CN115650247A - Cr/Ni doped Bi 4 Si 3 O 12 Preparation method of green inorganic pigment - Google Patents
Cr/Ni doped Bi 4 Si 3 O 12 Preparation method of green inorganic pigment Download PDFInfo
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Abstract
Cr/Ni doped Bi 4 Si 3 O 12 A green inorganic pigment and a preparation method thereof, belonging to the field of inorganic pigments. The chemical composition general formula of the pigment is Bi 4‑x Cr x Si 3 O 12 And Bi 4‑x Ni x Si 3 O 12 Wherein x is more than or equal to 0 and less than or equal to 0.6. The preparation steps are as follows: first Bi is added 2 O 3 ，SiO 2 ，Cr 2 O 3 Or NiO isStarting material according to Bi 4‑x Cr x Si 3 O 12 (x is more than or equal to 0 and less than or equal to 0.6) or Bi 4‑ x Ni x Si 3 O 12 (x is more than or equal to 0 and less than or equal to 0.6) according to the stoichiometric ratio. Ball milling is carried out for 6-12h by a planetary ball mill at the rotating speed of 200-500 r/min. And (3) putting the uniformly mixed raw material mixture into an oven, and drying for 6-12h at the temperature of 50-80 ℃. Tabletting the dried raw materials under the pressure of 10-30MPa and maintaining the pressure for 1-5min. Subsequently heating in a tube furnace with N 2 Sintering at 900 deg.C for 8-12h in a box furnace at 5-10 deg.C/min and 5-10 deg.C/min. And grinding the sample after the sample is cooled to room temperature to obtain the novel green inorganic pigment. The green inorganic pigment synthesized by the method is environment-friendly, nontoxic, bright in color, simple in preparation process, low in equipment requirement, good in high-temperature stability and chemical stability and expected to be produced industrially.
Description
Technical Field
The invention belongs to the technical field of inorganic pigments, and particularly relates to Cr/Ni doped Bi 4 Si 3 O 12 Green inorganic pigment and a preparation method thereof.
Background
The pigment can be divided into organic pigment and inorganic pigment according to the components, the organic pigment has bright color, but has poor stability, and cannot be used for a long time in a harsher environment, so that the application of the organic pigment is limited. The inorganic pigment has excellent high-temperature stability and chemical stability, is widely applied to various fields such as buildings, plastics, glass, porcelain, art and the like, and has important significance in the production and the life of people. Since natural minerals are rare and precious in color minerals, synthetic inorganic pigments account for a vast proportion of the inorganic pigments currently used. Research shows that the transition metal ions capable of developing color are doped into proper ligands, so that internal molecules are subjected to charge mass transfer and crystal field transition generated by the transition metal ions, and the color is generated. Therefore, the research of suitable oxide matrix and doping ions thereof is an effective means for expanding the preparation and application of inorganic pigments.
Disclosure of Invention
The invention relates to Bi 2 O 3 ，SiO 2 Is prepared from Cr through doping Cr 2 O 3 Or NiO is synthesized into a series of novel green inorganic pigments with adjustable chroma and a preparation method thereof. The novel green inorganic pigment prepared by the invention is realized by the following technical scheme.
Cr/Ni doped Bi 4 Si 3 O 12 Preparation of green inorganic pigmentThe preparation method is characterized in that the structure is a stable silica-type structure, a series of green pigments with adjustable chroma are prepared by adjusting the doping amount of chromium or nickel, and the chemical composition of the green pigments is Bi 4-x Cr x Si 3 O 12 And Bi 4-x Ni x Si 3 O 12 Wherein x is more than or equal to 0 and less than or equal to 0.6; further, the Cr/Ni is doped with Bi 4 Si 3 O 12 The novel green inorganic pigment is characterized in that Bi is +3 valent, si is +4 valent, cr is +3 valent and Ni is +2 valent.
Cr/Ni doped Bi as described above 4 Si 3 O 12 The preparation method of the green inorganic pigment is characterized by comprising the following steps:
(1) With Bi 2 O 3 ，SiO 2 ，Cr 2 O 3 Or NiO is taken as a raw material, and the raw material is accurately weighed by an electronic balance according to the stoichiometric ratio of the pigment phase;
(2) Putting the weighed powder raw materials into a ball milling tank, adding 50mL of absolute ethyl alcohol, and performing ball milling at room temperature by using a planetary ball mill to fully mix the raw materials;
(3) After the ball milling is finished, putting the mixed raw materials into an oven for standing and drying;
(4) And putting the dried raw materials into a tabletting mould, and carrying out dry pressing and forming by using a tabletting machine.
(5) Placing the pressed block into a corundum crucible, heating the corundum crucible in a tubular furnace according to a heating curve in N 2 Sintering at high temperature in atmosphere to obtain Bi 4-x Cr x Si 3 O 12 (0≤x≤0.6)。
(6) Putting the pressed and formed block into a corundum crucible, and sintering at high temperature in a box-type furnace according to a temperature rise curve to obtain Bi 4-x Ni x Si 3 O 12 (0≤x≤0.6)。
Further, the mass error of the raw material in the step (1) is ± 0.0005g.
Further, the ball milling condition in the step (2) is 200-500r/min and 6-12h.
Further, drying for 6-12h in an electrothermal blowing dry box at 50-80 ℃ in the step (3).
Further, the diameter of the tabletting mold in the step (4) is 10-20mm, the sample pressing pressure is 10-30MPa, and the pressure maintaining time is 1-5min.
Further, the sintering temperature of the sample in the step (5) is 900-950 ℃, and the sintering atmosphere is N 2 The sintering time is 8-12h, the heating rate is 5-10 ℃/min, and the cooling rate is 5-10 ℃/min.
Further, in the step (6), the sintering temperature of the sample is 900-950 ℃, the sintering atmosphere is air, the sintering time is 8-12h, the heating rate is 5-10 ℃/min, and the cooling rate is 5-10 ℃/min.
Compared with the prior art, the invention has the following advantages:
(1) The green inorganic pigment has bright color and luster, and the apparent color of the green inorganic pigment can be regulated and controlled by the doping amount of Ni ions and Cr ions.
(2) The green inorganic pigment has stable structure, good structural stability and chemical stability.
(3) The invention does not need to use mineralizer, has simple process and does not introduce other ions because of the use of the mineralizer.
(4) The invention uses absolute ethyl alcohol instead of acetone during ball milling mixing, reduces the use of organic reagents and reduces the harm to human bodies.
(5) The synthesis temperature used in the invention is 900 ℃, the sintering temperature is lower, and the energy is saved.
(6) The invention uses N 2 Atmosphere sintering to avoid generation of Cr with carcinogenic effect 6+ Ionic and therefore the pigment is less toxic.
Drawings
FIG. 1 (a) shows Bi 4-x Cr x Si 3 O 12 (x is more than or equal to 0 and less than or equal to 0.6) XRD pattern of green pigment powder, and (b) is Bi 4-x Ni x Si 3 O 12 (x is more than or equal to 0 and less than or equal to 0.6) an XRD pattern of the green pigment powder;
FIG. 2 (a) shows Bi 4-x Cr x Si 3 O 12 (x is more than or equal to 0 and less than or equal to 0.6) the UV-VIS-NIR spectrum of the green pigment powder, and (b) isBi 4- x Ni x Si 3 O 12 (x is more than or equal to 0 and less than or equal to 0.6) the UV-VIS-NIR spectrum of the green pigment powder.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The examples are merely illustrative of the invention and do not limit the invention. It will be understood by those skilled in the art that various modifications and equivalents may be made to the embodiments of the present invention without departing from the spirit and scope of the invention, and such modifications and equivalents are within the scope of the invention.
Example 1: preparation of 1g of Bi 3.9 Cr 0.1 Si 3 O 12 Inorganic pigments
According to Bi 3.9 Cr 0.1 Si 3 O 12 The chemical formula (A) is that Bi is respectively weighed by an electronic analytical balance according to a certain stoichiometric ratio 2 O 3 (0.8287g)，SiO 2 (0.1644g)，Cr 2 O 3 (0.0069 g), the mass tolerance is ± 0.0005g. The weighed raw materials are poured into a ball milling tank, and 50mL of absolute ethyl alcohol is added for ball milling for 10 hours. And after the ball milling is finished, putting the mixed raw materials into an oven, standing and drying for 10 hours. And putting the dried mixed raw materials into a stainless steel die with the diameter of 15mm, pressurizing the die through a tablet machine, and maintaining the pressure for 1min under the pressure of 10 MPa. Putting the pressed cylindrical block into a corundum crucible, putting the corundum crucible into a tube furnace, and adding N 2 Raising the temperature of the box furnace to 900 ℃ at the temperature rise rate of 5 ℃/min in the atmosphere, preserving the heat for 12h at the temperature of 900 ℃, reducing the temperature to room temperature at the temperature drop rate of 5 ℃/min after the heat preservation is finished, and finally taking out a sample and grinding to obtain the stable green inorganic pigment.
Example 2: preparation of 1g of Bi 3.9 Cr 0.4 Si 3 O 12 Inorganic pigments
According to Bi 3.9 Cr 0.4 Si 3 O 12 The chemical formula (A) is that Bi is respectively weighed by an electronic analytical balance according to a certain stoichiometric ratio 2 O 3 (0.7993g)，SiO 2 (0.1718g)，Cr 2 O 3 (0.0290 g), and the mass tolerance was. + -. 0.0005g. Will call outThe weighed raw materials are poured into a ball milling tank, 50mL of absolute ethyl alcohol is added, and ball milling is carried out for 12 hours. And after the ball milling is finished, putting the mixed raw materials into an oven, standing and drying for 12 hours. And putting the dried mixed raw materials into a stainless steel die with the diameter of 15mm, pressurizing the die through a tablet machine, and maintaining the pressure for 1min under the pressure of 15 MPa. Putting the pressed cylindrical block into a corundum crucible, putting the corundum crucible into a tubular furnace, and adding N 2 And (3) raising the temperature of the box furnace to 950 ℃ at a heating rate of 5 ℃/min in the atmosphere, preserving the heat for 12h at the temperature of 950 ℃, reducing the temperature to room temperature at a cooling rate of 5 ℃/min after the heat preservation is finished, and finally taking out a sample and grinding to obtain the stable green inorganic pigment.
Example 3: preparation of 2g of Bi 3.4 Ni 0.6 Si 3 O 12 Inorganic pigments
According to Bi 3.4 Cr 0.6 Si 3 O 12 Chemical formula (2), respectively weighing Bi by an electronic analytical balance according to a certain stoichiometric ratio 2 O 3 (1.5502g)，SiO 2 (0.3527 g), niO (0.0877 g), with a mass tolerance of. + -. 0.0005g. The weighed raw materials are poured into a ball milling tank, and 50mL of absolute ethyl alcohol is added for ball milling for 6 hours. And after the ball milling is finished, putting the mixed raw materials into an oven, standing and drying for 8 hours. And putting the dried mixed raw materials into a stainless steel die with the diameter of 15mm, pressurizing the die through a tablet machine, and maintaining the pressure for 2min under the pressure of 20 MPa. And (3) placing the pressed cylindrical block into a corundum crucible, then placing the corundum crucible into a box furnace, raising the temperature of the box furnace to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat at the temperature of 900 ℃ for 12 hours, reducing the temperature to room temperature at the cooling rate of 5 ℃/min after the heat preservation is finished, and finally taking out a sample and grinding to obtain the stable green inorganic pigment.
Claims (7)
1. Cr/Ni doped Bi 4 Si 3 O 12 The preparation method of green inorganic pigment is characterized by that its structure is stable silica type structure, and utilizes the regulation of chromium or nickel doping quantity to prepare a series of green pigments whose chroma can be regulated, and its chemical composition is Bi 4- x Cr x Si 3 O 12 And Bi 4-x Ni x Si 3 O 12 Wherein x is more than or equal to 0 and less than or equal to 0.6(ii) a Bi is +3 valence, si is +4 valence, cr is +3 valence, and Ni is +2 valence; the preparation steps are as follows: first Bi is added 2 O 3 ，SiO 2 ，Cr 2 O 3 Or NiO, according to Bi 4-x Cr x Si 3 O 12 (x is not less than 0 and not more than 0.6) and Bi 4-x Ni x Si 3 O 12 (x is more than or equal to 0 and less than or equal to 0.6) according to the stoichiometric ratio, and the green inorganic pigment is prepared by mixing, grinding, briquetting and sintering.
2. The Cr/Ni-doped Bi according to claim 1 4 Si 3 O 12 The preparation method of the green inorganic pigment is characterized by comprising the following steps:
(1) With Bi 2 O 3 ，SiO 2 ，Cr 2 O 3 Or NiO is taken as a raw material, and the raw material is accurately weighed by an electronic balance according to the stoichiometric ratio of the pigment phase;
(2) Putting the weighed powder raw materials into a ball milling tank, adding 50mL of absolute ethyl alcohol, and performing ball milling at room temperature by using a planetary ball mill to fully mix the raw materials;
(3) After the ball milling is finished, putting the mixed raw materials into an oven for standing and drying;
(4) Putting the dried raw materials into a tabletting mould, and carrying out dry pressing and forming by using a tabletting machine;
(5) Placing the pressed block into a corundum crucible, heating the corundum crucible in a tubular furnace according to a heating curve in N 2 Sintering at high temperature in atmosphere to obtain Bi 4-x Cr x Si 3 O 12 (0≤x≤0.6)；
(6) Putting the pressed and formed block into a corundum crucible, and sintering at high temperature in a box-type furnace according to a temperature rise curve to obtain Bi 4-x Ni x Si 3 O 12 (0≤x≤0.6)。
3. The Cr/Ni-doped Bi according to claim 2 4 Si 3 O 12 A process for producing a green inorganic pigment, characterized in that the mass error of the raw materials in the step (1) is. + -. 0.0005g.
4. The Cr/Ni-doped Bi according to claim 2 4 Si 3 O 12 The preparation method of the green inorganic pigment is characterized in that the grinding condition in the step (2) is that a planetary ball mill is used for ball milling for 6-12h at the rotating speed of 200-500 r/min.
5. The Cr/Ni-doped Bi of claim 2 4 Si 3 O 12 The preparation method of the green inorganic pigment is characterized in that the diameter of the tabletting mold in the step (3) is 10-20mm, the sample pressing pressure is 10-30MPa, and the pressure maintaining time is 1-5min.
6. The Cr/Ni doped Bi of claim 2 4 Si 3 O 12 The preparation method of the green inorganic pigment is characterized in that the sintering temperature in the step (4) is 900-950 ℃, the sintering time is 8-12h, and the sintering atmosphere is N 2 The heating rate is 5-10 ℃/min, and the cooling rate is 5-10 ℃/min.
7. The Cr/Ni-doped Bi according to claim 2 4 Si 3 O 12 The preparation method of the green inorganic pigment is characterized in that the sintering temperature in the step (5) is 900-950 ℃, the sintering time is 8-12h, the sintering atmosphere is air, the heating rate is 5-10 ℃/min, and the cooling rate is 5-10 ℃/min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4002943A1 (en) * | 1990-02-01 | 1991-08-08 | Bayer Ag | Stable bismuth chromium zirconium oxide mix phase pigment for lacquer - or plastics and prepd. by calcining co-precipitate or oxide mixt. or precursor |
| CN105968889A (en) * | 2016-05-11 | 2016-09-28 | 西安英诺维特新材料有限公司 | Low temperature lead-free green glass paste |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4002943A1 (en) * | 1990-02-01 | 1991-08-08 | Bayer Ag | Stable bismuth chromium zirconium oxide mix phase pigment for lacquer - or plastics and prepd. by calcining co-precipitate or oxide mixt. or precursor |
| CN105968889A (en) * | 2016-05-11 | 2016-09-28 | 西安英诺维特新材料有限公司 | Low temperature lead-free green glass paste |
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