CN111849204A - Chromophoric group cobalt-free blue glass pigment and method - Google Patents
Chromophoric group cobalt-free blue glass pigment and method Download PDFInfo
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- CN111849204A CN111849204A CN202010737963.5A CN202010737963A CN111849204A CN 111849204 A CN111849204 A CN 111849204A CN 202010737963 A CN202010737963 A CN 202010737963A CN 111849204 A CN111849204 A CN 111849204A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT 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
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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Abstract
The invention belongs to the field of glass decorative pigments, and relates to a cobalt-free blue glass pigment with a chromophoric group and a method thereof, wherein the chromophoric group is prepared from the following raw materials in percentage by mass: 37.0-58.0% of yttrium oxide, 5.6-54.0% of indium oxide, 1.0-36.0% of manganese oxide and 0.1-20% of auxiliary agent. The cobalt-free blue glass pigment is prepared from 5.0-30.0% by mass of chromophoric groups and a lead-free cooling flux: 70.0-95.0%. The invention has the advantages that: (1) the rare earth element is a chromophoric group which mainly comprises the rare earth element, does not contain cobalt element and meets the requirement of food sanitation and safety; (2) a low-temperature chromophoric group is prepared, and the chromophoric group has deep color when being compounded with a glass flux; (3) the composition of the chromophoric group influences the alkali resistance of the glass pigment, and alkali resistance meeting the product requirement is screened from a plurality of groups of formulas of the blue glass pigment.
Description
Technical Field
The invention belongs to the field of glass decoration pigments, and relates to a blue glass pigment containing no cobalt and a chromophoric group and a method.
Background
The glass pigment is sintered with glass product through roasting to decorate glass, and this method has the advantages of strong adhesion and good weather resistance. Is widely applied to the decoration of vessel glass, in particular recyclable glass beverage bottles, such as recyclable cola bottles, beer bottles, milk bottles and the like. One of the basic colors of blue is cobalt and aluminum or a sintered product of cobalt and silicon, which is the composition of blue glass pigment containing cobalt. In 2017, the world health organization international agency for research on cancer published cobalt and cobalt compounds in the list of class 2B carcinogens. The use of cobalt-free pigments is a future trend in view of food safety concerns for recycling beverage bottles.
The lead-free glass flux for recoverable glassware, which must meet food safety requirements, functionally has a resistance to alkali, has a system temperature in a fixed range, typically 500 to 650 ℃. Many inorganic composite oxide chromophoric groups roasted at 1100-1300 ℃ have light chromophoric colors when being compounded with glass flux, for example, the colors of sky blue of a vanadium-zirconium system and black of a cobalt-chromium system cannot meet the process requirements.
Disclosure of Invention
In light of the above deficiencies of the prior art, the present invention provides a chromophore, cobalt-free blue glass pigment and method
The chromophoric group is characterized by being prepared from the following raw materials in percentage by mass: 37.0-58.0% of yttrium oxide, 5.6-54.0% of indium oxide, 1.0-36.0% of manganese oxide and 0.1-20% of auxiliary agent.
Furthermore, the auxiliary agent is potassium fluoroaluminate and/or potassium carbonate.
In the present invention, the indium-yttrium composite metal oxide YINO3Has a unique triangular double-cone structure, when In3+Quilt Mn3+During substitution, the selective absorption of the visible spectrum is caused by the change of lattice distortion, ionic radius and orbital splitting energy, and a characteristic reflection peak appears at 400-500 nm, so that the composite metal oxide YIn1-xMnxO3Exhibits a blue hue and is accompanied by Mn3+The higher the occupancy of (b), the darker the blue hue. The auxiliary agent is potassium fluoroaluminate and/or potassium carbonate, and does not react with YIn in a solid-phase reaction system during the reaction1-xMnxO3The eutectic is formed instead of chemical reaction, so that a liquid phase appears at a lower temperature in the system, the diffusion and the dissolution of the solid are accelerated, and the solid reaction kinetics are promoted. In addition, it has polarization effect on the reaction ions to promote the system lattice distortion, pair YIn1-xMnxO3The color development of (2) also has a promoting effect.
The invention also provides a preparation method of the chromophoric group, which is carried out according to the following steps:
(1) putting yttrium oxide, indium oxide and manganese oxide into a ball mill, and grinding until the average particle size is 2.0 microns;
(2) continuously adding the auxiliary agent into the ball mill, continuously grinding until the average particle size is 1.5 microns, and then drying and crushing the materials until the materials are completely sieved by a 400-mesh sieve;
(3) placing the sieved powder in a refractory sagger, heating and roasting in air atmosphere, wherein a temperature rise curve is divided into two sections: in the first stage, the temperature is controlled to be between room temperature and 800 ℃, and the heating rate is controlled to be between 10 and 20 ℃/min; and in the second stage, the temperature is controlled to be between 1100 and 1200 ℃ from 800 ℃ to the set temperature, the heating rate is controlled to be between 5 and 10 ℃/min, the temperature is kept for 2 hours after the set temperature is reached, and the temperature is naturally cooled.
The cobalt-free blue glass pigment is prepared from the chromophoric group disclosed in claim 1 and a lead-free temperature reduction flux in a mass percentage of 5.0-30.0%: 70.0-95.0%.
Furthermore, the lead-free temperature-reducing flux is a powdered glass flux.
The invention also provides a preparation method of the cobalt-free blue glass pigment, which is characterized by comprising the following steps of: mixing the chromophoric group and the lead-free cooling flux in a ball mill, grinding the mixture by taking water as a grinding medium until the average particle size is 1.5 microns, drying the mixture, crushing the dried mixture, and sieving the crushed mixture by a 400-mesh sieve until the residue on the sieve is less than 0.5 wt%, thus obtaining the finished product.
The invention has the advantages that: (1) the rare earth element is a chromophoric group which mainly comprises the rare earth element, does not contain cobalt element and meets the requirement of food sanitation and safety; (2) a low-temperature chromophoric group is prepared, and the chromophoric group has deep color when being compounded with a glass flux; (3) the composition of the chromophoric group influences the alkali resistance of the glass pigment, and alkali resistance meeting the product requirement is screened from a plurality of groups of formulas of the blue glass pigment.
Detailed Description
The present invention will be further described with reference to examples and comparative examples.
Examples 1-3 and comparative examples 1-3 chromophoric groups and cobalt-free blue glass pigments were prepared according to the following formulations and parameter settings:
the above examples and comparative examples were carried out in the preparation of the chromophoric groups according to the following procedure:
(1) putting yttrium oxide, indium oxide and manganese oxide into a ball mill, and grinding until the average particle size is 2.0 microns;
(2) continuously adding the auxiliary agent into the ball mill, continuously grinding until the average particle size is 1.5 microns, and then drying and crushing the materials until the materials are completely sieved by a 400-mesh sieve;
(3) placing the sieved powder in a refractory sagger, heating and roasting in air atmosphere, wherein a temperature rise curve is divided into two sections: in the first stage, the temperature is controlled to be between room temperature and 800 ℃, and the heating rate is controlled to be between 10 and 20 ℃/min; and in the second stage, the temperature is controlled to be between 1100 and 1200 ℃ from 800 ℃ to the set temperature, the heating rate is controlled to be between 5 and 10 ℃/min, the temperature is kept for 2 hours after the set temperature is reached, and the temperature is naturally cooled.
The above examples and comparative examples were carried out in the preparation of a cobalt-free blue glass pigment according to the following procedure: mixing the chromophoric group and the lead-free cooling flux in a ball mill, grinding the mixture by taking water as a grinding medium until the average particle size is 1.5 microns, drying the mixture, crushing the dried mixture, and sieving the crushed mixture by a 400-mesh sieve until the residue on the sieve is less than 0.5 wt%, thus obtaining the finished product.
The Lab color model is a color model published by the International Commission on illumination (CIE) in 1976 and has an L value of 0 (white) to 100 (black). a comprises colors from dark green (low brightness value) to gray (medium brightness value) to bright pink (high brightness value); b is from bright blue (low brightness value) to gray (medium brightness value) to yellow (high brightness value).
The alkali resistance test method is described in ASTM C675-1991 (American society for testing and materials Standard-test method for alkali resistance of ceramic decorations on reusable glass beverage bottles).
In contrast to the firing temperatures of the above schemes, the firing temperature referred to herein is the lowest firing temperature at which the entire system develops color sufficiently, wherein the firing temperature of comparative example 1 is the highest, and the firing temperatures of other examples and comparative examples are reduced to different degrees because comparative example 1 does not contain any auxiliary components to reduce the temperature.
Comparative example 1 is the lightest comparing the L values of the above schemes because there is no component to lower the chromophoric group temperature. Comparative examples 2 and 3 were dark in color. However, the alkali resistance of comparative examples 2 and 3 did not meet the functional requirements of glass pigments. Therefore, by comparison, one or two of potassium fluoroaluminate and potassium carbonate are selected.
Examples 1, 2 and 3, potassium fluoroaluminate, potassium carbonate, potassium fluoroaluminate and potassium carbonate, respectively, show different effects in the following respects:
(1) compared with the example 1 and the example 2 with the same addition amount, the roasting temperature of the example 1 is high, and the roasting temperature of the example 2 is low, which shows that the cooling effect of the potassium fluoroaluminate is not as good as that of the potassium carbonate. Correspondingly, example 2 is deeper than example 1 in L value. Further, comparing the b values of the two, example 2 is darker in blue than example 1.
(2) In example 3, although the addition amount of the auxiliary agent is high, the roasting temperature of the example 2 is the same as that of the example 3, which shows that the additive effect on the temperature reduction cannot be realized. However, the L value in example 3 is deeper than in examples 1 and 2, and it is demonstrated that the combination has a superimposed effect on the depth of color development, and that the increase in the amount of the auxiliary added promotes the solid reaction kinetics and the lattice distortion, and increases the color development intensity.
Claims (6)
1. The chromophoric group is characterized by being prepared from the following raw materials in percentage by mass: 37.0-58.0% of yttrium oxide, 5.6-54.0% of indium oxide, 1.0-36.0% of manganese oxide and 0.1-20% of auxiliary agent.
2. A chromophoric group according to claim 1, wherein: the auxiliary agent is potassium fluoroaluminate and/or potassium carbonate.
3. A process for the preparation of the chromophoric group according to claim 1 or 2, which comprises the following steps:
(1) putting yttrium oxide, indium oxide and manganese oxide into a ball mill, and grinding until the average particle size is 2.0 microns;
(2) continuously adding the auxiliary agent into the ball mill, continuously grinding until the average particle size is 1.5 microns, and then drying and crushing the materials until the materials are completely sieved by a 400-mesh sieve;
(3) placing the sieved powder in a refractory sagger, heating and roasting in air atmosphere, wherein a temperature rise curve is divided into two sections: in the first stage, the temperature is controlled to be between room temperature and 800 ℃, and the heating rate is controlled to be between 10 and 20 ℃/min; and in the second stage, the temperature is controlled to be between 1100 and 1200 ℃ from 800 ℃ to the set temperature, the heating rate is controlled to be between 5 and 10 ℃/min, the temperature is kept for 2 hours after the set temperature is reached, and the temperature is naturally cooled.
4. A cobalt-free blue glass pigment characterized by: the chromophoric group of claim 1 and the lead-free temperature-reducing flux are 5.0-30.0% by mass: 70.0-95.0%.
5. A cobalt-free blue glass pigment according to claim 4, characterized in that: the lead-free temperature-reducing flux is a powdery glass flux.
6. A process for the preparation of a cobalt-free blue glass pigment according to claim 4 or 5, characterized in that it is carried out according to the following steps: mixing the chromophoric group and the lead-free cooling flux in a ball mill, grinding the mixture by taking water as a grinding medium until the average particle size is 1.5 microns, drying the mixture, crushing the dried mixture, and sieving the crushed mixture by a 400-mesh sieve until the residue on the sieve is less than 0.5 wt%, thus obtaining the finished product.
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| CN202010737963.5A CN111849204A (en) | 2020-07-28 | 2020-07-28 | Chromophoric group cobalt-free blue glass pigment and method |
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| CN202010737963.5A CN111849204A (en) | 2020-07-28 | 2020-07-28 | Chromophoric group cobalt-free blue glass pigment and method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105755A (en) * | 2021-04-06 | 2021-07-13 | 包头中科世纪科技有限责任公司 | Novel inorganic blue pigment of rare earth oxide doped indium and transition metal oxide and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| US20100317503A1 (en) * | 2009-06-11 | 2010-12-16 | State of Oregon acting by and through the State Board of Higher Education on behalf of | Materials with trigonal bipyramidal coordination and methods of making the same |
| CN103708849A (en) * | 2013-12-20 | 2014-04-09 | 佛山市三水区康立泰无机合成材料有限公司 | Color material for ceramic ink-jet printing and preparation method thereof |
| CN105419393A (en) * | 2015-11-25 | 2016-03-23 | 赖清甜 | Corrosion-resistant blue ceramic pigment and preparation method thereof |
| CN110437648A (en) * | 2019-09-10 | 2019-11-12 | 江西陶瓷工艺美术职业技术学院 | A kind of width colour gamut is free of the blue ceramic pigment of chromium, cobalt, vanadium |
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- 2020-07-28 CN CN202010737963.5A patent/CN111849204A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100317503A1 (en) * | 2009-06-11 | 2010-12-16 | State of Oregon acting by and through the State Board of Higher Education on behalf of | Materials with trigonal bipyramidal coordination and methods of making the same |
| CN103708849A (en) * | 2013-12-20 | 2014-04-09 | 佛山市三水区康立泰无机合成材料有限公司 | Color material for ceramic ink-jet printing and preparation method thereof |
| CN105419393A (en) * | 2015-11-25 | 2016-03-23 | 赖清甜 | Corrosion-resistant blue ceramic pigment and preparation method thereof |
| CN110437648A (en) * | 2019-09-10 | 2019-11-12 | 江西陶瓷工艺美术职业技术学院 | A kind of width colour gamut is free of the blue ceramic pigment of chromium, cobalt, vanadium |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113105755A (en) * | 2021-04-06 | 2021-07-13 | 包头中科世纪科技有限责任公司 | Novel inorganic blue pigment of rare earth oxide doped indium and transition metal oxide and preparation method thereof |
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