阅读说明：本技术 一种纳米氧化锆陶瓷用黑色颜料的制备方法 (Preparation method of black pigment for nano zirconia ceramic ) 是由 程兰兰 刘华锋 陈仁华 刘文明 廖艳勤 于 2021-09-30 设计创作，主要内容包括：本发明公开了一种纳米氧化锆陶瓷用黑色颜料的制备方法。该颜料的制备方法如下：1、将钴、铬、铝、铁等金属盐与碱或碱金属盐同时滴入水中,经压滤水洗烘干后获得前驱体A；2、将前驱体A与水按一定质量比装入球磨机中球磨后,再经水洗烘干后获得前驱体B；3、将前驱体B与助稳定性的钇等稀土化合物按一定质量比混合均匀后,在600℃-800℃下煅烧；4、将煅烧产物水洗、烘干、气流粉碎获得纳米氧化锆陶瓷用黑色颜料。本发明使黑色颜料的转晶温度降低至600℃-800℃,且转晶后物料不需二次研磨D100直接达到2微米以内,所得黑色颜料具有尖晶石结构、晶粒发育良好、高比表面及稳定的化学性等,符合氧化锆陶瓷领域的性能要求。(The invention discloses a preparation method of a black pigment for nano zirconia ceramics. The preparation method of the pigment comprises the following steps: 1. dripping metal salts of cobalt, chromium, aluminum, iron and the like and alkali or alkali metal salts into water at the same time, and obtaining a precursor A after filter pressing, washing and drying; 2. putting the precursor A and water into a ball mill according to a certain mass ratio, carrying out ball milling, washing with water, and drying to obtain a precursor B; 3. uniformly mixing the precursor B and a stabilizing rare earth compound such as yttrium according to a certain mass ratio, and calcining at 600-800 ℃; 4. and washing, drying and carrying out jet milling on the calcined product to obtain the black pigment for the nano zirconia ceramics. The invention reduces the crystal transformation temperature of the black pigment to 600-800 ℃, and the crystal transformed material can directly reach within 2 microns without secondary grinding of D100, and the obtained black pigment has a spinel structure, good crystal grain development, high specific surface, stable chemistry and the like, and meets the performance requirements of the field of zirconia ceramics.)

1. A preparation method of black pigment for nano zirconia ceramics is characterized by comprising the following steps:

(1) in molar ratio Co²⁺:Cr³⁺:Al³⁺:Fe³⁺Ni²⁺(0.1-0.2): (0.1-0.3): (0.005-0.01): (0.1-0.2) and (0.03-0.05), respectively weighing metal salts of cobalt salt, chromium salt, aluminum salt, iron salt and nickel salt, and then dissolving the metal salts in water to mark as A;

(2) weighing alkali or alkali metal salt, and dissolving in water, and marking as B;

(3) dissolving a dispersant in water to be marked as C;

(4) dripping A, B into C, stirring, and controlling pH as D;

(5) after dripping, washing D with water until no ions are washed out, and drying, and marking as E;

(6) e and water are put into a ball mill for ball milling, and marked as F;

(7) f, washing with water until no ions are washed out, and drying, and marking as G;

(8) adding a rare earth compound, crushing and sieving, and marking as H;

(9) and (3) putting the H into a crucible, calcining at 600-800 ℃ for 60-120 minutes, washing with water, drying, and then crushing with air flow to obtain the black pigment for the nano zirconia ceramics, which is marked as I.

2. The method for preparing the black pigment for nano zirconia ceramics according to claim 1, wherein in the step (1), the metal salt is chloride, nitrate or sulfate corresponding to metal ions.

3. The preparation method of the black pigment for the nano zirconia ceramics according to claim 1, wherein in the step (2), the alkali or alkali metal salt is sodium hydroxide, sodium carbonate or sodium hydroxy carbonate, and the molar ratio of the alkali or alkali metal salt to the metal salt in the step (1) is 1.1-1.3: 1.

4. The method for preparing the black pigment for the nano zirconia ceramics according to claim 1, wherein in the step (3), the dispersant is polyethylene glycol-1000, polyethylene glycol-2000 or sodium dodecyl benzene sulfonate, and the dosage of the dispersant is 0.05 to 0.2 percent of the total mass of the metal salt.

5. The method for preparing the black pigment for the nano zirconia ceramics according to claim 1, wherein the pH in the step (4) is 6 to 9.

6. The preparation method of the black pigment for nano zirconia ceramics according to claim 1, wherein in the step (6), the mass ratio of water to E is 1:1, and the ball milling time is 0.5h to 1 h.

7. The method for preparing the black pigment for the nano zirconia ceramics according to claim 1, wherein the drying temperature in the steps (5) and (7) is 100 to 150 ℃.

8. The method for preparing black pigment for nano zirconia ceramics according to claim 1, wherein in the step (8), the rare earth compound is one or two of yttrium and neodymium, and the amount of the rare earth compound is 0.1-1% of the mass E.

9. The method for preparing the black pigment for the nano zirconia ceramics according to claim 1, wherein in the step (8), the sieve is a sieve of 100 to 1000 meshes.

Technical Field

The invention relates to preparation of a pigment, in particular to a preparation method of a black pigment for nano zirconia ceramics.

Background

In recent years, high-end precision nano zirconia ceramics are widely applied to smart wearing and 5G smart phones, and show a great growth and rising trend. This is mainly because the high-end precision nano zirconia ceramics have high hardness, scratch resistance, stable chemical properties, good biological skin-friendly properties, and a moist, delicate and elegant appearance compared with aluminum-magnesium alloys. According to statistics, the shipment volume of the ceramic back plate of the mobile phone in 2018 reaches 500 ten thousand sheets, and terminal clients comprise millet, OPPO and the like; in 2019, the release of the Samsung ceramic mobile phone further promotes the market space; the rear cover of the ceramic black/white P40 Pro + in the classic style in 2020 is made of nano zirconia ceramic material. With the advent and popularity of the 5G era, metallic appearances for signal shielding will gradually come out of the market, while ceramics without signal shielding will have a larger market share.

Black has the image of high and precious, steady and scientific, and most of scientific products adopt black, such as televisions, sports cars, cameras, audios and the like. In life, the scientific and technological product which is quite magical is sometimes called 'black science and technology'. The solemn image of black is a main color which is always popular, and the space design, the living goods and the clothes design in some special occasions mostly use black to form high-priced images. At present, black pigments for zirconia ceramics mainly depend on import, and the black pigments for domestic nano zirconia ceramics have the problems of different degrees in the application process, such as impure and reddish color generation, poor stability, easy cracking and the like easily occurring in high-temperature zirconia ceramics.

Disclosure of Invention

The invention aims to provide a preparation method of a black pigment, which is suitable for high-end precision nano zirconia ceramics. The solid phase synthesis method is the most common preparation method, and the black pigment for the zirconia ceramics synthesized by the method has the defects of uneven grain size, different shapes, low tinting strength, low purity and the like, and is easy to decompose and can not stably develop color in the densification sintering process of the zirconia ceramics at high temperature (1350-1500 ℃). Therefore, the method adopts a chemical precipitation method, can refine and uniformly mix the raw materials, and has the advantages of simple process, low calcination temperature, short calcination time, good product performance and the like. Meanwhile, the invention combines the processes of ball milling and water washing the precursor synthesized by the liquid phase, doping rare earth elements such as yttrium and the like before calcining, and the like, so that the prepared black pigment has excellent performances of a spinel structure, good crystal grain development, high specific surface, good chemical stability and the like, and is suitable for the field of high-end precise nano zirconia ceramics.

The purpose of the invention is realized by the following technical scheme:

a preparation method of black pigment for nano zirconia ceramics comprises the following steps:

(1) in molar ratio Co²⁺:Cr³⁺:Al³⁺:Fe³⁺Ni²⁺(0.1-0.2): (0.1-0.3): (0.005-0.01): (0.1-0.2) and (0.03-0.05), respectively weighing metal salts of cobalt salt, chromium salt, aluminum salt, iron salt and nickel salt, and then dissolving the metal salts in water to mark as A;

(2) weighing alkali or alkali metal salt, and dissolving in water, and marking as B;

(3) dissolving a dispersant in water to be marked as C;

(4) dripping A, B into C, stirring, and controlling pH as D;

(5) after dripping, washing D with water until no ions are washed out, and drying, and marking as E;

(6) e and water are put into a ball mill for ball milling, and marked as F;

(7) f, washing with water until no ions are washed out, and drying, and marking as G;

(8) adding a rare earth compound, crushing and sieving, and marking as H;

(9) and (3) putting the H into a crucible, calcining at 600-800 ℃ for 60-120 minutes, washing with water, drying, and then crushing with air flow to obtain the black pigment for the nano zirconia ceramics, which is marked as I.

Further, in the step (1), the metal salt is a chloride salt, a nitrate salt or a sulfate salt corresponding to the metal ion.

Further, in the step (2), the alkali or alkali metal salt is sodium hydroxide, sodium carbonate or basic sodium carbonate, and the molar ratio of the alkali or alkali metal salt to the metal salt in the step (1) is 1.1-1.3: 1.

Further, in the step (3), the dispersant is polyethylene glycol-1000, polyethylene glycol-2000 or sodium dodecyl benzene sulfonate, and the dosage of the dispersant is 0.05-0.2% of the total mass of the metal salt.

Further, in the step (4), the pH is 5-10, preferably 6-9.

Further, in the steps (5) and (7), the drying temperature is 100-150 ℃.

Further, in the step (6), the mass ratio of water to E is 1:1, and the ball milling time is 0.5-2 h, preferably 0.5-1 h.

Further, in the step (8), the rare earth compound is one or two of yttrium and neodymium, has a high specific surface area, and is used in an amount of 0.1-1% of the mass of E.

Further, in the step (8), the sieve is preferably a sieve of 100-1000 meshes.

Compared with the prior art, the invention has the following advantages:

the invention adopts a chemical precipitation method and ball milling and water washing treatment on the precursor synthesized by the liquid phase, so that the crystal transformation temperature of the black pigment is reduced to 600-800 ℃, and the crystal transformation material can directly reach within 2 microns without secondary grinding of D100, and the obtained black pigment has a spinel structure, good crystal grain development, high specific surface, stable chemistry and the like, and meets the performance requirements in the field of zirconia ceramics; compared with the common chemical coprecipitation method, the method is easier to prepare the crystal grains with small particles and narrow particle size distribution. Meanwhile, rare earth elements such as yttrium and the like are doped, so that the prepared black pigment is not easy to decompose and is stable in coloring in the high-temperature (1350 ℃ -1500 ℃) densification sintering process of the zirconia ceramic.

Drawings

FIG. 1 is a block diagram of the process of the present invention.

FIG. 2 is an SEM photograph of a colorant sample obtained in example 6.

FIG. 2 is an SEM image of the black pigment prepared by the present invention, wherein the obtained black pigment has a spinel structure, good crystal grain development, and uniform crystal grain size of 100-200 nm.

Fig. 3 and fig. 4 are diagrams illustrating the effect of the black pigment synthesized by the liquid phase precipitation method and the solid phase method, respectively, applied to the zirconia ceramic, and it can be seen from fig. 3 that the chroma values of the pigment prepared by the liquid phase precipitation method (without polishing) are a ═ 0.15, b ═ 0.22, and L ═ 37.69; the chroma values after polishing were a-0.34, b-0.07, and L-35.06. As shown in fig. 4, the color material prepared by the solid phase method has chroma values a ═ 0.00, b ═ 0.21 and L ═ 37.28 when applied to zirconia ceramics (unpolished), and although the chroma value is not much as that of the black color material synthesized by the liquid phase, the black color material synthesized by the solid phase method has coarse particles, is not easy to be finely ground, has poor hue stability and high sintering temperature.

Detailed Description

The present invention will be further described with reference to specific examples, but the embodiments of the present invention are not limited thereto, and the process parameters not specifically described may be performed by referring to the conventional techniques.

Example 1

A preparation method of black pigment for nano zirconia ceramics comprises the following steps:

(1) 55.8g of CrCl was taken₃·6H₂O，41g CoCl₂·6H₂O，1g AlCl₃·6H₂O，43.1gFeCl₃·6H₂O,9.5g NiCl₂·6H₂Dissolving O in 500mL of water to obtain solution A; 100 g of Na₂CO₃Dissolving in 500mL of water to obtain solution B; 0.5g of polyethylene glycol-1000 is dissolved in 200mL of water to obtain C; dropping A and B into C, keeping pH at 7 to obtain solution D, stirring for 1 hr, washing with water until D has no ion, oven drying at 120 deg.C, and pulverizing to obtain powder E with 200 mesh; putting the E and water into a ball mill, ball-milling for 0.5 hour, washing with water until the F is washed out without ions, drying at 120 ℃, and crushing to pass through a 200-mesh sieve G; 0.5 wt% of yttrium and neodymium rare earth compound G is uniformly mixed and put into a crucible, calcined for 120 minutes at 600 ℃, washed by water and pulverized by air flow.

Example 2

55.8g of CrCl was taken₃·6H₂O，41g CoCl₂·6H₂O，1g AlCl₃·6H₂O，43.1gFeCl₃·6H₂O,9.5g NiCl₂·6H₂Dissolving O in 500mL of water to obtain solution A; 100 g of Na₂CO₃Dissolved in 500mL of water to form B₁Liquid; 0.5g of polyethylene glycol-1000 dissolved in 200mL of water is C₁(ii) a A is to be₁And B₁Co-dropping in C to maintain pH at 7 to obtain D₁Stirring for 1 hr, washing with water to D₁Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve E₁(ii) a Will E₁Putting the mixture and water into a ball mill, ball-milling for 0.5 hour, and washing with water to F₁Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve G₁(ii) a 0.5 wt% of yttrium and neodymium rare earth compound G₁Mixing, loading in crucible, calcining at 800 deg.C for 60 min, washing with water and jet pulverizing.

Example 3

55.8g of CrCl was taken₃·6H₂O，41g CoCl₂·6H₂O，1g AlCl₃·6H₂O，43.1gFeCl₃·6H₂O,9.5g NiCl₂·6H₂Dissolving O in 500mL of water to obtain solution A; 100 g of Na₂CO₃Dissolved in 500mL of water to form B₂Liquid; 0.5g of polyethylene glycol-1000 dissolved in 2000mL of water is C₂(ii) a A is to be₂And B₂Co-dropping in C to maintain pH at 7 to obtain D₂Stirring for 1 hr, washing with water to D₂Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve E₂(ii) a Will E₂Putting the mixture and water into a ball mill, ball-milling for 0.5 hour, and washing with water to F₂Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve G₂(ii) a G is to be₂Mixing, loading in crucible, calcining at 800 deg.C for 60 min, washing with water and jet pulverizing.

Example 4

55.8g of CrCl was taken₃·6H₂O，41g CoCl₂·6H₂O，1g AlCl₃·6H₂O，43.1gFeCl₃·6H₂O,9.5g NiCl₂·6H₂Dissolving O in 500mL of water to obtain solution A; 100 g of Na₂CO₃Dissolved in 500mL of water to form B₃Liquid; 0.5g of polyethylene glycol-1000 dissolved in 200mL of water is C₃(ii) a A is to be₃And B₃Is dropped on C₃Maintaining the pH at 7 to obtain D₃Stirring for 1 hr, washing with water to D₃Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve E₃(ii) a Will E₃Putting the mixture and water into a ball mill, ball-milling for 0.5 hour, and washing with water to F₃Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve G₃(ii) a 0.5 wt% of yttrium and neodymium rare earth compound and G₃Mixing, loading in crucible, calcining at 600 deg.C for 120 min, washing with water and jet pulverizing.

Example 5

Taking 102g Cr (NO)₃)₃·9H₂O，50.1g Co(NO₃)₂·6H₂O，2.95g Al(NO₃)₃·9H₂O，72.6g Fe(NO₃)₃·9H₂O，10.2g Ni(NO₃)₂Dissolving in 500mL of water to obtain A₄Liquid; 75 g NaOH dissolved in 500mL water as B₄Liquid; 0.5g polyethylene glycol-2000 dissolved in 200mL water is C₄(ii) a Dropping A and B together on C₄Maintaining the pH at 7 to obtain D₄Stirring for 1 hr, washing with water to D₄Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve E₄(ii) a Will E₄Putting the mixture and water into a ball mill, ball-milling for 0.5 hour, and washing with water to F₄Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve G₄(ii) a 0.5 wt% of yttrium and neodymium rare earth compound and G₄Mixing, loading in crucible, calcining at 800 deg.C for 60 min, washing with water and jet pulverizing.

Example 6

Taking 102g Cr (NO)₃)₃·9H₂O，50·1g Co(NO₃)₂·6H₂O，2.95g Al(NO₃)₃·9H₂O，72.6g Fe(NO₃)₃·9H₂O，10.2g Ni(NO₃)₂Dissolving in 500mL of water to obtain A₄Liquid; 158.5 g NaHCO₃Dissolved in 500mL of water to form B₅Liquid; 0.5g sodium dodecylbenzenesulfonate dissolved in 200mL water is C₅(ii) a A is to be₅And B₅Is dropped on C₅Maintaining the pH at 7 to obtain D₅Stirring for 1 hr, washing with water to D₅Ion-free washing outDrying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve to obtain powder E₅(ii) a Will E₅Putting the mixture and water into a ball mill, ball-milling for 0.5 hour, and washing with water to F₅Until no ion is washed out, drying at 120 deg.C, pulverizing, and sieving with 200 mesh sieve G₅(ii) a 0.5 wt% of yttrium and neodymium rare earth compound and G₅Mixing, loading in crucible, calcining at 800 deg.C for 60 min, washing with water and jet pulverizing.