吕沁洋,甄宇,陈明辉,王群昌,王福会.原位析出纳米氟化钙晶体的搪瓷涂层自润滑行为研究[J].表面技术,2022,51(12):72-81.
LYU Qin-yang,ZHEN Yu,CHEN Ming-hui,WANG Qun-chang,WANG Fu-hui.Self-lubrication Behavior of Enamel Coatings with in situ Precipitated Nano CaF2 Crystals[J].Surface Technology,2022,51(12):72-81
原位析出纳米氟化钙晶体的搪瓷涂层自润滑行为研究
Self-lubrication Behavior of Enamel Coatings with in situ Precipitated Nano CaF2 Crystals
  
DOI:10.16490/j.cnki.issn.1001-3660.2022.12.006
中文关键词:  搪瓷涂层  摩擦磨损  自润滑  CaF2  纳米晶体
英文关键词:enamel coating  friction and wear  self-lubrication  CaF2  nano crystals
基金项目:国家自然科学基金(51871051);工业和信息技术部项目(MJ–2017–J–99)
作者单位
吕沁洋 东北大学 沈阳材料科学国家研究中心,沈阳 110819 
甄宇 东北大学 沈阳材料科学国家研究中心,沈阳 110819 
陈明辉 东北大学 沈阳材料科学国家研究中心,沈阳 110819 
王群昌 东北大学 沈阳材料科学国家研究中心,沈阳 110819 
王福会 东北大学 沈阳材料科学国家研究中心,沈阳 110819 
AuthorInstitution
LYU Qin-yang Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China 
ZHEN Yu Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China 
CHEN Ming-hui Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China 
WANG Qun-chang Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China 
WANG Fu-hui Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China 
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中文摘要:
      目的 调控析出氟化钙晶体,赋予搪瓷涂层常温自润滑性能。方法 采用球磨和熔融2种方式向作为空白对照组的搪瓷配方中加入质量分数为3.5%的CaF2,制备出3种喷涂于304不锈钢上的搪瓷涂层。通过摩擦磨损实验、软化点测定和维氏硬度测定实验,分别评价搪瓷涂层的摩擦磨损性能、热性能和力学性能,并通过扫描电镜分析搪瓷的晶化情况和磨痕形貌,用电子探针显微分析仪分析磨痕表面的元素分布,探讨润滑机理。结果 采用球磨法加入CaF2制备的搪瓷基复合涂层中,CaF2颗粒的粒径较大且分布不均;在熔炼搪瓷时即加入CaF2颗粒,该氟化物可参与到搪瓷网络结构中,并在搪瓷涂层烧制时原位析出平均粒径为132 nm、大小均匀且弥散分布的纳米级CaF2晶体。结果显示,熔融添加质量分数为3.5%的CaF2,使得搪瓷涂层的摩擦因数由0.57降至0.37,磨损率也降低了2个数量级,而球磨添加质量分数为3.5%CaF2的搪瓷涂层的摩擦因数稍有降低,但磨损率基本无变化。熔融添加氟化物的搪瓷涂层,原位析出了纳米级CaF2晶体,诱使摩擦表面形成了润滑层。结论 CaF2的加入可在一定程度上提高搪瓷涂层在常温条件下的耐磨性和润滑性,当CaF2为原位析出的纳米级晶体时具备优异的减摩润滑效果。
英文摘要:
      The work aims to control the precipitated nano CaF2 crystals to make the enamel coating has self-lubrication at normal temperature. Three kinds of enamel coatings were prepared on 304 stainless steel substrate, i.e. the one without fluoride addition (Base), the one blended with 3.5wt.% CaF2 by ball-milling (MJ3.5), and the one with 3.5wt.% CaF2 added during the glaze smelting procedure (RJ3.5). Through the friction and wear experiment, the softening point and Vickers hardness tests, wear performances, thermal and mechanical properties of enamel were evaluated. By scanning electron microscopy (SEM) and electron probe microanalysis (EPMA), the crystallization of enamel, morphology and elements distribution at wear scar were investigated, and the self-lubricating mechanisms were finally discussed. For the enamel coating with CaF2 particles blended by ball-milling (MJ3.5), its fluoride crystals were of large size and uneven distribution. However, when CaF2 was introduced during the smelting procedure of enamel, the fluoride can take part in the construction of enamel network and precipitated out as nano crystals at the firing stage of the enamel coating. In this case, the crystals had uniform size of 132 nm and distributed evenly in the enamel coating RJ3.5. Friction coefficient was decreased from 0.57 to 0.37 by adding 3.5wt.% CaF2 (Base vs. RJ3.5), and the wear rate also decreased by two order of magnitude, i.e. decreased from 1.76×10–4 mm3/(N.m)to 5.03×10–6 mm3/(N.m), both friction coefficient and wear rate decreased significantly. In comparison, friction coefficient of the enamel coating MJ3.5 was slightly decreased from 0.57 to merely 0.49, and the wear rate was still kept at the order of 10–5 mm3/(N.m) as the enamel coating of Base, the improvement of tribological properties was not too much. After in-depth analysis of the worn morphologies of RJ3.5 enamel coating, it can be concluded that the lubrication mechanism of the RJ3.5 coating was as follows. The in situ precipitated nano crystals of CaF2 which added during the glaze smelting procedure (RJ3.5) had excellent bonding performance with the enamel itself, made the whole enamel coating have certain deformation ability. Therefore, no severe brittle fracture phenomenon occurred during the friction process, only small wear debris with nano CaF2 crystals were produced. The wear debris existed between the friction pair and the coating surface. Due to the small size and deformability of nano CaF2 crystals, the wear debris was easy to be compacted. After continuous friction and wear, CaF2 accumulated on the grinding crack surface and formed a lubricating layer which was rich in CaF2. The lubrication layer can separate the friction pair from the coating surface and protect the coating, so that RJ3.5 coating can also has excellent self-lubricating properties at normal temperature. RJ3.5 enamel coating was innovatively different from MJ3.5 enamel coating through different addition method. Apparently, only through this different method, RJ3 enamel coating shows far better performance than MJ3.5 enamel coating in crystal distribution, bonding ability, friction coefficient, wear rate and other aspects, this way of adding CaF2 to enamel coating provides a possibility and new idea for CaF2` to produce lubrication effect at normal temperature.
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