KR20200004969A - Vanadate-based pigment, and method of preparing the same - Google Patents

Abstract

The present invention relates to a vanadate-based pigment and a method for manufacturing the vanadate pigment. According to embodiments of the present disclosure, an environmentally friendly vanadate-based pigment can be manufactured that develops a turquoise color through a Mn^5+ ion content, change in annealing temperature, and flux addition.

Description

Vanadate pigments, and methods for preparing the same {VANADATE-BASED PIGMENT, AND METHOD OF PREPARING THE SAME}

This application relates to a vanadate pigment and a method for producing the vanadate pigment.

At present, commercially available pigments can be broadly divided into organic pigments and inorganic pigments. While organic pigments have good color development and colorability, but have poor durability, application fields are very limited, whereas inorganic pigments have excellent durability, so they can be used for a long time and have greater applicability than the organic pigments.

Typical applications for these inorganic pigments are paints, color cosmetics, printer inks and the like. Heavy metals such as Cr, Pb, Cd, etc. are required to improve the generation characteristics of the inorganic pigments, and these heavy metals are severely harmful to the environment and the human body, and thus their use is strictly restricted. In addition, since the pigment that does not contain the heavy metal contains expensive metals such as Co or Ni, there is a disadvantage that the price is not competitive, it is necessary to develop a new inorganic pigment.

Thus, an alternative has been to replace the cation at the parent tetrahedral center of the pigment with a Mn ⁵⁺ color activator. Here, the color activator means a substance directly participating in color development in the pigment. In the case of Mn ^{5 +} , when a cation at the center of the tetrahedron is replaced with Mn ^{5 +} , a blue-green color is generated depending on the parent. By doping the color activator, it is possible to solve the toxicity and high price problems due to heavy metals, which is a disadvantage of the existing blue-green pigment. According to the results of previous studies, blue-green color can be obtained when ions are replaced by Mn ^{5 +} in the mother, but the reflectance is low, the brightness is low, the addition of In is expensive, and Cl is included in the crystal structure. There was a problem that this was not good.

[Preceding technical literature]

Republic of Korea Publication No. 10-2012-0007989.

The present application is to provide a vanadate pigment and a method for producing the vanadate pigment.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application provides a vanadate pigment, represented by the following Chemical Formula 1:

[Formula 1]

Ba ₃ V _2-x Mn _x O ₈ ;

In Formula 1, 0 ≦ x ≦ 0.3.

A second aspect of the present application provides a method for producing a vanadate pigment according to the first aspect, comprising preparing a vanadate pigment represented by the following Chemical Formula 1 using a solid-state reaction method: do:

[Formula 1]

Ba ₃ V _2-x Mn _x O ₈ ;

In Chemical Formula 1, 0 ≦ x ≦ 0.3,

The solid phase method includes an oxide or carbonate of a metal selected from the group consisting of Ba, Ca, V, and combinations thereof; And mixing the oxide or carbonate of Mn in a temperature range of 100 ° C. to 1,000 ° C .; And annealing the calcined powder to obtain a vanadate pigment.

According to embodiments herein, Ba ₃ V _{2 - x} Mn _x O by using a solid-state reaction method and replacing Mn ⁵⁺ with tetrahedral central ions of the Ba ₃ V ₂ O ₈ parent _A novel vanadate pigment which has not been reported so far as ₈ can be produced.

According to the implementation of the present example it can be produced environment-friendly vanadate-based inorganic pigments that color the turquoise through Mn ^{5 +} ion content, a change in annealing temperature, and a flux (flux) was added.

1 shows an XRD pattern of Ba ₃ V _{2 - x} Mn _x O ₈ in one embodiment of the present application [x = (a) 0.02, (b) 0.04, (c) 0.06, (d) 0.08 And (e) 0.10].
2 (a) to 2 (c) show Rietveld refinement of Ba ₃ V _{2 − x} Mn _× O ₈ in one embodiment of the present application [x = (a) 0.02, (b) 0.06, and (c) 0.10].
FIG. 3 shows a unit cell of Ba ₃ V _{2 − x} Mn _× O ₈ in one embodiment of the present application [x = (a) 0.02, (b) 0.06, and (c) 0.10 ].
Figure 4, in one embodiment of the present application, shows a UV-VIS NIR spectrum of Ba ₃ V _{2 - x} Mn _x O ₈ .
5 is, in one embodiment of the present application, XRD of Ba ₃ V _{2- x} Mn _x O ₈ heat-treated at (a) 1000 ° C, (b) 1100 ° C, (c) 1200 ° C, and (d) 1300 ° C. The pattern is shown.
FIG. 6 shows, in one embodiment of the present application, UV of Ba ₃ V _{2 ×} Mn _× O ₈ heat treated at (a) 1000 ° C., (b) 1100 ° C., (c) 1200 ° C., and (d) 1300 ° C. FIG. -VIS NIR spectrum is shown.
Figure 7 (a) and (b), in one embodiment of the present application, Ba ₃ V _{2- x} prepared by adding (a) Na ₂ CO ₃ and (b) K ₂ CO ₃ flux (flux) XRD pattern of Mn _x O ₈ is shown.
FIG. 8 is a UV-VIS NIR of Ba ₃ V _{2- x} Mn _x O ₈ prepared by adding a) Na ₂ CO ₃ and (b) K ₂ CO ₃ flux in one embodiment of the present disclosure. The spectrum is shown.

DETAILED DESCRIPTION Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a part is said to be "connected" with another part, this includes not only the "directly connected" but also the "electrically connected" between other elements in between. do.

Throughout this specification, when a member is located “on” another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless otherwise stated. As used throughout this specification, the terms “about”, “substantially”, and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided, and an understanding of the present application may occur. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term “step of” or “step of” does not mean “step for”.

Throughout this specification, the term "combination (s) thereof" included in the expression of a makushi form refers to one or more mixtures or combinations selected from the group consisting of components described in the expression of makushi form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of “A and / or B” means “A or B, or A and B”.

Hereinafter, with reference to the accompanying drawings will be described embodiments and embodiments of the present application; However, the present disclosure may not be limited to these embodiments, examples, and drawings.

A first aspect of the present application provides a vanadate pigment, represented by the following Chemical Formula 1:

[Formula 1]

Ba ₃ V _{2 - x} Mn _x O ₈ ;

In Formula 1, 0 ≦ x ≦ 0.3.

In one embodiment of the present application, the vanadate pigment may have a rhombohedral crystal structure, but may not be limited thereto.

In one embodiment of the present application, the vanadate pigment may be blue, green, red, or yellow, but may not be limited thereto.

A second aspect of the present application provides a method for producing a vanadate pigment according to claim 1, comprising preparing a vanadate pigment represented by the following Chemical Formula 1 using a solid-state reaction method. do:

[Formula 1]

Ba ₃ V _{2 - x} Mn _x O ₈ ;

In Chemical Formula 1, 0 ≦ x ≦ 0.3,

The solid phase method includes an oxide or carbonate of a metal selected from the group consisting of Ba, Ca, V, and combinations thereof; And calcining the oxide or carbonate of Mn in a temperature range of 100 ° C. to 1,000 ° C .; And annealing the calcined powder to obtain a vanadate pigment according to claim 1.

With respect to the method for producing a vanadate pigment according to the second aspect of the present application, the detailed description of the overlapping parts with the first side of the present application has been omitted, even if the description is omitted, the contents described in the first aspect of the present application The same can be applied to the second aspect of.

In one embodiment of the present application, the solid phase method, the most common method of manufacturing a ceramic, by the solid phase method can easily and economically mass-produce the vanadate pigment, but may not be limited thereto.

In one embodiment of the present application, the calcination step may be performed to remove impurities such as organic matter, the calcination may be performed at a temperature range of about 100 ℃ to about 1,000 ℃, but is not limited thereto. You may not. For example, the calcining may be about 100 ° C. to about 1,000 ° C., about 100 ° C. to about 800 ° C., about 100 ° C. to about 600 ° C., about 100 ° C. to about 400 ° C., about 100 ° C. to about 200 ° C., about 200 ° C. To about 1,000 ° C, about 200 ° C to about 800 ° C, about 200 ° C to about 600 ° C, about 200 ° C to about 400 ° C, about 400 ° C to about 1,000 ° C, about 400 ° C to about 800 ° C, about 400 ° C to about 600 ° C, about 600 ° C to about 1,000 ° C, about 600 ° C to about 800 ° C, about 800 ° C to about 1,000 ° C, about 500 ° C to about 700 ° C, about 100 ° C to about 800 ° C, about 100 ° C to about 800 ° C Or, it may be performed in a temperature range of about 100 ℃ to about 800 ℃, but may not be limited thereto.

In one embodiment of the present application, the addition may be performed after the calcination, but may not be limited thereto. For example, a small amount of flux may be added after the calcining, but may not be limited thereto.

In one embodiment of the present application, the flux may be in a liquid form having a melting point lower than the annealing temperature, it may be to serve as a carrier between the reactants, but may not be limited thereto.

In one embodiment of the present application, the flux does not remain in the final product, it may be to promote crystal growth of the product.

In one embodiment of the present application, the flux may be, for example, an alkali metal, an alkaline earth metal, or a halogen compound, for example, Na ₂ CO ₃ or K ₂ CO ₃ , but may not be limited thereto. have.

In one embodiment of the present application, the heat treatment temperature may be lowered due to the flux, thereby reducing the production cost of the pigment, but may not be limited thereto.

In one embodiment of the present application, the annealing may be performed in a temperature range of about 1,000 ℃ to about 2,000 ℃, but may not be limited thereto. For example, when the annealing temperature is greater than about 2,000 ° C., the aggregation becomes severe, and when the annealing temperature is less than about 1,000 ° C., it may have a monoclinic crystal structure. Thus, the annealing may be performed at about 1,000 ° C. to about 2,000 ° C. It is preferably carried out in the temperature range.

In one embodiment of the invention, the annealing is about 1,000 ℃ to about 2,000 ℃, about 1,000 ℃ to about 1,800 ℃, about 1,000 ℃ to about 1,600 ℃, about 1,000 ℃ to about 1,400 ℃, about 1,000 ℃ to about 1,200 ℃ , About 1,200 ° C. to about 2,000 ° C., about 1,200 ° C. to about 1,800 ° C., about 1,200 ° C. to about 1,600 ° C., about 1,200 ° C. to about 1,400 ° C., about 1,400 ° C. to about 2,000 ° C., about 1,400 ° C. to about 1,800 ° C., about 1,400 ° C. to about 1,600 ° C., about 1,600 ° C. to about 2,000 ° C., about 1,600 ° C. to about 1,800 ° C., about 1,800 ° C. to about 2,000 ° C., or about 1,500 ° C. to about 1,700 ° C. It may not be limited.

In one embodiment of the present application, the annealing is a process of synthesizing ceramic crystals, the active material may enter the mother lattice through the annealing, but may not be limited thereto.

In one embodiment of the present application, the vanadate pigment may have a rhombohedral crystal structure through the annealing, but may not be limited thereto.

Hereinafter, the present invention will be described in more detail with reference to examples of the present application, but the following examples are merely illustrated to aid the understanding of the present application, and the content of the present application is not limited to the following examples.

[ Example ]

Ba ₃ V _{2 - x} Mn _x O ₈ Preparation of Pigments

In the present application, Ba ₃ V _{2 - x} Mn _x O ₈ After the composition was designed to synthesize (0.02 ≦ x ≦ 0.10) pigments, the composition was prepared by the solid phase synthesis method, and the composition, crystal structure and color development characteristics of each manufacturing process were studied. Starting materials for preparing the above pigments include barium carbonate (BaCO ₃ 99.95%, High Purity Chemical), ammonium vanadate (NH ₄ VO ₃ 99%, High Purity Chemical), and manganese dioxide (MnO ₂ 99.9% Alfa Aesar). Used. Acetone (CH ₃ COCH ₃ 99.5%, Duksan) was used as the solvent for wet mixing, and ethanol (C ₂ H ₅ OH 95%, Samchun) was used as the solvent for high-energy ball milling. It was. Sodium carbonate (Na ₂ CO ₃ 99%, High Purity Chemical) and potassium carbonate (K ₂ CO ₃ 99%, High Purity Chemical) were used as flux. To prepare the designed pigment, the powders used were weighed according to the composition, which was then placed in agate mortar with 5 mL of acetone and wet mixed for 15 minutes in a pestle at room temperature. The mixed powder was placed in an alumina crucible and calcined at 300 ° C. for 4 hours. To the calcined powder was added flux (0-9 wt% Na ₂ CO ₃ and K ₂ CO ₃ ) and acetone together in agate mortar and wet mixed for 20 minutes with a pestle. The mixed powder was annealed at 1000-1300 ° C. for 4 hours. Pigment annealed in a zirconia jar (jar), zirconia balls (diameter: 3φ, 5φ) and ethanol were added to the high energy ball milling for 30 minutes. The ground powder was dried in a 60 ° C. dryer for 24 hours to give a final Ba ₃ V _{2 - x} Mn _x O ₈ (0.02 ≦ x ≦ 0.3) A pigment was prepared.

Ba ₃ V _{2 - x} Mn _x O ₈ Pigment Analysis

Manufactured Ba₃V_{2 - x} Mn _x O₈ In order to analyze the constituent elements of the pigment and determine the valence of Mn, a transition metal, an X-ray photoelectron spectroscopy (XPS, Thermo Scientific Inc., K-alpha) analysis was performed. When the surface of the specimen absorbs X-rays, the photoelectrons are emitted, and by measuring the kinetic energy of the emitted photons, XPS can know the binding energy of the electrons. have. The related formula is as follows.

Where E _Kin is the kinetic energy of emitted photons , hv is the energy of X-rays incident on the surface of the specimen, E _B is the binding energy of electrons, and Φ is the work function.

X-ray diffractometer (X-ray Diffractometer: XRD, XPERT-PRO, Pan Analytical) was used to determine the crystal structure and crystallinity of the prepared Ba ₃ V _{2 - x} Mn _x O ₈ pigment. Voltage = 40 kV, current = 30 mA, target = Cu Kα ₁ , Scanning range (2θ) = 10-70 °, step size = 0.02626 °, scan rate = 50 s / step. The crystal size (D) was calculated using the XRD results and the Scherrer's equation. The Scherrer's equation is shown below.

), θ는 회절각, B는 2θ에서의 반치폭 (FWHM: full width at the half-maximum)이다.Where λ is Cu Kα ₁ X-ray wavelength due to radiation (1.540598

is the diffraction angle, B is the full width at the half-maximum (FWHM) at 2θ.

Rietveld analysis was performed to find information on the space group, atomic position, interatomic distance, thermal factors, etc. and XRD (X-ray Diffractometer: XPERT-PRO, Pan Analytical) was used. Voltage = 45 kV, current = 40 mA, target = Cu Kα ₁ , Scanning range (2θ) = 10-100 °, step size = 0.02626 °, scanning speed = 500s / step was measured under the analysis using the Fullprof program.

UV-VIS-NIR spectrometer (Cary 5000, Agilent) was used to measure the reflectance of the prepared Ba ₃ V _{2 - x} Mn _x O ₈ pigment. The wavelength range was set to 200-2500 nm, R928 PMT was used as a detector in the UV-VIS region, and cooling PbS was used as a detector in the NIR region.

Color development of the prepared Ba ₃ V _{2 - x} Mn _x O ₈ pigment was measured using a colorimeter (JCS-10, CHN Spec). Here, the LED lamp was used as a light source, and the angle between the sample and the incident light was measured at 90 °.

1-1. Ba ₃ V _{2 - x} Mn _x O ₈ (0.02≤ x ≤0.10) crystal structure of pigment

m 공간군을 가지고 있었고, 단일상을 형성하였다. Ba₃V_{2 - x} Mn _x O₈ (0.02≤x≤0.10) 안료의 주 피크 (0 1 5), (1 1 0), 및 (2 0 5)와 Scherrer 방정식을 이용하여 결정 크기를 산출한 결과, Mn의 함량이 0.02, 0.04, 0.06, 0.08, 및, 0.10 mol일 때, 그 크기는 각각 51.1, 53.9, 55.9, 59.6, 및 62.9 nm이었다. 이 결과는 Mn의 함량이 증가함에 따라 결정 크기가 증가하는 것을 나타낸다.Ba ₃ V _{2 - x} Mn _x O ₈ prepared in FIG. XRD results of the (0.02 ≦ x ≦ 0.10) pigment are shown. Prepared Ba ₃ V _{2 - x} Mn _x O ₈ The XRD diffraction peak of the (0.02 ≦ x ≦ 0.10) pigment was found in JCPDS No. of Ba ₃ V ₂ O ₈ . 29-0211, all pigments have rhombohedral crystal structure and R

It had m space groups and formed a single phase. Ba ₃ V _{2 - x} Mn _x O ₈ The crystal size was calculated using the main peaks (0 1 5), (1 1 0), and (2 0 5) of the (0.02≤ x ≤0.10) pigment and the Scherrer equation, and the Mn content was 0.02, 0.04, At 0.06, 0.08, and 0.10 mol, the sizes were 51.1, 53.9, 55.9, 59.6, and 62.9 nm, respectively. This result shows that the crystal size increases with increasing content of Mn.

1-2. Ba ₃ V _{2 - x} Mn _x O ₈ (0.02≤ x ≤0.10) of pigment Rietveld  analysis

Ba ₃ V _{1 . 98} Mn _{0 . 02} O ₈ , Ba ₃ V _{1 . 94} Mn _{0 . 06} O ₈ , and Ba ₃ V _{1 . 90} Mn _{0 . In} order to analyze the crystal structure and structural properties of ₁₀ O ₈ pigment, JCPDS card No. Rietveld analysis was performed with reference to 29-0211. Rietveld analysis results obtained in FIG. 2 are shown, Ba ₃ V _{1 . 98} Mn _{0 . 02} O ₈ , Ba ₃ V _1.94 Mn _0.06 O ₈ , and Ba ₃ V _{1 . 90} Mn _{0 .} The crystal structure, space group, lattice constant, and confidence index of the ₁₀ O ₈ pigment are shown in Table 1. The R _wp value of all the analyzed pigments is less than 12%, and this analysis result has great reliability. Based on these Rietveld analysis results, Ba ₃ V _1.98 Mn _0.02 O ₈ , Ba ₃ V _{1 . 94} Mn _{0 . 06} O ₈ , and Ba ₃ V _{1 . 90} Mn _{0 .} The unit cell of the ₁₀ 0 ₈ pigment is shown in FIG. 3.

1-3. UV- VIS - NIR  Spectroscopic analysis

Ba ₃ V _{2 - x} Mn _x O ₈ prepared in FIG. The UV-VIS-NIR spectrum of the (0.02 ≦ x ≦ 0.10) pigment is shown. When the content of Mn was 0.02 mol, the pigment was pale yellow. When the Mn content is more than 0.06 mol, it can be seen that as the Mn content is increased, both the reflection peak at the wavelength of ˜529 nm and the reflectance of the ³ A ₂ → ³ T ₁ ( ³ F) absorption band decrease. When Mn is doped, the brightness decreases due to the decrease in reflectance of the reflection peak at ~ 529 nm as the amount of Mn doping increases, and dark green due to the decrease in reflectance of the ³ A ₂ → ³ T ₁ ( ³ F) absorption band. Showed.

1-4. Color analysis

The color development of the pigment is due to the interrelationship between the pigment and the visible light energy. Light is a type of electromagnetic wave, and its properties vary depending on the wavelength. Visible light with a 400-800 nm wavelength visible to the naked eye is blue and short in short wavelengths, and red and long in short wavelengths. When studying color, color could not be quantified by color name, which made it difficult to express color. Therefore, the study quantified the color and established the color parameter by the Commission for International Lighting (CIE) and recommended to use it. The CIE color systems L ^* , a ^* , and b ^* allow you to express colors objectively. L ^* is brightness, where 100 means white and 0 means black. a ^* denotes red or green, and redness increases as the value of a ^* increases to a positive value, and greenness increases as a value increases to a negative value. b ^* represents yellow or blue and b ^* increases to a positive value and yellowness increases, and to a negative value increases blueness.

Table 2 shows the prepared Ba ₃ V _{2 - x} Mn _x O ₈ The CIE colorimetric results of the (0.02 ≦ x ≦ 0.10) pigments are shown. As expected, the L ^* value decreases as the amount of Mn doping increases, which is in good agreement with the decrease in reflectance of the reflection peak at 307-687 nm in FIG. As the Mn doping amount increases due to the reduced reflectivity of the absorption band due to the ^{_{3 A 2 → 3 T 1 (}} 3 F) transition of Mn ^{+ 5} can be seen that a ^* value decreases.

2. various Annealing  Manufactured at temperature Ba ₃ V _{One . 90} Mn _{0 . 10} O ₈ Pigment

2-1. Crystal structure

m 공간군을 가지며, 단일상을 형성하였다. 주 피크 (0 1 5), (1 1 0), 및 (2 0 5)와 Scherrer 방정식을 사용하여 결정 크기를 계산하였으며, 1000, 1100, 1200, 및 1300℃의 어닐링 온도에서 제조한 안료의 결정 크기는 각각 61.0, 62.3, 62.9, 및 64.3 nm이었으며, 상기 어닐링 온도가 증가함에 따라 결정 크기가 증가함을 알 수 있다.In Figure 5, Ba ₃ V ₁ prepared at various annealing temperatures _{. 90} Mn _{0 . 10} O ₈ The XRD results of the pigments are shown. All pigments have a rhombohedral crystal structure and R

m group of spaces, forming a single phase. Crystal sizes were calculated using the main peaks (0 1 5), (1 1 0), and (2 0 5) and the Scherrer equation, and crystals of pigments prepared at annealing temperatures of 1000, 1100, 1200, and 1300 ° C. The sizes were 61.0, 62.3, 62.9, and 64.3 nm, respectively, and it can be seen that the crystal size increases as the annealing temperature increases.

2-2. UV- VIS - NIR  Spectroscopic analysis

6 shows Ba ₃ V ₁ prepared at various annealing temperatures _{. 90} Mn _{0 . 10} O ₈ The UV-VIS-NIR spectrum of the pigment is shown. In the same way as described above the absorption peak at 251 and ~ 308 nm wavelength by the Mn ⁺ and ^5, the absorption band at ~ 687 nm wavelength. As the annealing temperature increases, the reflectance of the reflection peak at the wavelength of 308-687 nm decreases, thereby decreasing the brightness. Annealing at 1000 ℃ Ba ₃ V _{1. 90} Mn _{0 . 10} O ₈ The reflectance of the absorption band due to the ³ A ₂ → ³ T ₁ ( ³ F) transition of the pigment was higher than that of the pigment annealed at other temperatures, which is incomplete due to the low annealing temperature, resulting in incomplete oxidation of Mn in the doped MnO ₂ . I think because the content of Mn ^{5 +} wrote.

2-3. Color analysis

Table 3 shows Ba ₃ V ₁ prepared at various annealing temperatures _{. 90} Mn _{0 . 10} O ₈ The CIE color system results of the pigments are shown. As the annealing temperature increased, the L ^* value decreased, which is believed to be due to the decrease in reflectivity as mentioned in FIG. It can be seen that the a ^* value gradually decreases as the annealing temperature increases, which is due to the decrease in reflectance of the absorption band due to the transition ³ A ₂ → ³ T ₁ ( ³ F) as mentioned in FIG. 6. .

3. Na ₂ CO ₃  And K ₂ CO ₃ Ablation  Manufactured by addition Ba ₃ V _{One . 90} Mn _{0 . 10} O ₈ Pigment

3-1. Crystal structure

Ba ₃ V ₁ prepared by adding Na ₂ CO ₃ and K ₂ CO ₃ flux by 0-9 wt% _{. 90} Mn _{0 .} XRD results of the ₁₀ O ₈ pigment are shown in FIGS. 7A and 7B, respectively. Ba ₃ V ₁ prepared by adding Na ₂ CO ₃ flux by 0-3 wt% _{. 90} Mn _{0 . The 10} O ₈ pigment formed a single phase and has a rhombohedral crystal structure. However, Ba ₃ V _1. Prepared by adding 6-9 wt% of Na ₂ CO ₃ flux _{. 90} Mn _{0 . The 10} O ₈ pigment contains a small amount of the second phase which has not been identified. In FIG. 7A, the second phase is indicated by “”. All Ba ₃ V ₁ prepared by adding K ₂ CO ₃ flux _{. 90} Mn _{0 . The 10} O ₈ pigment has a rhombohedral crystal structure and can be seen that the intensity of the (0 1 8) peak increases as the content of the K ₂ CO ₃ flux increases, which selectively (0 1 8) plane It means to grow. Ba ₃ V ₁ prepared by adding K ₂ CO ₃ flux by 0-3 wt% _{. 90} Mn _{0 . The 10} O ₈ pigment formed a single phase, but was prepared by adding 6-9 wt% Ba ₃ V _{1 . 90} Mn _{0 . The 10} O ₈ pigment contains a small amount of the second phase which has not been identified. In FIG. 7B, the second phase is indicated by “”.

Ba ₃ V ₁ prepared by adding two kinds of fluxes using the Scherrer equation and (0 1 5), (1 1 0), and (2 0 5) peaks _{. 90} Mn _{0 .} The crystal size of the ₁₀ 0 ₈ pigment was calculated. Na ₂ CO ₃ Ba ₃ V ₁ when the addition amounts of flux are 0, 3, 6, and 9 wt% _{. 90} Mn _{0 .} The crystal sizes of the ₁₀ O ₈ pigments were 64.3, 66.1, 69.6, and 70.1 nm, respectively, and K ₂ CO ₃ The crystal sizes of Ba ₃ V _1.90 Mn _0.10 O ₈ pigments with addition amounts of flux 0, 3, 6, and 9 wt% are 64.3, 65.4, 66.2, and 66.8 nm, respectively. This result shows that the crystal size increases as the amount of flux added increases.

3-2. UV- VIS - NIR  Spectroscopic analysis

(A) and (b) of FIG. 8, Na ₂ CO ₃ and K ₂ CO ₃ Ba ₃ V ₁ prepared by adding flux _{. 90} Mn _{0 .} The UV-VIS-NIR spectra of the ₁₀ 0 ₈ pigments are shown respectively. In Ba ₃ V _1.90 Mn _0.10 O ₈ pigments prepared by the addition of two fluxes, ³ A ₂ → ³ T ₁ ( ³ P) transitions of LMCT and Mn ^{5 +} at 250 and 316 nm, respectively, as mentioned above The absorption peak by can be seen and the absorption band by the ³ A _2- > ³ T ₁ ( ³ F) transition of Mn ⁵⁺ at ˜687 nm. In addition, Ba ₃ V ₁ prepared without addition of flux _{. 90} Mn _{0 . The} peak peak of the reflection peak (~ 491 nm) of ₁₀ O ₈ pigment was Ba ₃ V _{1 . 90} Mn _{0 .} It is located in the longer wavelength direction than the ₁₀ O ₈ pigment. It is considered that sikyeotgi, flux is increased the size of the crystal piece Mn ^{5 +} as mentioned above.

Ba ₃ V ₁ prepared by adding Na ₂ CO ₃ flux _{. 90} Mn _{0 . 10} O ₈ Although the reflectance of the pigment due to the transition of ³ A ₂ → ³ T ₁ ( ³ F) of Mn ⁵⁺ did not change significantly, the reflectance of the reflection peak at the wavelength of 316-687 nm decreased and the brightness decreased. It is showing a dark green color.

Ba ₃ V ₁ prepared by adding K ₂ CO ₃ flux _{. 90} Mn _{0 . 10} O ₈ pigments are the more the added amount of flux increased with increasing the reflectance of the absorption band due to the ^{_{3 A 2 → 3 T 1 (}} 3 F) transition. Especially K ₂ CO ₃ When the flux content is high (6-9 wt%), the pigments produced have a much higher reflectance of the reflection peak at 400-550 nm than the pigments produced without the addition of flux, and are located in the short wavelength direction so that they are bright blue-green and The blue color shows a large blue-green color.

Infrared radiation reflectances were 67.9, 46.8, 43.8, and 40.1%, respectively, when Na ₂ CO ₃ was added at 0, 3, 6, and 9 wt%, resulting in decreased solar reflectance with increasing flux content. Means. When the amounts of K ₂ CO ₃ added were 0, 3, 6, and 9 wt%, infrared radiation reflectances were 67.9, 43.4, 65.6, and 63.3%, respectively, and K ₂ CO ₃ It can be seen that the infrared radiation reflectance decreases when the flux is added.

3-3. Color analysis

Table 4 and Table 5 show Na ₂ CO ₃ and K ₂ CO ₃ Ba ₃ V ₁ prepared by adding flux _{. 90} Mn _{0 .} The CIE colorimetric results of the ₁₀ 0 ₈ pigments are shown, respectively. The change in L ^* value of all Ba ₃ V _1.90 Mn _0.10 O ₈ pigments prepared using both fluxes exhibited the same behavior as the change in reflectance at the wavelength of 316-687 nm described above. Ba ₃ V ₁ prepared by adding Na ₂ CO ₃ flux _{. 90} Mn _{0 . For 10} 0 ₈ pigments, the a ^* value increased as the flux content increased due to a decrease in reflectance of the reflection peak at 316-687 nm. Ba ₃ V _{1 with} an amount of K ₂ CO ₃ flux added above 6 wt% _{. 90} Mn _{0 . The 10 * 8} pigment had a smaller b ^* value because the reflectance of the reflection peak at 400-550 nm was larger than the pigment prepared without the addition of flux.

In the present embodiment, after discovering a Ba ₃ V ₂ O ₈ matrix that forms a turquoise color by substituting Mn ^{5 +} for tetrahedral center ions, the content of Mn and the annealing temperature doped to the tetrahedral center of the parent and The effects of addition of Na ₂ CO ₃ and K ₂ CO ₃ flux on the crystal structure and color development of pigments were studied.

Furthermore, Ba ₃ V _{2 - x} Mn _x O ₈ In the case of pigments, when the Mn content is more than 0.04 mol, both the reflection peak at the wavelength of ~ 529 nm and the reflectances of the ³ A ₂ → ³ T ₁ ( ³ F) absorption bands of Mn ^{5 +} ions decrease, resulting in lower brightness. Looked dark green. Among the pigments prepared at various annealing temperatures, the pigments annealed at 1300 ° C. had the lowest reflectance of the absorption band due to the transition of ³ A ₂ → ³ T ₁ ( ³ F) of Mn ^{5 +} ions and showed a dark green color (a ^* = -31.34). Ba ₃ V ₁ prepared by adding Na ₂ CO ₃ flux _{. 90} Mn _{0 . 10} O ₈ The pigments decreased in brightness and became pale green with increasing flux, whereas K ₂ CO ₃ Ba ₃ V ₁ prepared by adding flux _{. 90} Mn _{0 . 10} O ₈ The pigments increased in brightness and appeared dark turquoise as the amount of flux increased from 3 wt% to 9 wt%.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application.

Claims (5)

Vanadate pigments represented by the following general formula (1):
[Formula 1]
Ba ₃ V _{2 - x} Mn _x O ₈ ;
In Chemical Formula 1,
0≤x≤0.3
The method of claim 1,
The vanadate pigment is a vanadate pigment having a rhombohedral crystal structure.
The method of claim 1,
The vanadate pigment is a vanadate pigment, which represents blue, green, red, or yellow.
A method for producing a vanadate pigment according to claim 1, comprising preparing a vanadate pigment represented by the following Chemical Formula 1 using a solid-state reaction method:
[Formula 1]
Ba ₃ V _{2 - x} Mn _x O ₈ ;
In Chemical Formula 1,
0≤x≤0.3,
The solid state method,
Oxides or carbonates of metals selected from the group consisting of Ba, Ca, V, and combinations thereof; And mixing the oxide or carbonate of Mn in a temperature range of 100 ° C. to 1,000 ° C .; And
Annealing the calcined powder to obtain a vanadate pigment,
A method for producing a vanadate pigment according to claim 1.
The method of claim 4, wherein
The annealing is carried out in a temperature range of 1,000 ℃ to 2,000 ℃, the method of producing a vanadate pigment according to claim 1.

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