包覆型氧化铁黄颜料微结构与耐热性能研究

doi:10.15541/jim20150253

摘要/Abstract

摘要：

氧化铁黄颜料因耐热性差而限制了在塑料加工和卷材涂料中的应用。本研究以氧化铁黄为前驱体, 采用沉淀法合成氢氧化铝包覆氧化铁黄颜料, 采用XRD、FT-IR、TG-DTA、SEM&EDS和TEM等方法表征包覆型铁黄颜料的结构, 探讨了反应pH对复合材料微结构以及耐热性能的影响。结果表明, pH为4时, 铁黄表面包覆层为无定型氢氧化铝; pH提高至6、8和10时, 表面包覆层为晶态薄水铝石相。包覆后氧化铁黄颜料耐热性有了较大提升。特别在pH为8、10时, 铁黄颜料 240℃下耐热处理30 min后色差值较小, 与表面包覆层形成的薄水铝石相密切相关。铁黄包覆前后, 保持了原先的针状结构, 未出现团聚; 当pH为10时, 包覆后铁黄颜料除针状结构外, 还出现了较粗的晶态棒状物, 可能与羟基氧化铝在反应过程中自身成核有关, 解释了DTA图谱上246℃处出现的特殊吸热峰。本研究为耐温铁黄颜料开发提供了理论与实践指导。

关键词: 氧化铁黄, 包覆, 氢氧化铝, 耐热性

Abstract:

Poor heat resistance of iron oxide yellow pigment limits its application in plastics processing and coil coatings. Yellow iron oxide pigments coating with aluminum hydroxide were synthesized by a precipitation method using yellow iron oxide as precursor. Structure of the composite pigment is characterized using XRD, FT-IR, TG-DTA, SEM-EDS, and TEM. The effect of pH on structure and heat resistance of the pigments was investigated. All results show that iron oxide yellow coating layer is amorphous aluminum hydroxide when pH is 4. When pH increases to 6, 8 and 10, the surface coating layer is boehmite phase. The heat resistance of coated yellow iron oxide pigments is greatly improved, and the color difference value of pigments after treatment at 240 ℃ for 30 min is low, owing to the surface coating layer of boehmite structure. After coating, the iron oxides yellow maintains the original acicular structure, and pigment does not aggregate. When pH is 10, the coated iron oxides yellow composed both large stick and needle like structure, possibly because of the nucleation formation of AlOOH in the reaction process. This result may explain the special endothermic peaks of 246 ℃ appeared on the DTA curves. This research might provide theoretical and practical guidance for developing heat resistant yellow iron oxide pigments.

Key words: yellow iron oxide, coating, aluminium hydroxide, heat resistance

中图分类号:

TQ174

潘国祥, 陈健, 倪哲明, 曹枫, 胡双双, 林凯, 李金花, 竺增林. 包覆型氧化铁黄颜料微结构与耐热性能研究[J]. 无机材料学报, 2016, 31(1): 75-80.

PAN Guo-Xiang, CHEN Jian, NI Zhe-Ming, CAO Feng, HU Shuang-Shuang, LIN Kai, LI Jin-Hua, ZHU Zeng-Lin. Microstucture and Heat Resistance of Coated Yellow Iron Oxide Pigment[J]. Journal of Inorganic Materials, 2016, 31(1): 75-80.

图/表 6

图1 包覆型氧化铁黄及其包覆层氢氧化铝的XRD图谱

Fig. 1 XRD patterns of coated yellow iron oxide and coating layer Aluminium hydroxides (a) Yellow iron oxide and coated pigments; (b) Coating layer Aluminium hydroxides

图2 包覆后铁黄及氢氧化铝层的红外图谱

Fig. 2 FT-IR patterns of coated yellow iron oxide and coating layer Aluminium hydroxides (a) Yellow iron oxide and coated pigments; (b) Coating layer Aluminium hydroxides

图3 包覆前后氧化铁黄颜料的SEM和TEM照片

Fig. 3 SEM(A-D) and TEM (E) images of yellow iron oxides before and after coating (a) FeOOH; (b) pH4/FeOOH; (c) pH6/FeOOH; (d) pH8/FeOOH; (e) pH8/FeOOH

图4 包覆铁黄pH10/FeOOH的SEM照片和EDS分析结果

Fig. 4 SEM image and EDS results of coated iron oxide yellow pH10/FeOOH

图5 不同pH条件下包覆铁黄的TG-DTA曲线

Fig. 5 TG(A)-DTA(B) curves of coated yellow iron oxides synthesized with different pH

表1 耐热测试前后铁黄样品的实物照片和色差数据

Table 1 Photoes with color difference of iron oxides yellow samples before and after heat treatment

参考文献 24

[1]	SHEYDAEI M, ABER S, KHATAEE A.Preparation of a novel gamma-FeOOH-GAC nano composite for decolorization of textile wastewater by photo fenton-like process in a continuous reactor.Journal of Molecular Catalysis A: Chemical, 2014, 392: 229-234.
[2]	LIU T Q, SONG L N.Preparation and properties of FeOOH-gelatin complex nano-particles.Acta Chimica Sinica, 2010, 68(11): 1057-1062.
[3]	PENG Y K, TSENG Y J, LIU C L, et al.One-step synthesis of degradable T-1-FeOOH functionalized hollow mesoporous silica nanocomposites from mesoporous silica spheres.Nanoscale, 2015, 7(6): 2676-2687.
[4]	CHEN R F, DENG J, SONG G Q, et al.Synthesis of different crystalline γ-FeOOH and their liquid phase transformation.Acta Chimica Sinica, 2008, 66(21): 2348-2352.
[5]	WANG X J, JIANG X H, GUO X Y, et al.Preparation and characterization of β-FeOOH nanowires.Acta Chimica Sinica, 2005, 63(11): 1033-1036.
[6]	MENG Z, JIA Z B, WEI Y.Research on the mechanism of the formation of nanoparticle of α-Fe2O3 powder in aqueous solution with amorphous δ-FeOOH.Acta Chimica Sinica, 2004, 62(5): 485-488.
[7]	XU J G, LI Y Q, YUAN B L, et al.Synthesis and characterization of 3D flower-like α-FeOOH nanostructures.Chemical Journal of Chinese Universities, 2015, 36(1): 48-54.
[8]	REN L R, YAN L, WANG Y, et al.Influence of Mn-dopant on the structure and morphology of α-FeOOH nanorods.Chinese Journal of Inorganic Chemistry, 2012, 28(6): 1111-1116.
[9]	DONG Y M, JIANG P P, ZHANG A M.Catalytic ozonation degradation of phenol in water by mesoporous α-FeOOH.Chinese Journal of Inorganic Chemistry, 2009, 25(9): 1595-1600.
[10]	YU H Y, CHEN G Z, SUN S X, et al.Preparation of α-Fe2O3 hollow spheres via random aggregation of β-FeOOH nanorods.Chinese Journal of Inorganic Chemistry, 2007, 23(12): 2115-2118.
[11]	NIE Y L, HU C, LI N N, et al.Inhibition of bromate formation by surface reduction in catalytic ozonation of organic pollutants over beta-FeOOH/Al2O3.Applied Catalysis B: Environmental, 2014, 147: 287-292.
[12]	LEE S, CHEON J Y, LEE W J, et al.Production of novel FeOOH/reduced graphene oxide hybrids and their performance as oxygen reduction reaction catalysts.Carbon, 2014, 80: 127-134.
[13]	ZHANG Y X, HAO X D, DIAO Z P, et al.One-pot controllable synthesis of flower-like CoFe2O4/FeOOH nanocomposites for high-performance supercapacitors.Materials Letters, 2014, 123: 229-234.
[14]	ZHU Y H, LI C Z, HU L M.Study on the interface of SiO2/α- FeOOH and SiO2/α-Fe2O3 fine particles.Acta Physico-Chimica Sinica, 1995, 11(9): 860-864.
[15]	LIANG K, TANG L Y, LI G H.Preparation and characterization of TiO2/α-Fe2O3 and TiO2/α-FeOOH nanocomposite.Journal of Synthetic Crystals, 2011, 40(4): 1011-1016.
[16]	SHENG O W, PAN G X, LI J H, et al.Progress of preparation technology of heat-resistant coated iron oxide yellow pigment.Chemical Industry and Engineering Progress, 2014, 33(1): 224-227.
[17]	SOICHIRO N, TAKASHI A, KAZUAKI A.Method for Improvement of Properties of Synthetic Yellow Iron Oxide. US, 3969494, 1976.07.13.
[18]	JIHEI S.Preparation of Improved Heat Stable Yellow Iron Oxide Pigments. US,4374677,1983.2.22.
[19]	JIHEI S.Heat Resistant Yellow Iron Oxide Pigment.US, 4376656, 1983.3.15.
[20]	ZHU Y H, LI C Z, LUO C Q, et al.Effect of silica coating on geothite dehydration process.Chinese Journal of Chemical Physics, 1995, 8(5): 416-423.
[21]	XUAN S F, LI Y E, CAO H M, et al.Study on surface modification of yellow iron oxide pigments with ethyl acetate as potential acid.China Powder Science and Technology, 2008, 14(4): 38-39.
[22]	潘国祥, 李金花, 沈辉, 等.一种具有阻燃功能的耐温氧化铁黄颜料及其制备方法. 中国发明专利, 103627214A, 2014.3.12.
[23]	LU J G, ZHANG J, DING W P, et al.Synthesis and characterization of boehmite AlOOH nanotubes.Chinese Journal of Inorganic Chemistry, 2007, 23(5): 899-900.
[24]	DU X L, SUN Y Z.Influence of pH value on crystal structure and microstructure of aluminum hydroxide.Journal of Zhengzhou University, 2001, 32(5): 39-44.