化，而显微硬度的变化趋势与其相反。热处理温度为630℃时光泽损失最小(26.4%)，显微硬度最大(6202 MPa)，耐磨等级达到3级(750转)。随着热处理温度的提高分散相的液滴尺寸和体积分数呈开口向下的抛物线变化。分相使碱-硼-铈富集在分散相中，分散相的尺寸和体积分数越大则连续相中的游离氧减少，即O/Si比减小，[SiO₄]及桥氧增多，网络聚合度提高。同时，熔剂具有致密的表面层，分相结构存在于熔剂内部，富碱-硼-铈相以滴状分散嵌入在富硅氧连续相中，富硅氧对碱硼相的保护使熔剂的耐磨性和显微硬度提高。

关键词 ：无机非金属材料, 玻璃与非晶, 低温熔剂, 热处理, 分相, 碱硼硅酸盐

Abstract：

The nucleation-growth type liquid-liquid nano-phase partitioned low-temperature frits were prepared via a two-step process: high-temperature melting and low-temperature heat treatment. The influence of the phase-partition on the gloss, gloss loss, microhardness and other properties of the ABS* lead-free low-temperature frit were assessed by means of high temperature microscopy, differential scanning calorimetry, X-ray diffractometer, scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. The results show that the size, volume fraction and distribution of the dispersed phase can be effectively adjusted with the aid of appropriate heat treatment processes. The heat-treated frits present microhardness and wear resistance much higher than those of the water-quenched ones. With the increasing heat treatment temperature, the gloss loss of the frits experienced a "Z" shaped variation and the microhardness experienced a reverse trend. Being heat treated at 630℃, the frit presents the smallest gloss loss of 26.4%, the largest hardness of 6202 MPa, whilst its wear resistance can be classified as grade 2 (750 revolutions). The size and the volume of the phase-partition generated dispersive droplets show a downward parabola-like variation as the heat treatment temperature increases. The phase partition facilitates the enrichment of alkali, cerium and boron in the dispersed phase. As the size and volume fraction of the dispersed phases in the frit increases, the free oxygen in the continuous matrix decreases, that is, the O/Si ratio decreases, while the amount of [SiO₄] and bridge oxygen increases and the polymerization degree of the network increases. Besides the frit has a dense surface layer, namely the phase-partitioning structure exists inside the frit. The phase rich in alkali, cerium and boron dispersed and embedded in the Si-rich continuous matrix as droplets, in other words the former is protected by the later one. Therefore, the wear resistance and microhardness of the frits were enhanced .

Key words： inorganic non-metallic materials glass and amorphous low-temperature frit heat treatment phase separation alkali borosilicate

收稿日期: 2021-01-13

ZTFLH:

TQ174.4

基金资助:国家自然科学基金(51862019);江西省教育厅基金(GJJ160883);景德镇市科技项目(20182GYDZ011-16)

作者简介: 汪鹏，男，1987年生，博士生

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https://www.cjmr.org/CN/10.11901/1005.3093.2021.005 或 https://www.cjmr.org/CN/Y2021/V35/I9/657

表1 基础配方R0的化学组成

表2 样品R0的非等温热处理制度

图1 熔剂样品R0的DSC曲线

图2 部分样品的XRD谱

图3 熔剂R0的高温显微镜照片

图4 试样的柱正投影面积与温度的关系

表3 非等温热处理对熔剂性能的影响

图5 光泽损失与终温热处理温度的关系

图6 显微维氏硬度与热处理温度的关系

图7 熔剂样品的横截面SEM照片

图8 熔剂分相液滴的尺寸分布

图9 熔剂中分相液滴的体积分数和平均尺寸

图10 样品R0的TEM照片

图11 样品R3的TEM照片

图12 样品R3的TEM照片和EDS能谱

表4 样品R3的TEM图中A、B、C三点的化学组成

图13 样品R3横截面的SEM照片

图14 样品的红外光谱

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