Microsoft Word - CET--006.docx CHEMICAL ENGINEERING TRANSACTIONS VOL. 59, 2017 A publication of The Italian Association of Chemical Engineering Online at www.aidic.it/cet Guest Editors: Zhuo Yang, Junjie Ba, Jing Pan Copyright © 2017, AIDIC Servizi S.r.l. ISBN 978-88-95608- 49-5; ISSN 2283-9216 Synthesis and Characterization of Red, Green and Blue Pigments for High Temperature Resistant Yamin Ma Pingdingshan University, Pingdingshan, Henan 467000, China mayami_pdsu@126.com Pigment is a kind of very important chemical raw material, non-toxic, stability of the pigment is a problem to be solved. This paper studied the synthesis and properties of red green and blue light non-toxic heat-resistant paint.In this paper we selected three systems were drilled blue (CoAl2O4) pigment, half red sulfide decorated r- Ce2S3 and green ZnO-CoO pigment, these three kinds of high temperature resistant pigments can be used not only in the color fluorescent powder coloring, and all of them have very wide application fields for example, the potential applications are printing ink, rubber, ceramics, glass, art and other fields. At present, our country uses the upscale high temperature resistant pigment, for example uses in the phosphor powder screen uses the high temperature blue color pigment blue, basically depends on the import. We hope to be able to produce better quality and lower cost of blue pigment to replace imported products to achieve the localization of the production of the pigment, thereby further reducing economic costs and improve economic efficiency. 1. Introduction There are many types of colors can be classified into red, orange, yellow, green, green, blue, purple, gray, white, black and other colors. They are not isolated, there exists a certain relationship between all kinds of color, a color can be made by three parameters, namely the hue, saturation and brightness. Microwave heating usually transforms the electromagnetic energy into heat energy by microwave dielectric effect (Ruan et al., 2004). Due to the fact that the dielectric materials are composed of polar molecules and nonpolar molecules, these polar molecules are shifted from the original random state to the polar orientation of the electric field under the action of electromagnetic field (Liu et al., 2016; Tong et al., 2016). Color hue is the difference between the characteristics, tone object determines the light spectral composition and surface reflection (or transmission) radiation at different wavelength ratio of human feeling, color reflects the relationship between color in terms of quality. Under the action of high frequency electromagnetic field, these orientations change according to the change of alternating electromagnetic field. At this time, the electromagnetic field energy can be transformed into the heat energy of the medium, so that the temperature of the medium is increased, which is the basic principle of microwave heating (Ma et al., 2013). The big red pigment γ-Ce2S3 brightness is not enough, is also the pigment L* value is not high enough, in the hope that the other performance of the same or increase the brightness of the pigment is approximately equal to the situation, make it more popular (Fouda et al., 2012). According to reports, the pigment in the air temperature resistance of only 350 °C, this study hopes to further improve the thermal stability of the pigment in the air, broaden the scope of application of the pigment (wang et al., 2012). Green high temperature pigment ZnO-CoO synthesis, hope to use different methods to synthesize the green pigment. The synthetic pigment is more green and brighter than the ordinary synthetic pigment, which makes the color of the pigment more vivid and more popular (Maat, 2016; Xu et al., 2013; Sakhmetova et al., 2016). Blue pigment blue high temperature drilling development the first problem to be solved is to develop drilling blue pigment synthesis method, a simple and only in this way, it is possible to achieve the industrial production of the pigment in the case of low cost (Fouad et al., 2012). The second is to solve the problem that the pigment raw material cost, and the cost of raw material is mainly caused by drilling, and drilling elements are widely believed to have certain harm to the environment, so how to reduce the pigment content in drilling elements into second problems to be solved. Once again, it is necessary to solve the problem of optical DOI: 10.3303/CET1759026 Please cite this article as: Yamin Ma, 2017, Synthesis and characterization of red,green and blue pigments for high temperature resistant, Chemical Engineering Transactions, 59, 151-156 DOI:10.3303/CET1759026 151 properties, particle size and distribution of the pigment, and hope to be more excellent than the optical properties of the blue pigment imported from abroad (Huang et al, 2014; Giustetto et al, 2012; Liventsova et al, 2016). 2. Effect of boric acid on the synthesis of γ-Ce2S3 red pigment 2.1 Experimental process Experimental reagent: Ce(SO4)2, CS2, H3BO3, Na2CO3 Experimental procedure: 1) Accurately called Ce(SO4)2, Na2CO3 and boric acid. Mixing and grinding evenly in agate bowl. Specific formulas are listed in Table 1. 2) The raw material mixture into the porcelain boat, placed in a closed tube furnace. 3) Nitrogen into the reaction system of furnace tube out of the air, and then began to rise. 4) Warm up to 380 °C, convert N2 atmosphere to N2 +CS2 atmosphere until the reaction is over. Which Vcs2/VN2 is 0.1, the flow rate of 0.18 L/min, heating rate of 1.2 °C/min, heating up to 900 °C insulation 3h. Cool to room temperature. 5) After grinding, washing, filtering and drying, the product is A1 to A8. Table 1. Component of mixture No. A1 A2 A3 A4 A5 A6 A7 A8 Ce(SO4)2/g 6.58 6.58 6.58 6.58 6.58 6.58 6.58 6.58 Na2CO3/g 0.112 0.112 0.112 0.112 0.112 0.112 0.112 0.112 H3BO3/g 0 0.11 0.21 0.31 0.41 0.51 0.61 0.71 2.2 Results and discussion Using METTLER TOLEDOTG TGA thermal gravimetric and differential determination of reactant and product scanning calorimetry TG-DSC curve; by Rigaku D/max2500 X ray diffraction analyses were conducted on samples of phase and structure, test conditions: 20°<2θ<80°, CuKa radiation, pressure is 40kV, the current is 30mA; the size and morphology of Sirion type field scanning electron microscopy observation of particles, the voltage is 20kV; with South Korea DARSAPRO 5000 PSI reflectance measuring the reflectivity of the sample and color coordinates, determination wavelength is 380~780mm. It can be seen from figure 1 that when the addition of boric acid is zero, there is a certain α-Ce2S3. When the addition of 0.1 g of boric acid, the α-Ce2S3 in the sample disappeared, which was γ-Ce2S3. It can be seen that boric acid and sodium carbonate can reduce the synthesis temperature of γ-Ce2S3. When the amount of boric acid was increased to 0.4 g, a new phase CeBO3 was formed, and finally, when the amount of boric acid was added to, it was not only CeBO3, but also a new substance B2S3. Figure 1: XRD patterns of samples 152 The samples of SEM images that changes with the addition of boric acid, the particle size of the sample size and morphology are essentially the same, showing irregular shaped or spherical structure, but with uniform particle size distribution, distribution range is about 0.5~2μm, the average particle size is about 1μm 3. Synthesis and characterization of green high temperature pigment CoOZnO − 3.1 Experimental process Based on the green pigment Znl-xCoxO formula, the precursor was prepared by co precipitation method, and the pigment was prepared by resistance heating and microwave heating. This paper mainly discusses the influence of the precipitating agent and heating method on the Znl-xCoxO, the reflection properties and the color coordinates of Znl-xCoxO. Under the condition of 25 °C in NaOH, NH3H2O and C2H2O4 the mixed precipitant solution is slowly added into Co(NO3)6H2O and Zn(NO3)6H2O, NaOH and NH3H2O titration end point pH value of 8 to 8.5 HZeZo; titration end point pH value is 6, the precipitation in the vacuum filter. The filtrate drops of NaOH solution with 2mol/L, no precipitate, Co2+ ten and Zn2+ have been precipitated completely. The resulting precipitate was dried for 2 hours under the condition of 110 DEG C, and the precursor of the sample was obtained after the precipitation was completely dried. The precursor after grinding in a high-temperature furnace in 110 °C calcined at 1.5 hours, the samples obtained were recorded as A1~A6. The oxalic acid as precipitant samples were divided into two, one in a high-temperature furnace at the temperature of 1100 °C to 1.5 hours, another by microwave heating to 1100 °C, heat for 10 minutes, the samples were designated as B1~B6, as shown in table 2. Table 2. Experiment design Sample number x/mol%CoO Precipitating agent Heating mode A1 0.09 NaOH Traditional heating A2 0.04 NaOH Traditional heating A3 0.18 NaOH Traditional heating A4 0.09 NH3H2O Traditional heating A5 0.04 NH3H2O Traditional heating A6 0.02 NH3H2O Traditional heating B1 0.12 H2C2O2 Traditional heating B2 0.04 H2C2O2 Traditional heating B3 0.01 H2C2O2 Traditional heating B4 0.09 H2C2O2 Traditional heating B5 0.04 H2C2O2 Traditional heating B6 0.18 H2C2O2 Traditional heating 3.2 Results and discussion It can be seen from figure 2, along with the increase of Co2+ concentration, the diffraction peak position than pure ZnO to small angle Co2+ is only visible to the ZnO solid solution in the lattice, and the crystal lattice increases, but does not change the basic structure. The pigment completely keeps the basic configuration of ZnO crystal. According to the reflectance spectra of the samples (Fig. 2), we can clearly see that with the increase of Co2+ concentration, the reflectance of green light and the red reflectance of 600 nm at the green 515 nm are gradually decreased. The sample L has the highest reflectivity at 515 nm, which is up to 51.32%, but the red reflectivity of the sample is too high and the color purity is only about 2.21, which is the lowest in the sample. The sample K has a high reflectivity at 44.12% 515 nm, but the color purity of the sample is not high, only about 2.61. However, the L*a*b value of the sample was 60, -32 and 8, the brightness of L' was about 55.21, and the a' value was a little brighter and more green than that of -32.54. The sample J is the most green in all samples, the a* value is 33.1, and the pigment has good color purity and brightness. Using oxalic acid as precipitant for the synthesis of pigment brightness and color purity is obviously better than sodium hydroxide and ammonia as precipitant of synthesized samples, so the oxalic acid is the best precipitant for preparing the pigment precursor. Compared with the traditional heating method, the microwave synthesis can obviously make the pigment brighter and greener. 153 (a) NaOH (b) H2C2O2 Figure 2: Preparation of sample reflectance spectra 4. Synthesis and characterization of blue pigment blue 4.1 Experimental process How to reduce the content of the elements in the pigment to make the pigment more economical and environmentally friendly become a trend in the development of blue pigment. However, for the requirements of application in reducing drilling elements must also improve the optical properties of pigment and color purity. Therefore, we hope to be able to prepare a composite reflective excellent blue pigment content of lower drill drill. Co (NO3)2▪(6H2O), Al2 (SO4)3▪18H2O and MgSO4▪7H2O, citric acid was added to the quality of the mixture of 4%, the use of anhydrous ethanol as grinding aids, mixing in the agate bowl grinding. The resulting mixture was dried at 115 °C for 1 hours, until completely dry samples after a high-temperature furnace 850 degrees burn 10 to 15 minutes, and then heated to 1100 DEG C to 100 minutes. The obtained products were obtained by grinding, washing, filtering and drying. The spinel blue powder was recorded as CA. In addition, the mixture of 1o50oC, 1o00oC and 950oC respectively under the condition of microwave radiation to 10 minutes, the heating time were 80 minutes, 72 minutes and 60 minutes, the microwave power is 200~1000W (with silicon carbide as microwave absorbent, alumina insulation materials), the samples were recorded as CB. 4.2 Results and discussion The mixture has 3 distinct stages of weightlessness. From 10 °C to 250 °C, weight loss of about 40%, which is the main part of the mixture decomposition loss of crystal water and citric acid and nitrate; From 250 °C to 700 °C is lost Al2 (SO4)3▪18H2O in another part of the water of crystallization and decomposition of citric acid. 154 It is the decomposition of Al2 (SO4) 3 from 700 °C to 820 °C. After 820 °C, there is almost no change in quality for the formation of blue diamond. Figure 3 showed that: 10 °C~250 °C for endothermic periods of intense, the only stage of citric acid combustion is an exothermic process, other reactions such as decomposition of the mixture and a part of crystal water nitrate is an endothermic process, because the quantity of citric acid is less, so the main performance for endothermic process. The stage of decomposition of aluminum, which is also endothermic process. After 820 °C, a stable exothermic peak appears in the process of the formation of the crystal and the phase transformation of the crystal. (a) TG_DTA curves of sample CA-2 (b) XRD patterns of cobalt blue powders of series samples Figure 3: TG_DTA curves of sample CA-2; XRD patterns of cobalt blue powders of series samples 5. Conclusion This article mainly introduces the contents of the following 3 parts: effect of boric acid on the synthesis of γ- Ce2S3 red pigment and synthesis and characterization of green high temperature pigment as well as synthesis and characterization of blue pigment blue.The red pigment γ-Ce2S3 was synthesized by high temperature solid state reduction method with anhydrous sulfuric acid, sodium carbonate and boric acid as main raw materials in 800 °C CS2+N2 atmosphere.With different precipitants, using a series of green pigment Znl-xCoxO was synthesized by co precipitation method, which using oxalic acid as precipitant, the sample obtained by the color purity of the best, and the pigment particles are distributed evenly, the average particle size is about 20μm. 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