金属有机化学气相沉积（MOCVD）法制备云母珠光颜料新工艺及应用研究
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摘要
珠光颜料是一种用途广泛的高档颜料，有绚丽的珠光光泽和璀璨的珠光效应，主要应用于涂料、油墨、化妆品、塑料、橡胶和皮革等行业。现在的珠光颜料生产方法都是液相水解工艺，该工艺存在着水解周期长、能耗大、有大量污水排放的缺点。随着工业的发展，对颜料的性能和色彩提出了更高的要求，珠光颜料也由单包覆层向多包覆层方向发展。传统的液相包覆技术受工艺和原料的限制，对多包覆层珠光颜料的制备不能进行精确调控，难以进行新产品的开发。金属有机化学气相沉积(MOCVD)法是获得各种特殊功能材料和薄膜(如高温超导膜、半导体膜等)最有效的方法，是将某些金属有机化合物蒸汽通过处于分解温度的物体，在其表面上反应并沉积一种氧化物薄膜或金属薄膜的化学镀方法；喷动流化床可解决超细粉体的流化，达到高效传热传质，迅速完成表面反应。本研究结合这两项新技术，在喷动流化反应器中用MOCVD法制备了单包覆及双包覆珠光颜料，该新工艺和液相包覆法相比，周期短、能耗小、无三废排放，是绿色化工工艺，并为开发多包覆层珠光颜料提供了一条新的工艺路线。
本研究论文主要研究了以下几个方面：
1．研究了用Fe(CO)_5为前体物，在喷动流化反应器中对云母粉包覆铁氧化物制备铁系珠光颜料的新工艺。用X衍射、电镜扫描、电子探针、色差仪等对颜料性能进行了表征，研究了各个工艺参数对产品质量的影响，结果表明：在沉积温度250℃，氧气流量3ml·s~(-1)，沉积时间5min时能得到棕色色泽的珠光颜料，随着沉积温度的提高和反应时间的延长，可获得红棕、金红、橙红、深红等不同色泽的珠光颜料；
2．对颜料的光学特征及其微结构研究发现：粒径分布均匀的水磨云母粉适于制备云母珠光颜料；MOCVD法制备云母珠光颜料是在微米级的片状超微粉体表面沉积纳米级其折射指数比基材云母高得多的氧化物微粒，获得的包覆膜分布均匀，结构致密；
3．用Ti(OC_4H_9)_4为前体物，在反应器中不同条件下对云母粉进行包覆。结果表明：在300℃时获得的主要是锐钛型的TiO_2，500℃时获得的主要是金红石型的TiO_2，当氧气充足时获得的镀层更加均匀和致密；
4．在包覆TiO_2的基础上，再包覆一层铁氧化物，获得的双包覆珠光颜料亮度更高，色泽更加丰富，色彩柔和，耐候性比单包覆层好；
5．在对喷动流化反应器传质、传热性能研究的基础上，对该工艺中羰基铁和钛丁脂酸的沉积热力学和动力学做了初步计算；
6．按照颜料的国家标准对试制的几种珠光颜料进行了法定检验，并分别应用
于汽车涂料、塑料、化妆品、墙体涂料中，效果好。
Pearlescent pigment has characteristics of florid pearl luster and bright pearl. It can be used in dope, ink printing, decorativeness, cosmetic, rubber and leather as a addition agent. The preparation method of pearlescent pigments was based on the liquid phase technique, which had the disadvantages of long hydrolyze cycle, large energy expending and plentiful sewage letting. With industry developing, The pigments with superior performance and more colorful are needed. Furthermore, the preparation of pearlescent pigments have a trend from one-coated layer to multi-coated layer. However, the liquid phase preparation method cannot control colour changing accurately, so it was very difficulty in exploiting new products.
Metal Organic Chemical Vapour Deposition (MOCVD) technique is an effective method for acquiring special function materials and membrane including superconductor in high temperature and semiconductors. It is based on the deposition of oxide thin membranes or metal thin membranes on the substrates with the gas phase reactions. This technique is also an important method of synthesizing solid materials that have potential applications in industrial field. On the other hand, spout-fluid bed technique can fluidize super-small particulates, obtain heat transfer and mass transfer with high efficiency, and give shape to speediness surface reaction. In the present work, the MOCVD technique coupled with spout-fluid bed technique was successfully applied to preparation of one-coated and two-coated mica pearlescent pigment. The proposed method has the advantages of short reaction cycle, small energy expending and no environmental problems. It is a green chemical technique and gives a new industry route for exploiting mul
ti-coated pearl pigment.
The main points of this paper are as follows:
1. Iron oxide-mica pearlescent pigment was prepared by Fe(CO)5 in a spout-fluidized bed using MOCVD technique. The pigments' capability was measured by X-ray Debey Powder Diffraction, Scanning Electron Microscope (SEM), Electron Microprobe and Chromatism Apparatus. It is proved that
brown pearlescent pigment can be prepared at 250℃ in oxygen flow of 3 ml-s"' and deposition time of 5 minutes. At higher temperature and longer deposition time, red-brown, golden-red and orange-red pigments were investigated too.
2. The microstructure and optical properties of pigments were also investigated. The results showed that the uniform diameter watermill mica was the best material for pearl pigment. The pigment prepared by the present MOCVD method is a nanometer oxide particle which refraction index is higher than mica. A distribute equably and structure compactly thin films was obtained.
3. The MOCVD procedures with tetrabutyl titanate (Ti(OC4H9)4) carried by pure nitrogen were employed under various conditions. Anatase TiO2 was obtained at 300℃. Denser coated rutile TiO2 on mica can be prepared at 500℃. When plenty oxygen was present, more uniform and denser coat could be obtained.
4. Iron oxide film coated on TiO2 has been successfully carried out. The results showed that two-coated mica pearlescent pigment has higher luminance, more plentiful color, mellower colour and more weather resistance than one-coated pigment.
5. Based on investigation of convective heat and mass transfer of spout-fluidized bed, the thermodynamics and kinetics of Fe(CO)5 and Ti(OC4H9)4 was calculated.
6. According to standard (GB), pigments were successfully applied to car paint, plastic, cosmetic and wall paint.
本研究论文主要研究了以下几个方面：
1．研究了用Fe(CO)_5为前体物，在喷动流化反应器中对云母粉包覆铁氧化物制备铁系珠光颜料的新工艺。用X衍射、电镜扫描、电子探针、色差仪等对颜料性能进行了表征，研究了各个工艺参数对产品质量的影响，结果表明：在沉积温度250℃，氧气流量3ml·s~(-1)，沉积时间5min时能得到棕色色泽的珠光颜料，随着沉积温度的提高和反应时间的延长，可获得红棕、金红、橙红、深红等不同色泽的珠光颜料；
2．对颜料的光学特征及其微结构研究发现：粒径分布均匀的水磨云母粉适于制备云母珠光颜料；MOCVD法制备云母珠光颜料是在微米级的片状超微粉体表面沉积纳米级其折射指数比基材云母高得多的氧化物微粒，获得的包覆膜分布均匀，结构致密；
3．用Ti(OC_4H_9)_4为前体物，在反应器中不同条件下对云母粉进行包覆。结果表明：在300℃时获得的主要是锐钛型的TiO_2，500℃时获得的主要是金红石型的TiO_2，当氧气充足时获得的镀层更加均匀和致密；
4．在包覆TiO_2的基础上，再包覆一层铁氧化物，获得的双包覆珠光颜料亮度更高，色泽更加丰富，色彩柔和，耐候性比单包覆层好；
5．在对喷动流化反应器传质、传热性能研究的基础上，对该工艺中羰基铁和钛丁脂酸的沉积热力学和动力学做了初步计算；
6．按照颜料的国家标准对试制的几种珠光颜料进行了法定检验，并分别应用
于汽车涂料、塑料、化妆品、墙体涂料中，效果好。
Pearlescent pigment has characteristics of florid pearl luster and bright pearl. It can be used in dope, ink printing, decorativeness, cosmetic, rubber and leather as a addition agent. The preparation method of pearlescent pigments was based on the liquid phase technique, which had the disadvantages of long hydrolyze cycle, large energy expending and plentiful sewage letting. With industry developing, The pigments with superior performance and more colorful are needed. Furthermore, the preparation of pearlescent pigments have a trend from one-coated layer to multi-coated layer. However, the liquid phase preparation method cannot control colour changing accurately, so it was very difficulty in exploiting new products.
Metal Organic Chemical Vapour Deposition (MOCVD) technique is an effective method for acquiring special function materials and membrane including superconductor in high temperature and semiconductors. It is based on the deposition of oxide thin membranes or metal thin membranes on the substrates with the gas phase reactions. This technique is also an important method of synthesizing solid materials that have potential applications in industrial field. On the other hand, spout-fluid bed technique can fluidize super-small particulates, obtain heat transfer and mass transfer with high efficiency, and give shape to speediness surface reaction. In the present work, the MOCVD technique coupled with spout-fluid bed technique was successfully applied to preparation of one-coated and two-coated mica pearlescent pigment. The proposed method has the advantages of short reaction cycle, small energy expending and no environmental problems. It is a green chemical technique and gives a new industry route for exploiting mul
ti-coated pearl pigment.
The main points of this paper are as follows:
1. Iron oxide-mica pearlescent pigment was prepared by Fe(CO)5 in a spout-fluidized bed using MOCVD technique. The pigments' capability was measured by X-ray Debey Powder Diffraction, Scanning Electron Microscope (SEM), Electron Microprobe and Chromatism Apparatus. It is proved that
brown pearlescent pigment can be prepared at 250℃ in oxygen flow of 3 ml-s"' and deposition time of 5 minutes. At higher temperature and longer deposition time, red-brown, golden-red and orange-red pigments were investigated too.
2. The microstructure and optical properties of pigments were also investigated. The results showed that the uniform diameter watermill mica was the best material for pearl pigment. The pigment prepared by the present MOCVD method is a nanometer oxide particle which refraction index is higher than mica. A distribute equably and structure compactly thin films was obtained.
3. The MOCVD procedures with tetrabutyl titanate (Ti(OC4H9)4) carried by pure nitrogen were employed under various conditions. Anatase TiO2 was obtained at 300℃. Denser coated rutile TiO2 on mica can be prepared at 500℃. When plenty oxygen was present, more uniform and denser coat could be obtained.
4. Iron oxide film coated on TiO2 has been successfully carried out. The results showed that two-coated mica pearlescent pigment has higher luminance, more plentiful color, mellower colour and more weather resistance than one-coated pigment.
5. Based on investigation of convective heat and mass transfer of spout-fluidized bed, the thermodynamics and kinetics of Fe(CO)5 and Ti(OC4H9)4 was calculated.
6. According to standard (GB), pigments were successfully applied to car paint, plastic, cosmetic and wall paint.
引文
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[2]ESSELBORN REINER, BERNHARD HORST, Rutile-containing lustrous pigments [P]. U. S.4086100,1978-04-25
[3]BERNHARD HORST(AT),ESSELBORN REFNER(DE).Process for the preparation of nacreous pigments with improved gloss properties, products thereof, and compositions using said pigments[P]. U.S.4537636, 1985-08-27
[4]BERNHARD HORST;HESSE REINER;RUSSMANN HORST;etc. Colored pigments[P]. U.S. 3951679,1976-04-20
[5]ARMANINI LOUIS. Iron blue nacreous pigments[P]. U.S.43094801982-01-05
[6]a. BERNHARD HORST, ESSELBORN REINER. Nacreous pigments and process for the production thereof[P]. U.S.3874890,1975-04-01;b. ARMANINI LOUIS,BAGALA FRANK.Iron oxide coated mica nacreous pigments[P]. DE2723871,1979-03-27;C. BERNHARD HORST (AT).Nacreous pigments having improved light fastness, their preparation and use[P]. U.S.4509988,1985-04-09.
[7]JP50=039738, 1975-04-12
[8]BERNHARD HORST, HESSE REINER,RUSSMANN HORST, ESSELBORN REINER.IRON-CONTAINING MICA FLAKE PIGMENTS[PI. U.S.3926659,1975-12-16.
[9]a. BERNHARD HORST (AT).Yellow nacreous pigments having calcined CR oxide and phosphate layer for improved light-fastness, process and use[P]. DE3137808,1984-06-26;b. BERNHARD HORST (AT).Green nacreous pigments having calcined Cr oxide and phosphate layer, their preparation, and use[P]. DE3137809, 1984-07-03
[10]BERNHARD HORST (AT).Nacreous pigments having improved light fastness, their preparation and use[P]. DE3151343,1986-01-21
[11]a. JP01-158077;b. JP59-160571
[12]徐杨群．我国云母钛珠光颜料质量差距及改经措施[J]．涂料工业，1998(8)，17-20
[13]MEARL CORP(US),Intensely colored nacreous pigments[P].U.S.5273576, 1994-04-27
[14]MEARL CORP, Exterior grade titanium dioxide coated mica[P]. U. S.4134776, 1979-01-16
[15]MERCK PATENT GMBH,Dyed lustrous pigments[P].U.S.4084983, 1978-04-18
[16]NISSAN MOTOR CO LTD, Iron-coating nacreous pigment[P]. JP. 64-085255,1989-03-30
[17]NIEKERK JOHANNES W VAN(ZA),Twin coil apparatus and energizing structure therefor[P].DE3203017,1989-12-05
[18]DU PONT(US),Alurninum-silica-aluminum flake pigments[P].U.S.3438796, 1969-04-15
[19]OPTICAL COATING LABORATORY INC (US),Article and method for forming thin film flaked and coatings[P].U.S.4434010, 1984-02-28
[20]BASF AG (DE),Luster pigments with a metal sulfide coating[P].U.S.5401306, 1995-03-28
[21]BASF AG (DE),Mutiply coated metallic luster pigments[P].GB708154, 1997-03-04
[22]BASF AG (DE),Goniochromatic brilliant pigments based on transparent non-metallic platy substrates[P].DE.19525503, 1997-01-15
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