CN117143467A - Gray pigment for low-temperature glaze and preparation method thereof - Google Patents

Gray pigment for low-temperature glaze and preparation method thereof Download PDF

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Publication number
CN117143467A
CN117143467A CN202311113551.4A CN202311113551A CN117143467A CN 117143467 A CN117143467 A CN 117143467A CN 202311113551 A CN202311113551 A CN 202311113551A CN 117143467 A CN117143467 A CN 117143467A
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parts
low
pigment
gray pigment
titanium dioxide
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刘位浪
廖宇
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Guangdong Fenglin New Material Technology Co ltd
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Guangdong Fenglin New Material Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0009Pigments for ceramics

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention discloses a gray pigment for low-temperature glaze and a preparation method thereof, wherein the gray pigment comprises the following components in parts by weight: 89.5 to 97.5 parts of titanium dioxide, 1 to 4 parts of vanadium pentoxide and 1.5 to 6.5 parts of antimonous oxide, the prepared gray pigment is colored and is not transparent in low-temperature glaze, the covering power of the pigment is strong, the preparation process is simple, and the prepared gray pigment has good coloring performance in low-temperature glaze.

Description

Gray pigment for low-temperature glaze and preparation method thereof
Technical Field
The invention relates to the technical field of low-temperature glazes, in particular to a gray pigment for a low-temperature glaze and a preparation method thereof.
Background
The gray inorganic pigment for glaze is not very various, and comprises antimony tin ash, zirconium ash and gray prepared by mixing various pigments such as black, cobalt blue, vanadium zirconium blue and the like according to the components, and the pigments are suitable for high-temperature glaze with the temperature of more than 1100 ℃. Aiming at the low-temperature glaze in the temperature range of 700-850 ℃, the gray inorganic pigments have the defects of weak color, poor coverage and the like, for example, zirconium ash presents green tone in the low-temperature glaze, mixed modulation ash presents dark brown in the low-temperature glaze, and the prior gray pigments are difficult to present ideal gray.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the gray pigment for the low-temperature glaze and the preparation method thereof, the prepared gray pigment has the advantages of color rendering, no penetration of bottom in the glaze, strong covering power, simple preparation process and good coloring performance in the low-temperature glaze.
One of the technical schemes adopted for solving the technical problems is as follows:
the gray pigment for the low-temperature glaze comprises the following components in parts by weight: 89.5 to 97.5 parts of titanium dioxide, 1 to 4 parts of vanadium pentoxide and 1.5 to 6.5 parts of antimonous oxide, wherein the sum of the weight parts of the titanium dioxide, the vanadium pentoxide and the antimonous oxide is 100 parts.
Preferably, the composition comprises the following components in parts by weight: 93.5 parts of titanium dioxide, 2 parts of vanadium pentoxide and 4.5 parts of antimonous oxide.
Preferably, zinc oxide is further contained in an amount of 0.1 to 1 part.
Preferably, the composition comprises the following components in parts by weight: 93.5 parts of titanium dioxide, 2 parts of vanadium pentoxide, 4.5 parts of antimonous oxide and 0.5 part of zinc oxide.
The titanium dioxide is a white pigment with titanium dioxide as a main component, and comprises titanium plate type titanium dioxide, anatase type titanium dioxide and rutile type titanium dioxide. Wherein the titanium plate is an unstable crystal form, and can be converted into a stable rutile form at the temperature of more than 650 ℃, and is not generally applied to industrial production; the anatase titanium dioxide has no melting point and boiling point, and can be converted into rutile titanium dioxide at a high temperature of 900 ℃. Therefore, whichever titanium white powder is used as the raw material is the stable rutile titanium white powder finally during calcination.
Zinc oxide is added as mineralizer to enter grey pigment, so that solid phase reaction can be promoted, reactivity is increased, calcining temperature during reaction is reduced, solid phase reaction is accelerated, calcining time and heat preservation time are reduced, ion replacement is complete, coloring ions fully enter titanium dioxide crystal lattice, and color forming effect is improved.
Preferably, the titanium dioxide is rutile titanium dioxide.
Preferably, the particle size D100 of the titanium dioxide is less than 10 mu m.
According to the solid phase reaction kinetics, yang Deer equation and the Stirling lattice equation show that the smaller the particle size is, the larger the specific surface area of the reaction system is, the reaction section and the diffusion section are correspondingly increased, and the reaction rate is further increased. Therefore, the titanium dioxide with the particle size smaller than 10 mu m is adopted, so that the raw materials can be mixed more fully, and the reaction can be promoted better.
Preferably, the purity of the vanadium pentoxide is greater than 99.5%.
The second technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the gray pigment for the low-temperature glaze comprises the following steps:
s1: the components are proportioned according to the proportion, evenly mixed in a mixer, and then subjected to powder grinding treatment in a claw-type powder grinding machine to obtain a premixed raw material;
s2: ball milling the pre-mixed raw materials to obtain mixed raw materials, wherein D50 of the mixed raw materials is smaller than 5 mu m;
s3: calcining the mixed raw materials in a kiln to obtain a calcined product, wherein the calcining temperature is 1090-1150 ℃ and the heat preservation time is 1-3 h;
s4: pre-crushing the calcined product to obtain a calcined product with a particle size smaller than 2cm;
s5: carrying out jet milling treatment on the pre-crushed calcined product to obtain calcined powder, wherein the particle size of the calcined powder is smaller than 10 mu m;
s6: and uniformly mixing and stirring the calcined powder to obtain the gray pigment.
If the titanium dioxide in the raw materials is anatase, in the calcining process of the step S3, the anatase titanium dioxide starts to be converted into a stable rutile crystal structure at about 900 ℃.
Specifically, when the calcination temperature is 1090-1150 ℃, the vanadium pentoxide and the antimony trioxide can be subjected to non-equivalent ion substitution with titanium dioxide, and V in the vanadium pentoxide 5+ And Sb in antimony trioxide 3+ Will replace part of Ti in the titanium dioxide 4+ Obtaining the non-equivalent substitution solid solution, and obtaining the gray pigment applied to the low-temperature glaze material at 700-850 ℃. Because the replacement process occurs in the temperature range of 1090-1150 ℃, the gray pigment has stable performance and good color forming effect in the use process of the low-temperature glaze.
The claw type powder mill is adopted to further mix the pre-mixed raw materials so as to ensure the uniform occurrence of the solid phase reaction.
Further, in step S5, the calcined powder has a particle diameter D100 of less than 10 μm and a particle diameter D50 of 1 to 1.5. Mu.m.
Further, in step S3, the total calcination time of the mixed raw materials is 10 to 12 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. the grey pigment provided by the invention is color-proof and bottom-proof in low-temperature glaze, has strong pigment covering power, and simple preparation process, and the prepared grey pigment has good coloring performance in low-temperature glaze.
2. Part of Ti in the titanium dioxide is replaced by non-equivalent ions 4+ Substitution to V during solid phase reaction 5+ And Sb (Sb) 3+ The prepared reaction product presents gray, can be applied to low-temperature glaze materials with the temperature of 700-850 ℃, is prepared by a solid-phase method, has good coloring performance in the low-temperature glaze materials, has simple preparation process and is suitable for large-scale production.
Drawings
FIG. 1 is a graph of the color forming effect of example 1.
FIG. 2 is a graph of the color forming effect of comparative example 2.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described below with reference to the accompanying drawings and embodiments.
Example 1
The gray pigment for the low-temperature glaze comprises the following components in parts by weight: 93.5 parts of titanium dioxide, 2 parts of vanadium pentoxide and 4.5 parts of antimonous oxide.
Wherein the titanium dioxide is anatase titanium dioxide, the granularity D100 of the titanium dioxide is smaller than 10 mu m, and the purity of the vanadium pentoxide is larger than 99.5%.
The preparation method of the gray pigment for the low-temperature glaze comprises the following steps:
s1: mixing the titanium dioxide, the vanadium pentoxide and the antimonous oxide according to the proportion, uniformly mixing in a mixer, and then carrying out powder grinding treatment in a claw type powder grinding machine to obtain a premixed raw material;
s2: ball milling the pre-mixed raw materials to obtain mixed raw materials, wherein D50 of the mixed raw materials is smaller than 5 mu m;
s3: calcining the mixed raw materials in a kiln to obtain a calcined product, wherein the calcining temperature is 1120 ℃, the heat preservation time is 3 hours, and the total calcining time is 12 hours;
s4: pre-crushing the calcined product to obtain a calcined product with a particle size smaller than 2cm;
s5: carrying out jet milling treatment on the pre-crushed calcined product to obtain calcined powder, wherein the particle size D100 of the calcined powder is smaller than 10 mu m, and the particle size D50 of the calcined powder is 1-1.5 mu m;
s6: and uniformly mixing and stirring the calcined powder to obtain the gray pigment.
The prepared gray pigment is applied to glass ink for coloring, the color forming effect is shown in figure 1, the color is in a color without penetrating bottom, and the covering power of the pigment is strong.
Example 2
The gray pigment for the low-temperature glaze comprises the following components in parts by weight: 97.5 parts of titanium dioxide, 1 part of vanadium pentoxide and 1.5 parts of antimonous oxide.
Wherein the titanium dioxide is rutile titanium dioxide, the granularity D100 of the titanium dioxide is smaller than 10 mu m, and the purity of the vanadium pentoxide is larger than 99.5%.
The preparation method of the gray pigment for the low-temperature glaze comprises the following steps:
s1: mixing the titanium dioxide, the vanadium pentoxide and the antimonous oxide according to the proportion, uniformly mixing in a mixer, and then carrying out powder grinding treatment in a claw type powder grinding machine to obtain a premixed raw material;
s2: ball milling the pre-mixed raw materials to obtain mixed raw materials, wherein D50 of the mixed raw materials is smaller than 5 mu m;
s3: the mixed raw materials are put into a kiln for calcination to obtain a calcination product, wherein the calcination temperature is 1150 ℃, the heat preservation time is 2 hours, and the total calcination time is 10 hours;
s4: pre-crushing the calcined product to obtain a calcined product with a particle size smaller than 2cm;
s5: carrying out jet milling treatment on the pre-crushed calcined product to obtain calcined powder, wherein the particle size D100 of the calcined powder is smaller than 10 mu m, and the particle size D50 of the calcined powder is 1-1.5 mu m;
s6: and uniformly mixing and stirring the calcined powder to obtain the gray pigment.
Example 3
The gray pigment for the low-temperature glaze comprises the following components in parts by weight: 89.5 parts of titanium dioxide, 4 parts of vanadium pentoxide and 6.5 parts of antimonous oxide.
Wherein the titanium dioxide is rutile titanium dioxide, the granularity D100 of the titanium dioxide is smaller than 10 mu m, and the purity of the vanadium pentoxide is larger than 99.5%.
The preparation method of the gray pigment for the low-temperature glaze comprises the following steps:
s1: mixing the titanium dioxide, the vanadium pentoxide and the antimonous oxide according to the proportion, uniformly mixing in a mixer, and then carrying out powder grinding treatment in a claw type powder grinding machine to obtain a premixed raw material;
s2: ball milling the pre-mixed raw materials to obtain mixed raw materials, wherein D50 of the mixed raw materials is smaller than 5 mu m;
s3: calcining the mixed raw materials in a kiln to obtain a calcined product, wherein the calcining temperature is 1090 ℃, the heat preservation time is 3 hours, and the total calcining time is 11 hours;
s4: pre-crushing the calcined product to obtain a calcined product with a particle size smaller than 2cm;
s5: carrying out jet milling treatment on the pre-crushed calcined product to obtain calcined powder, wherein the particle size D100 of the calcined powder is smaller than 10 mu m, and the particle size D50 of the calcined powder is 1-1.5 mu m;
s6: and uniformly mixing and stirring the calcined powder to obtain the gray pigment.
Example 4
The gray pigment for the low-temperature glaze comprises the following components in parts by weight: 95 parts of titanium dioxide, 2 parts of vanadium pentoxide and 3 parts of antimonous oxide.
Wherein the titanium dioxide is anatase titanium dioxide, the granularity D100 of the titanium dioxide is smaller than 10 mu m, and the purity of the vanadium pentoxide is larger than 99.5%.
The preparation method of the gray pigment for the low-temperature glaze comprises the following steps:
s1: mixing the titanium dioxide, the vanadium pentoxide and the antimonous oxide according to the proportion, uniformly mixing in a mixer, and then carrying out powder grinding treatment in a claw type powder grinding machine to obtain a premixed raw material;
s2: ball milling the pre-mixed raw materials to obtain mixed raw materials, wherein D50 of the mixed raw materials is smaller than 5 mu m;
s3: calcining the mixed raw materials in a kiln to obtain a calcined product, wherein the calcining temperature is 1110 ℃, the heat preservation time is 2.5h, and the total calcining time is 10.5h;
s4: pre-crushing the calcined product to obtain a calcined product with a particle size smaller than 2cm;
s5: carrying out jet milling treatment on the pre-crushed calcined product to obtain calcined powder, wherein the particle size D100 of the calcined powder is smaller than 10 mu m, and the particle size D50 of the calcined powder is 1-1.5 mu m;
s6: and uniformly mixing and stirring the calcined powder to obtain the gray pigment.
Comparative example 1
Comparative example 1 differs from example 1 in that:
the gray pigment for low temperature glaze further comprises 0.1 part of zinc oxide, step S1: mixing titanium dioxide, vanadium pentoxide, antimony trioxide and zinc oxide according to a proportion, uniformly mixing in a mixer, and performing powder grinding treatment in a claw-type powder grinding machine to obtain a premixed raw material.
Comparative example 2
Comparative example 2 is different from example 1 in that:
the gray pigment for low temperature glaze further comprises 0.4 part of zinc oxide, step S1: mixing titanium dioxide, vanadium pentoxide, antimony trioxide and zinc oxide according to a proportion, uniformly mixing in a mixer, and performing powder grinding treatment in a claw-type powder grinding machine to obtain a premixed raw material.
The prepared gray pigment is applied to glass ink for coloring, the color forming effect is shown in figure 2, the color is in a color without penetrating bottom, and the covering power of the pigment is strong.
Comparative example 3
Comparative example 3 is different from example 1 in that:
the gray pigment for low temperature glaze further comprises 0.4 part of zinc oxide, step S1: mixing titanium dioxide, vanadium pentoxide, antimony trioxide and zinc oxide according to a proportion, uniformly mixing in a mixer, and performing powder grinding treatment in a claw-type powder grinding machine to obtain a premixed raw material; in step S3, the holding time was 2h and the total calcination time was 11h.
Comparative example 4
Comparative example 4 differs from example 1 in that:
the gray pigment for low temperature glaze further comprises 0.4 part of zinc oxide, step S1: mixing titanium dioxide, vanadium pentoxide, antimony trioxide and zinc oxide according to a proportion, uniformly mixing in a mixer, and performing powder grinding treatment in a claw-type powder grinding machine to obtain a premixed raw material; in step S3, the holding time is 1h, and the total calcination time is 10h.
Comparative example 5
Comparative example 5 is different from example 1 in that:
the gray pigment for the low-temperature glaze further comprises 1 part of zinc oxide, and the step S1: mixing titanium dioxide, vanadium pentoxide, antimony trioxide and zinc oxide according to a proportion, uniformly mixing in a mixer, and performing powder grinding treatment in a claw-type powder grinding machine to obtain a premixed raw material; in step S3, the holding time was 1h, and the total calcination time was 11h.
Performance testing
Optical density testing was performed on gray pigments using a densitometer, chromaticity testing was performed on gray pigments using a colorimeter, and the test results of examples 1 to 4 and comparative examples 1 to 5 are shown in table 1. Wherein the value of L: a brightness value; a value: representing a range from green to red; b value: indicating a range from blue to yellow.
Table 1 results of the colorimetric test for examples 1 to 4 and comparative examples 1 to 5
Project OD L a b
Example 1 4.20 47.9 +1.5 -2.7
Example 2 4.10 48.2 +1.5 -2.8
Example 3 4.25 48.4 +1.5 -2.7
Example 4 4.16 49.1 +1.6 -2.8
Comparative example 1 4.27 47.8 +1.5 -2.7
Comparative example 2 4.36 48.2 +1.5 -2.7
Comparative example 3 4.32 48.0 +1.5 -2.7
Comparative example 4 4.18 48.2 +1.6 -2.7
Comparative example 5 4.31 48.0 +1.5 -2.7
The optical density is a representation of the light shielding capacity of the material, the higher the OD value of the optical density is, the higher the covering power is, and as can be seen from the data in table 1, the OD values of examples 1-4 and comparative examples 1-4 are greater than or equal to 4.10, the gray light shielding capacity is strong, the color formation is not transparent when the material is added to low-temperature glaze, and the good covering power is achieved; specifically, the OD value of comparative example 1 was higher than that of example 1, which suggests that the addition of a trace amount of zinc oxide has a large influence on the hiding effect; as the zinc oxide content increases, the greater the OD value, the higher the hiding power; the OD of comparative example 4 was slightly lower than that of example 1 and the OD of comparative example 3 was significantly higher than that of example 1, which suggests that the addition of zinc oxide can promote the solid phase reaction, shorten the reaction time, shorten the calcination time by adding a trace amount of zinc oxide, achieve the desired color forming effect, and effectively reduce the production cost.
As can be seen from the data in Table 1, the gray pigments prepared in examples 1 to 4 and comparative examples 1 to 4 have good gray shades, in which the L values of examples 1 to 4 and comparative examples 1 to 4 are in the range of 47.9 to 49.1, the a values are in the range of +1.5 to +1.6, and the b values are in the range of-2.8 to-2.7.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (10)

1. The gray pigment for the low-temperature glaze is characterized by comprising the following components in parts by weight: 89.5 to 97.5 parts of titanium dioxide, 1 to 4 parts of vanadium pentoxide and 1.5 to 6.5 parts of antimonous oxide, wherein the sum of the weight parts of the titanium dioxide, the vanadium pentoxide and the antimonous oxide is 100 parts.
2. The gray pigment for low-temperature glazes according to claim 1, which comprises the following components in parts by weight: 93.5 parts of titanium dioxide, 2 parts of vanadium pentoxide and 4.5 parts of antimonous oxide.
3. The gray pigment for low temperature glazes according to claim 1, further comprising zinc oxide in an amount of 0.1 to 1 part.
4. A gray pigment for low temperature glazes according to claim 3, which comprises the following components in parts by weight: 93.5 parts of titanium dioxide, 2 parts of vanadium pentoxide, 4.5 parts of antimonous oxide and 0.5 part of zinc oxide.
5. The gray pigment for low-temperature glazes according to claim 1, wherein the titanium pigment is rutile titanium pigment.
6. The gray pigment for low temperature glazes according to claim 1, wherein the particle size D100 of the titanium pigment is less than 10 μm.
7. The gray pigment for low temperature glazes according to claim 1, wherein the purity of the vanadium pentoxide is more than 99.5%.
8. The method for producing a gray pigment for low-temperature glazes according to any one of claims 1 to 7, comprising the steps of:
s1: the components are proportioned according to the proportion, evenly mixed in a mixer, and then subjected to powder grinding treatment in a claw-type powder grinding machine to obtain a premixed raw material;
s2: ball milling the pre-mixed raw materials to obtain mixed raw materials, wherein D50 of the mixed raw materials is smaller than 5 mu m;
s3: calcining the mixed raw materials in a kiln to obtain a calcined product, wherein the calcining temperature is 1090-1150 ℃ and the heat preservation time is 1-3 h;
s4: pre-crushing the calcined product to obtain a calcined product with a particle size smaller than 2cm;
s5: carrying out jet milling treatment on the pre-crushed calcined product to obtain calcined powder, wherein the particle size of the calcined powder is smaller than 10 mu m;
s6: and uniformly mixing and stirring the calcined powder to obtain the gray pigment.
9. The method for producing a gray pigment for low-temperature glazes according to claim 8, wherein in step S5, the calcined powder has a particle diameter D100 of less than 10 μm and a particle diameter D50 of 1 to 1.5 μm.
10. The method for producing a gray pigment for low-temperature glazes according to claim 8, wherein in step S3, the total calcination time of the mixed raw materials is 10 to 12 hours.
CN202311113551.4A 2023-08-31 2023-08-31 Gray pigment for low-temperature glaze and preparation method thereof Pending CN117143467A (en)

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