Study on the effect of zinc or aluminium salt treatments on the surface properties of TiO2
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摘要: 硫酸法钛白生产工艺中，盐处理剂的选择对金红石二氧化钛晶体的表面性质有着重大影响，有必要对不同盐处理剂造成的钛白粉表面性质差异进行深入研究，揭示不同盐处理剂所引发的表面性质差异。采用SEM、XPS、BET等仪器分别研究了锌系盐处理和铝系盐处理的金红石样品的表面形貌、晶体表面缺陷、表面羟基的差异。结果表明：铝系盐处理的金红石样品呈现长条形，在沉降过程中受更大的沉降阻力，且铝系盐处理金红石样品表面存在更多的晶体缺陷、表面羟基，同时对水分子的解离作用更明显，在水分散体系有更高的表面电位，更容易形成更稳定的分散体系。Abstract: In the production process of titanium dioxide by sulfuric acid method, the selection of salt treatment agents has a significant impact on the surface properties of rutile titanium dioxide crystals. Thus it is necessary to carry out an in-depth study to reveal the differences in the surface properties of titanium dioxide caused by different salt treating agents. In this study, the differences in surface morphology, crystal surface defects, and surface hydroxyl groups of rutile samples treated with zinc-based salt and aluminium-based salt were investigated using SEM, XPS, and BET instruments, respectively. The results show that the aluminium salt-treated rutile samples present elongated shape and suffer from greater sedimentation resistance during the sedimentation process. Meanwhile, the aluminium salt-treated rutile samples have more crystal defects and surface hydroxyls on the surface than the zinc salt-treated samples, and also have more pronounced dissociative effects on water molecules, higher surface potential in the water-dispersed system, and are more capable of forming more stable dispersed systems.
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图 1 （a）锌系金红石TiO2样品SEM形貌；（b）铝系金红石TiO2样品SEM形貌；（c）锌系样品径长比分布；（d）铝系样品径长比分布。
Figure 1. SEM image of zinc-based rutile TiO2 sample (a), SEM image of aluminium-based rutile TiO2 sample (b), diameter-to-length ratio distribution of zinc-based sample (c) and diameter-to-length ratio distribution of aluminium-based sample(d)
图 2 金红石TiO2纳米颗粒的Ti 2p XPS分析
（a）锌系-1#样品；（b）锌系-2#样品；（c）铝系-3#样品；（d）铝系-4#样品
Figure 2. Ti 2p XPS analysis of rutile TiO2 nanoparticles
图 3 金红石TiO2纳米颗粒的O 1s XPS分析
（a）锌系-1#样品；（b）锌系-2#样品；（c）铝系-3#样品；（d）铝系-4#样品。
Figure 3. O 1s XPS analysis of rutile TiO2 nanoparticles
表 1 主要试验仪器
Table 1. Primary test instruments
仪器 型号 厂家 三头研磨机 RK/XPM-Ø120×3 武汉洛克粉磨设备
制造有限公司扫描电子显微镜 Gemini SEM 300 德国ZEISS X射线光电子能谱仪 K-Alpha 美国Thermo Scientific 热重分析仪 TG 209 F1 德国Netzsch 全自动比表面及
孔隙度分析仪ASAP 2460 美国Micromeritics Zeta电位分析仪 Zetasizer Nano ZS90 Malvern 
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表 2 TiO2 NPs上的Ti化学种类定量分析
Table 2. Quantitative analysis of Ti chemical species on TiO2 NPs
% TiO2 NPs 锌系-1# 锌系-2# 铝系-3# 铝系-4# Ti4+ 91.63 89.63 86.75 86.68 Ti3+ 8.57 10.37 13.25 13.32
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表 3 TiO2 NPs上的O化学种类定量分析
Table 3. Quantitative analysis of O chemical species on TiO2 NPs
% 类别 锌系-1# 锌系-2# 铝系-3# 铝系-4# Ti-O 78.97 70.84 65.33 68.11 Ti-OHb 14.76 22.51 26.74 20.85 Ti-OHt 6.26 6.65 7.92 11.04
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表 4 Zn/Al掺杂金红石TiO2相对表面羟基密度测定结果
Table 4. Relative surface hydroxyl density measurements of Zn/Al doped rutile TiO2
样品 热失重/% BET测试结果/（m²·g−1) NOH /nm2 锌系-1# 0.152 6.1235 16.6 锌系-2# 0.237 6.0489 26.2 铝系-3# 0.268 5.5840 32.1 铝系-4# 0.296 5.7895 34.25
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表 5 Zn/Al掺杂金红石TiO2水分散液Zeta电位测定结果
Table 5. Zeta potential measurement results of Zn/Al doped rutile TiO2 aqueous dispersions
样品 Zeta电位/mV 10%锌系-1# −24.7 10%锌系-2# −28.2 10%铝系-3# −39.2 10%铝系-4# −42.3
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