阅读说明：本技术 掺有Cr和Co的硅酸锆基色料及其制备方法 (Zirconium silicate-based colorant doped with Cr and Co and method for preparing same ) 是由 李鹏 杨秋红 张少伯 于 2020-06-03 设计创作，主要内容包括：本申请涉及无机材料领域,公开了掺有Cr和Co的硅酸锆基色料及其制备方法,所述硅酸锆基色料的化学通式为：(Cr<Sub>2x</Sub>,Co<Sub>x</Sub>)-Zr<Sub>(1-3x)</Sub>SiO<Sub>4</Sub>,其中x为原子摩尔分数,x＝0.01～0.04；所述方法包括如下步骤：S1将ZrO<Sub>2</Sub>,SiO<Sub>2</Sub>,Cr<Sub>2</Sub>O<Sub>3</Sub>,Co<Sub>2</Sub>O<Sub>3</Sub>按照化学通式进行称量；S2将上述步骤S1中的原料加入Li<Sub>2</Sub>CO<Sub>3</Sub>后充分混合均匀,混合物放在去离子水中湿法球磨；S3将上述步骤S2中球磨后的混合物放在烘箱中烘干；S4将上述步骤S3中烘干后的粉料充分研磨均匀；S5将S4研磨均匀后的粉料放入马弗炉煅烧制得(Cr,Co)-ZrSiO<Sub>4</Sub>粉料。本申请所提供的制备方法具有操作简单,能大批量工业化生产的优点,并且能够在低温980℃成功合成,样品拥有良好的色度值,有很好的应用前景。(The application relates to the field of inorganic materials, and discloses a zirconium silicate-based pigment doped with Cr and Co and a preparation method thereof, wherein the chemical general formula of the zirconium silicate-based pigment is as follows: (Cr) 2x ,Co x )‑Zr (1‑3x) SiO 4 Wherein x is an atomic mole fraction, and x is 0.01-0.04; the method comprises the following steps: s1 ZrO 2 ，SiO 2 ，Cr 2 O 3 ，Co 2 O 3 Weighing according to a chemical formula; s2 adding Li to the raw material in the step S1 2 CO 3 Then fully and uniformly mixing, and putting the mixture into deionized water for wet ball milling; s3, putting the mixture ball-milled in the step S2 into an oven for drying; s4, fully and uniformly grinding the dried powder in the step S3; s5 putting the powder obtained by grinding S4 uniformly into a muffle furnace to be calcined to obtain (Cr, Co) -ZrSiO 4 And (3) powder lot. The preparation method provided by the application has the advantages of simple operation and large-scale industrial production, and can be successfully synthesized at the low temperature of 980 ℃, and the sample has good chromatic value and good color valueThe application prospect of (1).)

1. A method for preparing a zirconium silicate-based colorant doped with Cr and Co, wherein the zirconium silicate-based colorant has a chemical formula of:

(Cr_2x,Co_x)-Zr_(1-3x)SiO₄wherein x is an atomic mole fraction, and x is 0.01-0.04;

the method comprises the following steps:

s1 ZrO₂，SiO₂，Cr₂O₃，Co₂O₃Weighing according to a chemical formula;

s2 adding Li to the raw material in the step S1₂CO₃Then fully and uniformly mixing, and putting the mixture into deionized water for wet ball milling;

s3, putting the mixture ball-milled in the step S2 into an oven for drying;

s4, fully and uniformly grinding the dried powder in the step S3;

s5 putting the powder obtained by grinding S4 uniformly into a muffle furnace to be calcined to obtain (Cr, Co) -ZrSiO₄And (3) powder lot.

2. The method according to claim 1, wherein in the step S1, the raw materials used include: 99 wt% ZrO₂，99.5wt％SiO₂，99.5wt％Cr₂O₃，99wt％Co₂O₃，99wt％Li₂CO₃。

3. Method according to claim 2, characterized in that in said stepIn S1, in the step S1, the Li₂CO₃As mineralizer, the Li₂CO₃Is 0.5 wt% of the total amount of the raw materials.

4. The method of claim 1, wherein in the step S2, the wet ball milling time is 2h and the rotation speed is 225 r/min.

5. The method as claimed in claim 1, wherein in the step S3, the drying temperature is 90 ℃ and the drying time is 8-10 h.

6. The method of claim 1, wherein in the step S3, the grinding time is 15-20 min.

7. The method according to claim 1, wherein in the step S4, the muffle furnace calcination temperature is 980 ℃, the holding time is 3h, and the temperature rise rate is 200 ℃/h.

8. A zirconium silicate-based colorant doped with Cr and Co, wherein said zirconium silicate-based colorant doped with Cr and Co is prepared by the method of any one of claims 1 to 7.

Technical Field

The invention relates to the field of inorganic materials, in particular to a zirconium silicate-based pigment doped with Cr and Co and a preparation method thereof.

Background

In recent years, with the increasing living standard and aesthetic value of people, the market demand for green high-temperature ceramic pigment is increased. The zirconium silicate-based ceramic pigment has the advantages of various varieties, bright colors and stable color generation, is deeply favored by people, and is also developed vigorously. However, the synthesis temperature of zirconium silicate is too high, the synthesis temperature of zirconium silicate is often above 1500 ℃ by using a conventional method, the too high synthesis temperature not only increases energy consumption, but also increases the purchase cost of factory equipment, and more importantly, the too high sintering temperature affects the color of a ceramic pigment, so that the reduction of the synthesis temperature of zirconium silicate is particularly important.

Zirconium silicate (ZrSiO)₄) Good chemical stability, high temperature resistance and corrosion resistance, and is a matrix material of high-temperature glaze and ceramic pigment with excellent performance. The zirconium silicate-based ceramic pigment is widely applied and researched in the fields of ceramic decoration and glaze.

In order to synthesize zirconium silicate-based ceramic colorants at low temperatures, most researchers have started with the idea of lowering the phase transition temperature of the starting material. In recent years, technological means for lowering the synthesis temperature of zirconium silicate have been developed. For example, the sol-gel method is a common method for lowering the synthesis temperature of zirconium silicate, and is a method of using zirconium oxychloride (ZrOCl)₂·8H₂O) and tetraethoxysilane Si (OC)₄H₉)₄The raw materials are fluoride as a mineralizer, the fluoride is dissolved in a solvent, sol is obtained through polycondensation, and the sol is dried and calcined to obtain zirconium silicate-based pigment powder. Although the sol-gel method can reduce the synthesis temperature of zirconium silicate, the raw material metal alkoxide used by the sol-gel method has the defects of high price, difficult precursor washing, complex production process, long preparation period, easy powder agglomeration, low yield and the like, and is not beneficial to large-scale industrial production. Chenrenhua et al used coprecipitation method with ZrOCl₂·8H₂O、Na₂SiO₃·5H₂O and PrCl₃·7H₂O is used as a main raw material, LiF is used as a mineralizer, and Pr-ZrSiO is synthesized by sintering at 860 DEG C₄(praseodymium zirconium yellow) coloring material. Although the coprecipitation method reduces the synthesis temperature of zirconium silicate, the coprecipitation method requires acid washing, water washing and other steps, and is easy to cause environmental pollution. In addition, the washing step also causes loss of coloring ions, resulting in different color of the colorant from batch to batch, which is not suitable for industrial productionAnd (5) industrial large-scale production. Therefore, the seeking of the zirconium silicate-based ceramic pigment which has simple preparation method, easily obtained raw materials and large-scale industrial production at low temperature has great scientific research and practical application significance.

Disclosure of Invention

In order to solve the problem that the color of a zirconium-based pigment is affected by overhigh synthesis temperature of zirconium silicate, the application provides a preparation method of the zirconium-based pigment doped with Cr and Co, wherein the chemical general formula of the zirconium-based pigment is as follows:

(Cr_2x,Co_x)-Zr_(1-3x)SiO₄wherein x is an atomic mole fraction, and x is 0.01-0.04;

the method comprises the following steps:

s1 ZrO₂，SiO₂，Cr₂O₃，Co₂O₃Weighing according to a chemical formula;

s2 adding Li to the raw material in the step S1₂CO₃Then fully and uniformly mixing, and putting the mixture into deionized water for wet ball milling;

s3, putting the mixture ball-milled in the step S2 into an oven for drying;

s4, fully and uniformly grinding the dried powder in the step S3;

s5 putting the powder obtained by grinding S4 uniformly into a muffle furnace to be calcined to obtain (Cr, Co) -ZrSiO₄And (3) powder lot.

The application also provides a zirconium silicate-based pigment doped with Cr and Co, wherein the zirconium silicate-based pigment doped with Cr and Co is prepared by the method.

Optionally, in the step S1, the raw materials used include: 99 wt% ZrO₂，99.5wt％SiO₂，99.5wt％Cr₂O₃，99wt％Co₂O₃，99wt％Li₂CO₃。

Optionally, in the step S1, in the step S1, the Li₂CO₃As mineralizer, the Li₂CO₃Is 0.5 wt% of the total amount of the raw materials.

Optionally, in the step S2, the duration of the wet ball milling is 2h, and the rotation speed is 225 r/min.

Optionally, in the step S3, the drying temperature is 90 ℃ and the drying time is 8-10 h.

Optionally, in the step S3, the grinding time is 15-20 min.

Optionally, in the step S4, the muffle furnace calcination temperature is 980 ℃, the holding time is 3h, and the temperature rise rate is 200 ℃/h.

The technical scheme of the application has the advantages that:

the synthesis method provided by the application has the advantages of simple operation and low cost, and can be successfully synthesized at the low temperature of 980 ℃, so that the method is more suitable for large-scale industrial production.

The pigment prepared by the method has good chemical stability and strong coloring capacity, and the chromatic value is similar to that of commercial powder, so that the pigment is a powerful substitute for powder in the prior art.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be clear that the drawings in the following description are only intended to illustrate some embodiments of the present application, and that for a person skilled in the art, it is possible to derive from these drawings, without inventive effort, technical features, connections or even method steps not mentioned in the other drawings.

FIG. 1 shows the (Cr) produced_2x,Co_x)-Zr_(1-3x)SiO₄(x is 0.01 to 0.04, and is represented by F1, F2, F3, and F4, respectively) a photograph of a ceramic coloring material. The samples all showed bright green color, indicating strong coloring ability and good high temperature stability.

FIG. 2 shows the (Cr) produced_2x,Co_x)-Zr_(1-3x)SiO₄(x is 0.01 and denoted by F1) XRD pattern of the ceramic coloring material. From the figure, it can be seen that the sample is ZrSiO₄Single crystal phase, indicating good crystallinity of the sample.

FIG. 3 shows the (Cr) produced_2x,Co_x)-Zr_(1-3x)SiO₄(x is 0.02 and denoted by F2) XRD pattern of the ceramic coloring material. From the figure, it can be seen that the sample is ZrSiO₄Single crystal phase, indicating good crystallinity of the sample.

FIG. 4 shows the (Cr) produced_2x,Co_x)-Zr_(1-3x)SiO₄(x is 0.03 and denoted by F3) XRD pattern of the ceramic coloring material. From the figure, it can be seen that the sample is ZrSiO₄Single crystal phase, indicating good crystallinity of the sample.

FIG. 5 shows the (Cr) produced_2x,Co_x)-Zr_(1-3x)SiO₄(x is 0.04 and denoted by F4) XRD pattern of the ceramic coloring material. From the figure, it can be seen that the sample is ZrSiO₄Single crystal phase, indicating good crystallinity of the sample.

FIG. 6 shows the (Cr) produced_2x,Co_x)-Zr_(1-3x)SiO₄(x is 0.01 to 0.04 and is represented by F1, F2, F3 and F4) in the visible light (400-780 nm). The reflectance of the samples was found to decrease with increasing Cr and Co content.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

The present invention will be described in further detail with reference to the accompanying drawings.

The application provides a preparation method of a zirconium silicate-based pigment doped with Cr and Co, wherein the chemical general formula of the zirconium silicate-based pigment is as follows:

(Cr_2x,Co_x)-Zr_(1-3x)SiO₄wherein x is an atomic mole fraction, and x is 0.01-0.04;

the method comprises the following steps:

s1 ZrO₂，SiO₂，Cr₂O₃，Co₂O₃Weighing according to a chemical formula;

s2 adding Li to the raw material in the step S1₂CO₃Then fully and uniformly mixing, and putting the mixture into deionized water for wet ball milling;

s3, putting the mixture ball-milled in the step S2 into an oven for drying;

s4, fully and uniformly grinding the dried powder in the step S3;

s5 putting the powder obtained by grinding S4 uniformly into a muffle furnace to be calcined to obtain (Cr, Co) -ZrSiO₄And (3) powder lot.

The application also provides a zirconium silicate-based pigment doped with Cr and Co, wherein the zirconium silicate-based pigment doped with Cr and Co is prepared by the method.

Optionally, in the step S1, the raw materials used include: 99 wt% ZrO₂，99.5wt％SiO₂，99.5wt％Cr₂O₃，99wt％Co₂O₃，99wt％Li₂CO₃。

Optionally, in the step S1, in the step S1, the Li₂CO₃As mineralizer, the Li₂CO₃Is 0.5 wt% of the total amount of the raw materials.

Optionally, in the step S2, the duration of the wet ball milling is 2h, and the rotation speed is 225 r/min.

Optionally, in the step S3, the drying temperature is 90 ℃ and the drying time is 8-10 h.

Optionally, in the step S3, the grinding time is 15-20 min.

Optionally, in the step S4, the muffle furnace calcination temperature is 980 ℃, the holding time is 3h, and the temperature rise rate is 200 ℃/h.

The synthesized sample was subjected to XRD measurement and reflectance spectrum measurement.

XRD test:

and (3) putting the synthesized sample into a mortar, fully and uniformly grinding until no granular sensation exists, putting the ground powder into a sample tank, and testing by adopting an XRD diffractometer.

And (3) reflection spectrum measurement:

and fully and uniformly grinding the synthesized sample until no granular sensation exists, putting the ground powder into a sample tank, and performing reflection spectrum measurement by using an ultraviolet-visible spectrometer.