CN115572494B - Red brown ceramic pigment, preparation method thereof and application thereof in ceramic inkjet printing ink - Google Patents
Red brown ceramic pigment, preparation method thereof and application thereof in ceramic inkjet printing ink Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 145
- 239000000049 pigment Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000004615 ingredient Substances 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 10
- 239000000976 ink Substances 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 29
- 238000010304 firing Methods 0.000 claims description 28
- 239000003086 colorant Substances 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 20
- 238000011161 development Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 15
- 239000011885 synergistic combination Substances 0.000 abstract description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 96
- 230000000052 comparative effect Effects 0.000 description 52
- 239000011787 zinc oxide Substances 0.000 description 48
- 230000005389 magnetism Effects 0.000 description 13
- 238000005245 sintering Methods 0.000 description 11
- 230000005291 magnetic effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000001058 brown pigment Substances 0.000 description 9
- 238000004321 preservation Methods 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000005415 magnetization Effects 0.000 description 7
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C09C1/0009—Pigments for ceramics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Abstract
The invention belongs to the technical field of ceramic pigment, and provides a reddish brown ceramic pigment, a preparation method thereof and application thereof in ceramic inkjet printing ink, wherein the preparation method comprises the following steps: fe2O3 and ZnO are mixed according to a mass ratio of 160:81-105 ingredients, uniformly stirring, presintering for 4-6 hours at 950-1000 ℃, crushing and fine processing to obtain presintering materials; 45-53 parts of presintered material, 30-36 parts of Cr2O3, 16-19 parts of ZnO and 0.2-0.5 part of V2O5 are mixed uniformly, and are fired for 5-7 hours at 1160-1200 ℃ for crushing and fine treatment, thus obtaining the red brown ceramic pigment. In the preparation method, the color development performance is ensured and meanwhile the weak-magnetism red-brown ceramic pigment can be obtained through the synergistic combination of the presintering process, the raw material proportion of the presintering material and the pigment and a small amount of V2O5, so that the quality of the red-brown ceramic ink-jet printing ink can be further improved.
Description
Technical Field
The invention relates to the technical field of ceramic pigments, in particular to a reddish brown ceramic pigment, a preparation method thereof and application thereof in ceramic inkjet printing ink.
Background
Ceramic inkjet printing technology has undergone less than ten years of development and has essentially replaced the original conventional printing technology. In recent years, various ceramic tile products with wood grain imitation and marble patterns are popular, and the design style is widely used for all-polished glaze, archaized bricks and ceramic rock plate products, so that the red-brown ceramic ink-jet printing ink is one of the most important colors, and the use amount of the red-brown ceramic ink-jet printing ink is also rapidly increased.
At present, the pigment in the commercial red brown ceramic ink is basically prepared by adopting a traditional solid phase method, namely, the pigment is prepared by homogenizing raw materials of chromium oxide, ferric oxide and zinc oxide according to a certain proportion and then firing at high temperature. For example, publication number CN109401437a provides a red brown pigment for ceramic inkjet printing and a method for producing the same, the crystal phase of which is composed of zinc ferrite spinel, zinc chromium spinel and zinc aluminum spinel, wherein the weight percentage of the zinc chromium spinel in the red brown pigment is 40-45%; in the red brown pigment, the mass ratio of the zinc ferrite spinel to the zinc chromium spinel is 1.1-1.2:1, a step of; the invention adopts chemical raw materials, has low cost, and the obtained red brown pigment has bright color, high redness value and stable color, and when the prepared red brown pigment is used for ceramic inkjet printing, the color development of the obtained ceramic ink is stable, and the color gamut range of the pigment is widened. However, the applicant found that the red brown pigment prepared by the invention has strong magnetism as the red brown pigment produced by the prior art, and the ceramic ink-jet printing ink prepared by the red brown pigment has high magnetism, so that on one hand, the pigment particles are easy to attract each other in the ink, and agglomeration and precipitation of the particles are accelerated; on the other hand, since magnetic coloring material particles are easily adsorbed to some corners inside the nozzle hole to cause abnormal printing, these ceramic inkjet printing inks are easily aggregated and clogged in the nozzle. Therefore, there is a need to develop a red-brown pigment for a weakly magnetic ceramic inkjet printing ink.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a reddish brown ceramic pigment, a preparation method and application thereof, so as to prepare the reddish brown ceramic pigment which is weak in magnetism and suitable for ceramic ink-jet printing ink, and further improve the quality of the existing reddish brown ceramic ink-jet printing ink.
Based on the above, the invention discloses a preparation method of a reddish brown ceramic pigment, which comprises the following preparation steps:
step S1, preparation of a presintering material (namely presintering process):
fe is added to 2 O 3 And ZnO in a mass ratio of 160:81-105, stirring uniformly, presintering for 4-6h at 950-1000 ℃,crushing and fine-processing the presintered powder to obtain presintered material;
step S2, preparing the pigment:
45-53 parts of presintering material and 30-36 parts of Cr 2 O 3 16-19 parts of ZnO and 0.2-0.5 part of V 2 O 5 And (3) preparing materials, stirring uniformly, firing for 5-7 hours at 1160-1200 ℃, and crushing and refining the fired pigment to obtain the red brown ceramic pigment.
Preferably, in the step S1, fe is added to 2 O 3 And ZnO in a mass ratio of 160: 81-89.
Further preferably, in the step S2, 45.2-52.7 parts of pre-sintering material and 30.3-35.6 parts of Cr are mixed 2 O 3 16.6-19 parts of ZnO and 0.2-0.4 part of V 2 O 5 And (5) batching.
Further preferably, in the step S1, fe is added to 2 O 3 And ZnO in a mass ratio of 160:81, and the ingredients are dosed.
In the invention, fe in the presintered material is optimized 2 O 3 And ZnO, so as to further improve the color development performance of the red brown ceramic pigment while obtaining the red brown ceramic pigment with weak magnetism.
Still more preferably, in the step S2, 45.2 parts of the presintered material and 35.6 parts of Cr are mixed 2 O 3 19 parts of ZnO and 0.2 part of V 2 O 5 And (5) batching.
In the invention, the raw material Fe of the presintered material is optimized 2 O 3 And ZnO, and further optimizing the raw materials (i.e. presintered material and Cr 2 O 3 、ZnO、V 2 O 5 ) The content of the red brown ceramic pigment is such that the prepared red brown ceramic pigment has excellent weak magnetism and color development performance at the same time, and further the stability and the inkjet printing performance (the inkjet printing performance is shown in: ink is not prone to problems such as agglomeration, settling, clogging of the jets and filters).
Preferably, in the step S1, the fineness of the pre-sintered material is less than or equal to 325 mesh; in the step S2, the fineness of the red brown ceramic pigment is less than or equal to 325 meshes. The fineness of the presintered material and the red-brown ceramic pigment is strictly controlled so as to meet the preparation requirement of the ceramic inkjet printing ink.
Preferably, in the step S1 and the step S2, a mixer, preferably a screw mixer, is used for stirring, so as to ensure that the materials are fully and uniformly stirred and better adapt to batch and continuous preparation modes; the tunnel kiln is adopted for presintering and firing, so that the continuous large-scale preparation requirement is met, the fuel is saved, the preparation period is shortened, and the presintering and firing quality is improved; crushing and fine treatment are carried out by adopting a powder grinding machine, so that the fine treatment process is more convenient, efficient, sanitary and safe.
The invention also discloses a reddish brown ceramic pigment, which is prepared by adopting the preparation method disclosed by the invention.
The invention also discloses an application of the reddish brown ceramic pigment in ceramic inkjet printing ink, which comprises the following steps: mixing the dispersing agent with the solvent, stirring and dispersing, adding the red brown ceramic pigment, and grinding to obtain the ceramic inkjet printing ink.
Preferably, the solid content of the ceramic ink-jet printing ink is 35-45 percent, and the fineness D 50 0.3-0.5 μm; so that the ceramic ink-jet printing ink can better meet the requirement of ink-jet printing.
Compared with the prior art, the invention at least comprises the following beneficial effects:
1. the applicant has found through experiments that, in the process of preparing the reddish brown ceramic pigment, feCr is introduced into the reddish brown ceramic pigment 2 O 4 The reddish brown ceramic pigment will generate magnetism, feCr 2 O 4 The higher the content, the stronger the magnetism of the reddish brown ceramic pigment; moreover, if the Fe is not consumed by the way of presintering material 2 O 3 To make it form ZnFe with ZnO in advance 2 O 4 Pre-sintering material, unreacted Fe 2 O 3 Fe is generated at high temperature 3 O 4 Thereby making the red-brown ceramic pigment magnetic. Thus, to avoid FeCr 2 O 4 And/or Fe 3 O 4 In the preparation method of the present invention, fe is prepared first 2 O 3 And ZnO, and controlling Fe in the preparation process of the pre-sintered material 2 O 3 And ZnO, adopting a pre-sintering process with a small excess of ZnO to ensure that Fe 2 O 3 As complete a formation of ZnFe as possible 2 O 4 Thereby weakening the magnetism of the prepared red-brown ceramic pigment. Further, the applicant found that if the amount of ZnO added is further increased during the preparation of the pre-firing material, the magnetism of the red-brown ceramic colorant can be further reduced, but that excessive ZnO in the pre-firing material affects the color development performance of the red-brown ceramic colorant and ink.
2. V is introduced in the process of preparing the red brown ceramic pigment 2 O 5 The magnetism of the prepared red-brown ceramic pigment can be further weakened. At the same time V 2 O 5 Has good fluxing effect, is introduced in a small amount, can improve the reaction degree of the raw materials in the preparation process of the red brown ceramic pigment, and reduces the firing temperature. The experiment shows that 0.2-0.5 part of V is introduced 2 O 5 The firing temperature can be reduced by 30-50 ℃.
3. In addition, in the process of preparing the red brown ceramic pigment, znCr generated by firing 2 O 4 With ZnFe 2 O 4 The relative content of the two can be adjusted to achieve the purpose of adjusting the color.
In summary, in the preparation method of the present invention, fe is prepared in advance 2 O 3 And ZnO, and for Fe in the pre-sintered material 2 O 3 The mass ratio of the catalyst to ZnO is strictly controlled, and the pre-sintering material and Cr are strictly regulated and controlled 2 O 3 And ZnO content, and small amount of V is also added 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the Thus, through the presintering process, the raw material proportion of presintering material and pigment and a small amount of V 2 O 5 The synergistic combination of the above can ensure the color development performance and obtain the weak magnetic reddish brown ceramic pigment, so that the quality of reddish brown ceramic ink-jet printing ink can be further improved.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
The preparation method of the red-brown ceramic pigment comprises the following preparation steps:
step 1, preparing a presintering material:
will F e2 O 3 And ZnO according to m (Fe 2 O 3 ): m (ZnO) =160: 81, placing the mixture into a spiral mixer, uniformly stirring, then placing the mixture into a tunnel kiln for pre-firing, wherein the firing temperature is 990 ℃, the heat preservation time is 4 hours, crushing and fine processing are carried out on the pre-fired powder by using a powder grinding machine until the fineness is 325 meshes of all-pass or smaller, and the pre-fired material is obtained.
Step 2, preparing pigment:
the pre-sintering material and the rest raw materials are mixed according to the following formula in parts by weight:
placing the ingredients into a spiral mixer for stirring uniformly, then placing the ingredients into a tunnel kiln for firing, wherein the firing temperature is 1190 ℃ and the heat preservation time is 6 hours, crushing and fine processing are carried out on the fired pigment through a powdering machine until the fineness is 325 meshes or less, thus obtaining the red brown ceramic pigment of the embodiment, and bagging for later use.
Example 2
The preparation method of the red-brown ceramic pigment comprises the following preparation steps:
step 1, preparing a presintering material:
will F e2 O 3 And ZnO according to m (Fe 2 O 3 ): m (ZnO) =160: 85, placing the mixture into a spiral mixer, uniformly stirring, then placing the mixture into a tunnel kiln for presintering, wherein the sintering temperature is 970 ℃, the heat preservation time is 5 hours, crushing and fine processing are carried out on the presintered powder by using a powder grinding machine until the fineness is 325 meshes of full pass or less, and the presintering material is obtained.
Step 2, preparing pigment:
the pre-sintering material and the rest raw materials are mixed according to the following formula in parts by weight:
placing the ingredients into a spiral mixer for stirring uniformly, then placing the ingredients into a tunnel kiln for firing, wherein the firing temperature is 1180 ℃, the heat preservation time is 5 hours, crushing and fine processing are carried out on the fired pigment through a powdering machine until the fineness is 325 meshes or less, and the red brown ceramic pigment of the embodiment is obtained and is packaged for standby.
Example 3
The preparation method of the red-brown ceramic pigment comprises the following preparation steps:
step 1, preparing a presintering material:
will F e2 O 3 And ZnO according to m (Fe 2 O 3 ): m (ZnO) =160: 89, mixing materials, placing the materials into a spiral mixer, uniformly stirring, placing the materials into a tunnel kiln for presintering, wherein the sintering temperature is 950 ℃, the heat preservation time is 6 hours, crushing and fine processing are carried out on the presintered powder by using a powder grinding machine until the fineness is 325 meshes full-pass or smaller, and the presintering materials are obtained.
Step 2, preparing pigment:
the pre-sintering material and the rest raw materials are mixed according to the following formula in parts by weight:
placing ingredients into a spiral mixer for uniformly stirring, then placing the ingredients into a tunnel kiln for firing, wherein the firing temperature is 1160 ℃, the heat preservation time is 5 hours, crushing and fine processing are carried out on the fired pigment through a powdering machine until the fineness is 325 meshes or less, and then the red brown ceramic pigment of the embodiment is obtained and is packaged for standby.
Example 4
The preparation method of the red-brown ceramic pigment in this embodiment specifically refers to embodiment 1, and differs from embodiment 1 only in that: in step 1, F e2 O 3 And ZnO according to m (Fe 2 O 3 ): m (ZnO) =160: 105.
Thus, referring again to step 1-2 of example 1, the red brown ceramic colorant of this example is prepared and bagged for use.
Comparative example 1
The preparation method of the red brown ceramic pigment of the comparative example comprises the following preparation processes:
not preparing Fe 2 O 3 And ZnO, but directly adding Fe to the pre-sintered material 2 O 3 、Cr 2 O 3 ZnO and V 2 O 5 The actual weight parts of each oxide used in the red brown ceramic colorant of example 1 were compounded as follows:
after the ingredients are mixed, the ingredients are placed in a spiral mixer to be stirred uniformly, then the mixture is placed in a tunnel kiln to be fired, the firing temperature is 1190 ℃, the heat preservation time is 6 hours, the fired pigment is crushed and fine treated by a powder grinding machine until the fineness is 325 meshes full-pass or smaller, and the red brown ceramic pigment of the comparative example is obtained and is packaged for standby.
Comparative example 2
The preparation method of the red-brown ceramic pigment of the comparative example, specifically referring to example 1, is different from example 1 only in that: in step 1, F e2 O 3 And ZnO according to m (Fe 2 O 3 ): m (ZnO) =180: 81, and the ingredients are dosed.
Thus, referring again to step 1-2 of example 1, the red brown ceramic colorant of this comparative example was prepared and bagged for use.
Comparative example 3
The preparation method of the red brown ceramic pigment of the comparative example comprises the following preparation steps:
step 1, preparing a presintering material:
the pre-sinter was prepared with reference to step 1 of example 1.
Step 2, preparing pigment:
in the process of batching, V is not added 2 O 5 Instead, 0.2 part of V in step 2 of example 1 is used 2 O 5 The pre-sintering material is replaced by the same weight part, and the weight parts of the rest raw materials are unchanged.
The ingredients are then placed in a spiral mixer to be uniformly stirred, then the mixture is placed in a tunnel kiln to be fired, the firing temperature is 1220 ℃, the heat preservation time is 6 hours, the fired pigment is crushed and fine treated by a powdering machine until the fineness is 325 meshes of full pass or less, and the red brown ceramic pigment of the comparative example is obtained and is packaged for standby.
Comparative example 4
The preparation method of the red brown ceramic pigment of the comparative example comprises the following preparation processes:
not preparing Fe 2 O 3 And ZnO, but directly adding Fe to the pre-sintered material 2 O 3 、Cr 2 O 3 ZnO and V 2 O 5 The actual weight parts of each oxide used in the red brown ceramic pigment of comparative example 2 are as follows:
after the ingredients are mixed, the ingredients are placed in a spiral mixer to be stirred uniformly, then the mixture is placed in a tunnel kiln to be fired, the firing temperature is 1190 ℃, the heat preservation time is 6 hours, the fired pigment is crushed and fine treated by a powder grinding machine until the fineness is 325 meshes full-pass or smaller, and the red brown ceramic pigment of the comparative example is obtained and is packaged for standby.
Performance testing
1. The following performance tests were conducted on the red-brown ceramic colorants prepared in examples 1 to 4 and comparative examples 1 to 4, respectively.
1.1 processing red-brown ceramic pigment into powder with 200 meshes, spreading 100g of powder on paper, touching the powder with a magnet rod with magnetic induction intensity of 10000GS, rotating the magnet rod to make the powder uniformly contact with the powder in all directions, and adsorbing the powder with strong magnetism by the magnet rod. The mass lost, i.e. adsorbed, of the powder was recorded and the test results are shown in table 1 below:
TABLE 1 quality of adsorbed powders of Red-Brown ceramic pigments
| Numbering device | Adsorbed powder mass (g) |
| Example 1 | 2.76 |
| Example 2 | 2.58 |
| Example 3 | 2.44 |
| Example 4 | 2.08 |
| Comparative example 1 | 24.83 |
| Comparative example 2 | 18.66 |
| Comparative example 3 | 8.24 |
| Comparative example 4 | 88.89 |
The data in table 1 shows that:
examples 1 to 3 all adjusted Cr within a reasonable range 2 O 3 、Fe 2 O 3 Proportioning ZnO and preparing F by presintering process e2 O 3 And ZnO, and proper amount of V is added 2 O 5 The powder of the red brown ceramic pigment prepared in examples 1-3 was less than 3% in mass and the three were not very different, indicating that the red brown ceramic pigment prepared by the preparation method of examples 1-3 was very weak and substantially nonmagnetic.
The ZnO of example 4 was added in a relatively excessive amount in the same manner as in example 1, and the powder of the reddish brown ceramic colorant obtained in example 4 was least adsorbed in terms of mass; it can be seen that the addition amount of ZnO is relatively excessive, and the magnetism of the prepared red-brown ceramic pigment can be further reduced.
Comparative example 1 preparation of F without the burn-in process e2 O 3 And ZnO, the powder of the red brown ceramic pigment prepared in comparative example 1 is adsorbed up to 24.83% in mass even though the other preparation conditions are the same as those in example 1; in the preparation method of the invention, F is prepared by adopting a presintering process e2 O 3 And a pre-firing material of ZnO, which has a great influence on the magnetic properties of the resulting red-brown ceramic colorant.
Comparative example 2 used the presintering process, but Fe in the presintering material 2 O 3 Excessive amount, even though the other preparation conditions were the same as in example 1, the powder of the red brown ceramic colorant obtained in comparative example 2 was adsorbedUp to 18.66% by mass; description in the burn-in process, if the deviation from F in the burn-in material e2 O 3 Mass ratio with ZnO, fe 2 O 3 The excessive amount increases the magnetism of the resulting reddish brown ceramic colorant.
Comparative example 4 does not employ a presintering process, and Fe in the presintering material 2 O 3 Excessive pre-sintering material has unsuitable material proportion, and the quality of the red brown ceramic pigment powder prepared in comparative example 4 is 88.89%.
It can be seen that in the preparation method of the red brown ceramic pigment, the presintering process and F in the presintering material e2 O 3 The magnetic property of the prepared red-brown ceramic pigment can be greatly reduced by the synergistic cooperation of the ZnO and the ZnO in mass ratio.
In addition, comparative example 3 uses a presintering process in which F in the presintered material e2 O 3 The mass ratio of the zinc oxide and ZnO is proper, but no V is added 2 O 5 The other preparation conditions were substantially the same as in example 1 (to ensure more complete reaction of the raw materials to ensure firing effect of the red-brown ceramic colorant, slightly raise firing temperature of the red-brown ceramic colorant), and the powder of the red-brown ceramic colorant prepared in comparative example 3 was adsorbed by 8.24% by mass, which is higher than 3%; in the preparation method of the red brown ceramic pigment, a proper amount of V is added 2 O 5 The magnetic effect of the red-brown ceramic pigment can be further reduced in an auxiliary manner.
1.2 the red brown ceramic colorants prepared in examples 1 to 4 and comparative examples 1 to 4 were sent to a professional detection facility to detect the saturation magnetization of each red brown ceramic colorant, and the test results are shown in Table 2 below:
TABLE 2 saturation magnetization of reddish brown ceramic pigments
| Numbering device | Saturation magnetization (emu/g) |
| Example 1 | 8.76 |
| Example 2 | 8.89 |
| Example 3 | 9.02 |
| Example 4 | 7.88 |
| Comparative example 1 | 24.83 |
| Comparative example 2 | 20.33 |
| Comparative example 3 | 15.66 |
| Comparative example 4 | 37.44 |
In view of the data of each of the examples and comparative examples in Table 2 above, the saturation magnetization of the reddish brown ceramic colorant was reduced from 37.44emu/g to 7.88emu/g at the highest, and the reduction in amplitude was significant. Wherein the saturated magnetization intensity of the red brown ceramic pigment prepared in the examples 1-4 is smaller and is basically below 9.02 emu/g; the preparation method of comparative examples 1-4, however, lacks the presintering process and/or the presintering material raw material ratio is deviated, or V is not added 2 O 5 Therefore, the red brown ceramic pigments prepared in comparative examples 1 to 4 all have significantly larger saturation magnetization. The test results are the same as the tendency of the powder of each of the reddish brown ceramic pigments in Table 1 to be adsorbed by the mass.
2、The same conventional dispersing agent and solvent formulation are adopted, after stirring and dispersing, the red brown ceramic pigment prepared in examples 1 to 4 and comparative examples 1 to 4 are respectively added, and then the red brown ceramic pigment is put into a sand mill for grinding by adopting the same conventional grinding parameters, so as to respectively prepare 500g of red brown ceramic pigment with the solid content of 40 percent and the fineness of D 50 Ceramic inkjet printing ink=0.4 μm. The following performance tests were performed on the ceramic inkjet printing inks of examples 1 to 4 and comparative examples 1 to 4, respectively.
2.1 color development Properties of ink
The ink is uniformly printed on the special archaized glaze for detection by using a printing screen with 200 meshes, the special archaized glaze is placed in a test electric kiln for firing, the color development performance is represented by Lab values, L values represent brightness, a values represent red and green values, b values represent Huang Lanzhi, and specific data are shown in the following table 3:
TABLE 3 color development Properties of the inks
| Numbering device | L* | a* | b* |
| Example 1 | 31.6 | 17.3 | 11.1 |
| Example 2 | 31.8 | 17.5 | 11.2 |
| Example 3 | 31.5 | 17.7 | 11.4 |
| Example 4 | 32.1 | 17.9 | 12.2 |
| Comparative example 1 | 32.1 | 16.6 | 11.4 |
| Comparative example 2 | 31.2 | 16.9 | 10.8 |
| Comparative example 3 | 31.5 | 17.1 | 10.9 |
| Comparative example 4 | 31.9 | 16.4 | 11.1 |
The data in Table 3 shows that all of the above inks can normally burn to reddish brown, but that there is a difference in color development intensity between certain inks, as follows:
in the pre-firing formulation of the red brown ceramic colorant used in the ceramic inkjet printing inks of examples 1 to 3, the ZnO content was gradually increased within a suitable range, so that the values of a and b were also gradually increased, but the difference was not large, and the overall color development was good.
In the pre-firing formulation of the red brown ceramic pigment used in the ceramic inkjet printing ink of example 4, the ZnO content continues to increase, and although the quality of the powder of the red brown ceramic pigment adsorbed by the magnet rod and the saturation magnetization are lower than those of examples 1 to 3, and the a value is slightly increased, the degree of magnetic decrease is limited, and the b value is relatively increased to a larger extent, so that the red brown ceramic pigment is yellow, and the color development strength of the ceramic inkjet printing ink is affected to a certain extent. As can be seen, in the preparation method of the red-brown ceramic pigment, if the excessive amount of ZnO in the presintered material is further increased, F e2 O 3 And the proportion of ZnO is deviated from the proper range, so that the red-brown ceramic pigment is obviously yellow, and the color development performance of the ceramic inkjet printing ink is affected.
The ceramic inkjet printing inks of comparative examples 1-4 generally exhibited lower color development intensity than example 1, and were characterized primarily by the lower a-values of the ceramic inkjet printing inks of comparative examples 1-4, with the colorant exhibiting a darker hue.
2.2 viscosity Change
The rate of change of the ink viscosity is also fast or slow depending on the magnetic strength of the colorant. The ceramic ink-jet printing ink was shaken for 15 minutes before the detection, the viscosity of the ink at this time and the viscosity of the ink after standing for 24 hours were detected, and the measured viscosity data are shown in table 4 below:
TABLE 4 viscosity variation of individual ceramic inkjet printing inks
The data in table 4 shows that:
the viscosity change rate of the ceramic inkjet printing ink after 24 hours of standing in examples 1-4 is not more than 0.3%, and there is no significant change compared with that before standing.
The viscosity change rate of the ink of comparative examples 1 to 3 after standing for 24 hours is improved to a certain extent compared with that of example 1, and the value of the viscosity change rate has an influence on the quality of the ink within the range of 1.1 to 1.8%; and comparative example 4 after standing for 24 hoursThe viscosity change rate of the ink is as high as 5% or more, and the viscosity performance of the ink is seriously affected. As can be seen, in the preparation method of the red-brown ceramic pigment of comparative examples 1 to 4, the presintering process and/or the presintering raw material ratio is deviated or V is not added 2 O 5 All of which affect the quality of the ink to different extents.
2.3 precipitation Rate
50g of ceramic ink-jet printing ink was poured into a special glass bottle, capped and sealed, placed in an oven at 60 ℃ for 7 days, poured out of the ceramic ink-jet printing ink and the sedimentation quality of the bottom of the bottle was recorded, and the sedimentation rate of the ceramic ink-jet printing ink for 7 days was measured as shown in Table 5 below.
TABLE 5 precipitation Rate of ink for inkjet printing of ceramics
| Numbering device | Ink quality (g) | Precipitation amount (g) | Precipitation rate |
| Example 1 | 50.21 | 0.76 | 1.51％ |
| Example 2 | 50.14 | 0.80 | 1.60％ |
| Example 3 | 49.88 | 0.78 | 1.56％ |
| Example 4 | 49.98 | 0.85 | 1.70％ |
| Comparative example 1 | 50.06 | 1.68 | 3.36％ |
| Comparative example 2 | 50.12 | 1.44 | 2.87％ |
| Comparative example 3 | 49.78 | 1.46 | 2.93％ |
| Comparative example 4 | 49.86 | 2.58 | 5.17％ |
The data in table 5 shows that:
the 7 day settling rate of the ceramic inkjet printing inks of examples 1-4 was 1.51-1.70%, at a lower level, and the three were not very different.
The 7-day settling rate of the inks of comparative examples 1-3 increased to 2.87-3.36% with a large gap from examples 1-4; the 7-day precipitation rate of the ink of the comparative example 4 is higher than 5%, and the precipitation rate is obviously improved. This further evidenceAs apparent from the above, in the method for producing the reddish brown ceramic colorant of comparative examples 1 to 4, compared with example 1, the presintering process was absent and/or the proportions of the presintering raw materials were deviated, or V was not added 2 O 5 The quality of the ink is affected to different degrees, the stability of the ink is poor, and the ink jet printing performance is easily affected (such as agglomeration, precipitation, nozzle blockage and filter blockage are easily caused).
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the scope of the embodiments of the invention.
The foregoing has outlined rather broadly the more detailed description of the invention in order that the detailed description of the invention that follows may be better understood, and in order that the present principles and embodiments may be better understood; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (8)
1. The preparation method of the reddish brown ceramic pigment is characterized by comprising the following preparation steps:
step S1, preparation of a presintering material:
fe is added to 2 O 3 And ZnO in a mass ratio of 160:81-89, uniformly stirring, presintering for 4-6 hours at 950-1000 ℃, and crushing and finely processing the presintered powder to obtain presintering material;
step S2, preparing the pigment:
45.2-52.7 parts of presintering material and 30.3-35.6 parts of Cr 2 O 3 16.6-19 parts of ZnO and 0.2-0.4 part of V 2 O 5 And (3) preparing materials, stirring uniformly, firing for 5-7 hours at 1160-1200 ℃, and crushing and refining the fired pigment to obtain the red brown ceramic pigment.
2. The method for preparing a reddish brown ceramic colorant according to claim 1, wherein in the step S1, fe is added 2 O 3 And ZnO in a mass ratio of 160:81, and the ingredients are dosed.
3. The method for preparing a reddish brown ceramic colorant according to claim 2, wherein 45.2 parts of the presintered material and 35.6 parts of Cr are mixed in the step S2 2 O 3 19 parts of ZnO and 0.2 part of V 2 O 5 And (5) batching.
4. The method for preparing a reddish brown ceramic colorant according to claim 1, wherein in the step S1, the fineness of the pre-sintered material is less than or equal to 325 mesh;
in the step S2, the fineness of the red brown ceramic pigment is less than or equal to 325 meshes.
5. The method for preparing a reddish brown ceramic colorant according to claim 1, wherein in the step S1 and the step S2, stirring is performed by using a mixer; presintering and firing by adopting a tunnel kiln; crushing and fine treatment by a powder grinding machine.
6. A reddish brown ceramic colorant prepared by the method of any one of claims 1-5.
7. The use of a reddish brown ceramic colorant in ceramic inkjet printing inks according to claim 6 wherein the method of application is: mixing the dispersing agent with the solvent, stirring and dispersing, adding the red brown ceramic pigment, and grinding to obtain the ceramic inkjet printing ink.
8. The use of a reddish brown ceramic pigment according to claim 7 in a ceramic ink-jet printing ink, wherein the ceramic ink-jet printing ink has a solids content of from 35 to 45% and fineness D 50 0.3-0.5 μm.
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