CN112126249A - Black pigment for ceramics, preparation process and ceramic tile using black pigment - Google Patents
Black pigment for ceramics, preparation process and ceramic tile using black pigment Download PDFInfo
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- CN112126249A CN112126249A CN202011008191.8A CN202011008191A CN112126249A CN 112126249 A CN112126249 A CN 112126249A CN 202011008191 A CN202011008191 A CN 202011008191A CN 112126249 A CN112126249 A CN 112126249A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 96
- 239000000049 pigment Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910052742 iron Inorganic materials 0.000 claims abstract description 53
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000011206 ternary composite Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 11
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 29
- 238000011161 development Methods 0.000 abstract description 26
- 238000005245 sintering Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 9
- 230000001737 promoting effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 53
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 40
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 31
- 239000011780 sodium chloride Substances 0.000 description 20
- 238000004040 coloring Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 15
- 238000013329 compounding Methods 0.000 description 14
- 239000011651 chromium Substances 0.000 description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000001089 mineralizing effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000295 complement effect Effects 0.000 description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
- C09C1/0009—Pigments for ceramics
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a black pigment for ceramics, which is prepared by roasting the following raw materials in percentage by mass: 65% -79% of cold-rolled/hot-rolled iron scale and Cr2O320-35% and 1-2% of ternary composite mineralizer. By adding the components, a pure black pigment can be obtained, the adding proportion of the cold-rolled/hot-rolled iron scale can be 65-79%, the black pigment for ceramics in the scheme is prepared by utilizing waste iron scale resources, the environment is protected, the energy is saved, and the production cost of the pigment is saved. In addition, Na is added into the scheme2CO3NaF and Sb2O3The formed ternary composite mineralizer is used as a raw material for promoting the stable color development of the pigment, reduces the sintering temperature of the pigment and promotes the pigment to have a better color development effect in a ceramic tile blank.
Description
Technical Field
The invention relates to the technical field of ceramic pigments, in particular to a black pigment for ceramics, a preparation process and a ceramic tile using the black pigment.
Background
The ceramic tile has good decoration effect, and also has the advantages of easy cleaning, long service life and low production cost, thus being widely used in the household building industry.
The conventional black coloring materials for ceramics mainly use transition metal oxides such as iron (Fe), chromium (Cr), nickel (Ni), manganese (Mn), and cobalt (Co) as raw materials, and as the prices of these raw materials are increasing, the black coloring materials increase in price due to the increase in cost, so that it is imperative to search for low-price raw materials and develop a black coloring material having a low price, a good color development effect, and stable color development. In the existing steelmaking process, after a strip steel is subjected to a hot rolling procedure, iron scales are generated on the surface of the strip steel during curling and cooling, in order to ensure that the iron scales do not influence the service life of equipment and the surface quality and the processing performance of a cold-rolled sheet, the iron scales are removed by using methods such as grinding wheel grinding, bending, shot blasting, straightening, acid pickling and the like, so that the better performance of the strip steel is maintained, and the removed iron scales are usually directly treated as wastes and cannot be utilized, so that the condition of resource waste is caused.
Disclosure of Invention
The invention mainly aims to provide a black pigment for ceramics, a preparation process and a ceramic tile using the black pigment, and aims to solve the technical problems that the existing black pigment is high in manufacturing cost, and waste iron scales are not utilized to reduce the production cost.
In order to achieve the purpose, the invention provides a black pigment for ceramics, which is prepared by roasting the following raw materials: 65% -79% of cold-rolled/hot-rolled iron scale and Cr2O320-35% and 1-2% of ternary composite mineralizer.
Preferably, the ternary complex mineralizer comprises Na2CO3NaF and Sb2O3。
Preferably, the Na2CO3The NaF and the Sb2O3The mass ratio of (1.5-2.5): 1: 1.
in addition, the invention also provides a preparation process of the black pigment for ceramics, which comprises the following steps:
(1) respectively weighing cold-rolled/hot-rolled iron scale and Cr according to mass percentage2O3、Na2CO3NaF and Sb2O3；
(2) Adding water into cold-rolled/hot-rolled iron scale and sodium tripolyphosphate, mixing and ball-milling in ball-milling equipment, and drying.
(3) The cold-rolled/hot-rolled iron scale and Cr dried in the step (2)2O3、Na2CO3NaF and Sb2O3And uniformly mixing in a stirring device, roasting, and finely grinding to obtain the black pigment for ceramics.
Preferably, the roasting temperature is 1000-1030 ℃ and the roasting time is 4-5 h.
Preferably, the drying temperature is 190-210 ℃ and the drying time is 2-3 h.
Preferably, the fineness of the cold/hot rolled scale after drying is 1.9-2.7 μm.
Preferably, the particle size of the black pigment for ceramics after fine grinding is 3 to 7 μm.
In addition, the invention also provides a ceramic tile prepared by using any one of the ceramic black pigments.
The black pigment and the ceramic tile using the same have the following beneficial effects: utilizes the waste cold-rolled/hot-rolled iron scale which is rich in FeO and Fe3O4And Fe2O3The iron oxide can be used as a raw material of a black pigment instead of the existing iron oxide, and the cold-rolled/hot-rolled iron oxide scale is different from the common stainless steel slag, and the components of the iron oxide scale, such as silicon oxide, aluminum oxide, magnesium oxide, titanium dioxide and calcium oxide, which reduce the blackness of the pigment are much less, and the iron oxide scale also contains a component which partially promotes the color development, such as Fe3O4、MnO、Cr2O3And NiO, etc., wherein Fe3O4And Cr2O3The main component is added with 20-35% of Cr2O3As a complement, black Fe is formed during sintering of the colorant2O3·Cr2O3Corundum-like, in addition MnO and NiO in cold-rolled/hot-rolled scale can be mixed with Fe3O4And Cr2O3Form a solid solution with a spinel structure, and complement the colors to obtain a purer black pigment. The adding proportion of the cold rolling/hot rolling iron scale is 65-79%, and the waste iron scale resources are utilized to manufacture the black pigment for ceramics in the scheme, so that the environment is protected, the energy is saved, and meanwhile, the production cost of the pigment is saved. In addition, Na is added into the scheme2CO3NaF and Sb2O3The formed ternary composite mineralizer is used as a raw material for promoting the stable color development of the pigment, reduces the sintering temperature of the pigment and promotes the pigment to have a better color development effect in a ceramic tile blank.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of a black pigment example 4 for ceramics according to the present invention;
FIG. 2 is an X-ray diffraction pattern of comparative example 3 which is a black coloring material for ceramics according to the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a black pigment for ceramics. The black pigment for ceramics is mainly added into a ceramic brick blank for color matching, the color development effect is stable, the prepared black ceramic tile has good decoration effect, the firing temperature of the pigment is reduced, the waste cold-rolled/hot-rolled iron scale is utilized, and the production cost is saved.
In one embodiment of the invention, the black pigment for ceramics is prepared by roasting the following raw materials in percentage by mass: 65% -79% of cold-rolled/hot-rolled iron scale and Cr2O320-35% and 1-2% of ternary composite mineralizer.
Specifically, the black pigment for ceramics in the scheme is prepared by compounding 3 components, wherein chromium oxide is one of main components of the black pigment for ceramics, and the addition proportion of the chromium oxide in the pigment is 20-35%, so that the color saturation of the pigment is gradually enhanced, and the color-assisting effect is achieved; the other component is cold rolling/hot rolling iron scale which is rich in FeO and Fe3O4And Fe2O3The iron oxide can be used as a raw material of a black pigment instead of the existing iron oxide, and the cold-rolled/hot-rolled iron oxide scale is different from the common stainless steel slag, and the components of the iron oxide scale, such as silicon oxide, aluminum oxide, magnesium oxide, titanium dioxide and calcium oxide, which reduce the blackness of the pigment are much less, and the iron oxide scale also contains a component which partially promotes the color development, such as Fe3O4、MnO、Cr2O3And NiO, etc., wherein Fe3O4And Cr2O3As main component, and 20-35% of the additiveCr2O3As a complement, black Fe is formed during sintering of the colorant2O3·Cr2O3Corundum-like, in addition MnO and NiO in cold-rolled/hot-rolled scale can be mixed with Fe3O4And Cr2O3The solid solution with a spinel structure is formed, the colors are complementary, a pure black pigment is obtained, the adding proportion of the cold-rolled/hot-rolled iron scale is 65-79%, the waste iron scale resource is utilized to manufacture the black pigment for ceramics in the scheme, the environment is protected, the energy is saved, and the production cost is saved. In addition, the scheme is also added with a ternary composite mineralizer as a raw material for promoting the stable color development of the pigment, so that the color development effect of the pigment in the ceramic tile blank is promoted.
Further, the ternary complex mineralizer comprises Na2CO3NaF and Sb2O3. Thus, the ternary complex mineralizer is composed of Na2CO3NaF and Sb2O3The three components are compounded and formed, have lower eutectic temperature, can promote the liquid phase to generate at lower temperature in the pigment sintering process, thereby reducing the sintering temperature of the pigment, further promoting the color development effect of the black pigment for ceramics, and stabilizing the color development condition of the pigment when the cold-rolled/hot-rolled iron scale component is increased, and ensuring the purity of the black pigment.
Further, Na2CO3NaF and Sb2O3The mass ratio of (1.5-2.5): 1: 1. in particular, Na in a ternary complex mineralizer2CO3The ratio is maximum, so that the mineralizer has better effect of promoting the growth of crystal forms, and Na2CO3NaF and Sb2O3The mass ratio of (1.5-2.5): 1:1, the coloring effect of the ceramic black coloring material is most enhanced.
In addition, the invention also provides a preparation process of the black pigment for ceramics, which comprises the following steps:
(1) respectively weighing cold-rolled/hot-rolled iron scale and Cr according to mass percentage2O3、Na2CO3NaF and Sb2O3；
(2) Adding water into cold-rolled/hot-rolled iron scale and sodium tripolyphosphate, mixing and ball-milling in ball-milling equipment, and drying.
(3) The cold-rolled/hot-rolled iron scale and Cr dried in the step (2)2O3、Na2CO3NaF and Sb2O3Uniformly mixing in a stirring device, roasting, and finely grinding to obtain the black pigment for ceramics.
Specifically, after weighing the components according to the mass ratio, firstly processing the cold-rolled/hot-rolled iron scale, specifically, adding water into the cold-rolled/hot-rolled iron scale and sodium tripolyphosphate, then mixing and ball-milling, wherein the adding proportion of the sodium tripolyphosphate is about 0.3% of that of the cold-rolled/hot-rolled iron scale, the sodium tripolyphosphate is used for assisting ball-milling, the ball-milling time is 8-10h, drying is carried out to obtain the cold-rolled/hot-rolled iron scale with smaller fineness, and then the cold-rolled/hot-rolled iron scale and Cr are mixed2O3、Na2CO3NaF and Sb2O3The components are stirred and mixed for 1-2h in a stirring device, the mixture is uniformly mixed and then roasted, and as the granularity of the pigment added into the ceramic tile green body is smaller, the color development effect in the ceramic tile green body is better, a further fine grinding process is carried out after roasting, and the black pigment for ceramics is prepared after fine grinding.
Furthermore, the roasting temperature is 1000-1030 ℃ and the roasting time is 4-5 h. Because the components are added into the black pigment for ceramics in the scheme, the effect of reducing the sintering temperature is achieved, the roasting temperature in the scheme is 1000-1030 ℃, the production cost is further reduced, but the roasting time of 4-5 hours needs to be ensured, so that all the components in the pigment are completely melted, and the final effect of the pigment product is ensured.
Furthermore, the drying temperature is 190-210 ℃ and the drying time is 2-3 h. It can be understood that the drying process reduces the water content of the cold-rolled/hot-rolled iron scale after ball milling, thereby facilitating the subsequent pigment preparation.
Furthermore, the fineness of the cold-rolled/hot-rolled iron scale after drying is 1.9-2.7 μm. Thus, the fineness of the cold-rolled/hot-rolled scale, particularly 1.9 to 2.7 μm, needs to be kept small to promote the respective components in the cold-rolled/hot-rolled scale to function better during the roasting process.
Further, the particle size of the black coloring material for ceramics after fine grinding is 3 to 7 μm. It can be understood that the black pigment for ceramics is screened by the screen, the pigment is kept below the granularity, the fine grinding cost can be relatively reduced while the color development effect of the ceramic adobe is ensured, and the method is favorable for industrial production.
In addition, the invention also provides a ceramic tile prepared by using any one of the ceramic black pigments. The ceramic tile prepared by the embodiment also has a good color development effect, and is not described in detail herein.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
A preparation process of a black pigment for ceramics comprises the following steps:
(1) respectively weighing 79% of cold-rolled/hot-rolled iron scale and 20% of Cr2O31% of ternary composite mineralizer (the mass ratio of KCL to NaCl to calcium fluoride is 2.5: 1: 1);
(2) adding water into cold-rolled/hot-rolled iron scale and sodium tripolyphosphate, mixing and ball-milling in a ball mill for 9h, wherein the fineness of the cold-rolled/hot-rolled iron scale is 2 mu m, and then drying at 190 ℃ for 3 h;
(3) the cold-rolled/hot-rolled iron scale and Cr dried in the step (2)2O3The KCL, the NaCl and the calcium fluoride are uniformly mixed in a stirrer, then roasting is carried out, the roasting temperature is 1030 ℃, the roasting time is 4.5 hours, and the black pigment for the ceramics is obtained after fine grinding, wherein the fineness of the black pigment for the ceramics is 7 mu m.
Adding the black pigment for ceramics into a known ceramic blank by 3 percent (the content of chromophoric metal ions in the blank is less than 0.5 percent), performing ball milling and dry pressing to prepare a round cake type sample with the diameter of 55mm, drying, and firing to prepare a ceramic tile sample blank, wherein the firing temperature is 1105 ℃.
Example 2
A preparation process of a black pigment for ceramics comprises the following steps:
(1) respectively weighing 73% of cold-rolled/hot-rolled iron scale and 25.5% of Cr2O31.5 percent of ternary composite mineralizer (KCL, NaF and KNO)3The mass ratio of (1): 1: 1) (ii) a
(2) Adding water into cold-rolled/hot-rolled iron scale and sodium tripolyphosphate, mixing and ball-milling in a ball mill for 8.5h, wherein the fineness of the cold-rolled/hot-rolled iron scale is 2.7 mu m, and then drying at 195 ℃ for 2.5 h;
(3) the cold-rolled/hot-rolled iron scale and Cr dried in the step (2)2O3KCl, NaCl and KNO3Uniformly mixing the materials in a stirrer, roasting at 1020 ℃ for 5 hours, and finely grinding to obtain the black pigment for ceramics, wherein the fineness of the black pigment for ceramics is 4 mu m.
Adding the black pigment for ceramics into a known ceramic blank by 3 percent (the content of chromophoric metal ions in the blank is less than 0.5 percent), performing ball milling and dry pressing to prepare a round cake type sample with the diameter of 55mm, drying, and firing to prepare a ceramic tile sample blank, wherein the firing temperature is 1105 ℃.
Example 3
A preparation process of a black pigment for ceramics comprises the following steps:
(1) respectively weighing 68% of cold-rolled/hot-rolled iron scale and 30% of Cr2O32% of ternary composite mineralizer (KCL, NaCl and KNO)3The mass ratio of (A) to (B) is 1.5: 1: 1) (ii) a
(2) Adding water into cold-rolled/hot-rolled iron scale and sodium tripolyphosphate, mixing and ball-milling in a ball mill for 8 hours, wherein the fineness of the cold-rolled/hot-rolled iron scale is 2.5 mu m, and then drying at 205 ℃ for 2.5 hours;
(3) will be step (2)Dried cold-rolled/hot-rolled iron scale and Cr2O3KCL, NaCl and KNO3Uniformly mixing the materials in a stirrer, roasting at 1005 ℃ for 4 hours, and finely grinding to obtain the black pigment for ceramics, wherein the fineness of the black pigment for ceramics is 3 mu m.
Adding the black pigment for ceramics into a known ceramic blank by 3 percent (the content of chromophoric metal ions in the blank is less than 0.5 percent), performing ball milling and dry pressing to prepare a round cake type sample with the diameter of 55mm, drying, and firing to prepare a ceramic tile sample blank, wherein the firing temperature is 1105 ℃.
Example 4
A preparation process of a black pigment for ceramics comprises the following steps:
(1) respectively weighing 70% of cold-rolled/hot-rolled iron scale and 28% of Cr2O32 percent of ternary composite mineralizer (Na)2CO3NaF and Sb2O3The mass ratio of (A) to (B) is 2:1: 1) (ii) a
(2) Adding water into cold-rolled/hot-rolled iron scale and sodium tripolyphosphate, mixing and ball-milling in a ball mill for 9h, wherein the fineness of the cold-rolled/hot-rolled iron scale is 2.3 mu m, and then drying at the drying temperature of 200 ℃ for 2 h;
(3) the cold-rolled/hot-rolled iron scale and Cr dried in the step (2)2O3、Na2CO3NaF and Sb2O3Uniformly mixing the materials in a stirrer, roasting at 1025 ℃ for 4.5 hours, and finely grinding to obtain the black pigment for ceramics, wherein the fineness of the black pigment for ceramics is 5 microns.
Adding the black pigment for ceramics into a known ceramic blank by 3 percent (the content of chromophoric metal ions in the blank is less than 0.5 percent), performing ball milling and dry pressing to prepare a round cake type sample with the diameter of 55mm, drying, and firing to prepare a ceramic tile sample blank, wherein the firing temperature is 1105 ℃.
The examples 1-4 were tested for performance and the specific test results are shown in table 1 below:
TABLE 1
Wherein, L is a brightness value, a is a red value, b is a yellow value, and the standard value is the Lab value when the black purity of the ceramic tile manufactured by the known ceramic blank is the highest.
Evaluation items: black purity test: the sample blank of the ceramic tile is detected by a CM-2600-.
The above examples show that the black pigment for ceramics prepared by the components and the mixture ratio of the scheme is compared with the Lab value of the standard black pigment, and the color deviation value Delta E of the examples 1-4 is small, and Delta E is less than or equal to 1.25, and the color deviation value Delta E of the optimal example and the standard black pigment is only 0.48, so that the purity of the black pigment for ceramics is high, the ceramic tile prepared by the method under the condition of low sintering temperature of the pigment can keep good color development effect, and the production cost of the black pigment for ceramics is further reduced.
Comparative example 1
The comparative example was conducted under the same conditions as in example 4 except that: this comparative example uses iron oxide instead of cold/hot rolled scale.
Comparative example 2
The comparative example was conducted under the same conditions as in example 4 except that: the mineralizer used in this comparative example was NaCl.
Comparative example 3
The comparative example was conducted under the same conditions as in example 4 except that: the mineralizer used in this comparative example was KCl.
Comparative example 4
The comparative example was conducted under the same conditions as in example 4 except that: the mineralizer used in the comparative example is a compound composition of KCl and NaCl, and the mass ratio of the KCl to the NaCl is 2: 1.
Comparative example 5
The conditions in this comparative example were the same as in comparative example 2, except that: the calcination temperature was 1150 ℃.
Comparative example 6
The conditions in this comparative example were the same as in comparative example 3, except that: the calcination temperature was 1150 ℃.
Comparative example 7
The conditions in this comparative example were the same as in comparative example 4, except that: the calcination temperature was 1150 ℃.
Comparative examples 1-7 were tested for performance and the specific test results are shown in table 2 below:
TABLE 2
According to the test results of the above comparative examples, it is understood that the difference between the color deviation value Δ E of comparative example 1 and example 4 is small compared with the Lab value of the standard black coloring material, and the black coloring material for ceramics obtained by replacing iron oxide with the waste cold-rolled/hot-rolled scale has a good color development effect. According to comparative examples 2 to 4, when a mineralizing agent consisting of a single component or a mineralizing agent consisting of a combination of two components is used, the coloring effect of the prepared coloring material is general, and after comparing with the Lab value of a standard black coloring material, the Delta E is more than 1.5, and according to the detection results of comparative examples 5 to 7, the coloring effect of the coloring material is improved only when the roasting temperature of the coloring material is increased, but the coloring effect of the mineralizing agent consisting of a single component or the mineralizing agent consisting of a combination of two components is still lower than that of example 4 after the roasting temperature is increased.
In addition, the scheme also carries out X-ray diffraction detection on example 4 and comparative example 3, XRD qualitative analysis is carried out on the pigments prepared in example 4 and comparative example 3 by using an X-ray diffractometer, the test results are shown in figures 1 to 2, and by comparing the diffraction intensities of the two, under the same conditions, compared with the conventional mineralizer KCl, the ternary composite mineralizer in the scheme has the advantages that the crystal form development of the pigments is more complete, and the color development effect is better.
Example 5
The conditions in this example are the same as in example 4, except that: the mineralizer used in this comparative example was formed by compounding KCL, NaCl and calcium fluoride.
Example 6
The conditions in this example are the same as in example 4, except that: the mineralizers used in this comparative example were KCl, NaF and KNO3And (4) compounding to form.
Example 7
The conditions in this example are the same as in example 4, except that: the mineralizers used in this comparative example were KCL, NaCl and KNO3And (4) compounding to form.
The examples 5-7 were tested for performance and the specific test results are shown in Table 3 below:
TABLE 3
| Mineralizing agent | L | a | b | △E | |
| Example 4 | Na2CO3：NaF：Sb2O3＝2：1：1 | 32.61 | 1.15 | -0.61 | 0.48 |
| Example 5 | KCL: NaCl: calcium fluoride ═ 2:1:1 | 31.81 | 1.43 | -0.3 | 0.95 |
| Example 6 | KCl：NaF：KNO3＝2：1：1 | 31.91 | 1.23 | -0.24 | 0.83 |
| Example 7 | KCL：NaCl：KNO3＝2：1：1 | 32.11 | 1.13 | -0.3 | 0.65 |
| Standard of merit | / | 32.32 | 0.85 | -0.85 | / |
Testing according to the above comparative exampleAs a result, it was found that the difference between the color deviation DeltaE of example 4 and examples 5 to 7 was large as compared with the Lab value of the standard black coloring material, and Na was used in each group of examples2CO3NaF and Sb2O3When the pigment is compounded, the color development effect is optimal, and KCL + NaCl + calcium fluoride, KCl + NaCl + KNO are adopted3And KCL + NaF + KNO3During compounding, the color deviation value Delta E of a ceramic tile sample blank prepared by sintering is relatively large, and the color development effect is better than that of Na2CO3NaF and Sb2O3The composition is poor.
Example 8
The comparative example was conducted under the same conditions as in example 4 except that: the addition proportion of each component is adjusted to 73 percent of ferric oxide, 25 percent of chromic oxide and 2 percent of ternary composite mineralizer.
Example 9
The conditions in this example are the same as those in example 8, except that: the mineralizer used in this comparative example was formed by compounding KCL, NaCl and calcium fluoride.
Example 10
The conditions in this example are the same as those in example 8, except that: the mineralizers used in this comparative example were KCl, NaF and KNO3And (4) compounding to form.
Example 11
The conditions in this example are the same as those in example 8, except that: the mineralizers used in this comparative example were KCL, NaCl and KNO3And (4) compounding to form.
Example 12
The comparative example was conducted under the same conditions as in example 4 except that: the addition proportion of each component is adjusted to 75 percent of ferric oxide, 23 percent of chromic oxide and 2 percent of ternary composite mineralizer.
Example 13
The conditions in this example are the same as in example 12, except that: the mineralizer used in this comparative example was formed by compounding KCL, NaCl and calcium fluoride.
Example 14
Conditions and implementations of the examplesExample 12 the same, except: the mineralizers used in this comparative example were KCl, NaF and KNO3And (4) compounding to form.
Example 15
The conditions in this example are the same as in example 12, except that: the mineralizers used in this comparative example were KCL, NaCl and KNO3And (4) compounding to form.
Example 16
The comparative example was conducted under the same conditions as in example 4 except that: the addition proportion of each component is adjusted to 78 percent of ferric oxide, 20 percent of chromic oxide and 2 percent of ternary composite mineralizer.
Example 17
The conditions in this example are the same as in example 12, except that: the mineralizer used in this comparative example was formed by compounding KCL, NaCl and calcium fluoride.
Example 18
The conditions in this example are the same as in example 12, except that: the mineralizers used in this comparative example were KCl, NaF and KNO3And (4) compounding to form.
Example 19
The conditions in this example are the same as in example 12, except that: the mineralizers used in this comparative example were KCL, NaCl and KNO3And (4) compounding to form.
The examples 8-15 were tested for performance and the specific test results are shown in table 4 below:
TABLE 4
The above materialsThe examples show that Na is used2CO3NaF and Sb2O3When the composite mineralizer is compounded, the components of the cold-rolled/hot-rolled iron scale are added, the difference value of the color deviation value delta E is less than or equal to 0.04, and the black purity difference of the prepared ceramic tile is small, so that the influence on the color development effect of the ceramic tile is small when the adding proportion of the cold-rolled/hot-rolled iron scale is increased, the color development effect is good, and the production cost is further reduced. When other mineralizers are compounded into the ternary mineralizer, the color development effect of the prepared ceramic tile sample blank is unstable, the difference value of the color deviation value delta E is not less than 0.1, and the prepared ceramic tile product has relatively large color difference.
Example 20
The conditions in this example are the same as in example 4, except that: na in composite mineralizer2CO3NaF and Sb2O3The mass ratio of (A) to (B) is 1.5: 1: 1.
example 21
The conditions in this example are the same as in example 4, except that: na in composite mineralizer2CO3NaF and Sb2O3The mass ratio of (A) to (B) is 2.5: 1: 1.
comparative example 9
The comparative example was conducted under the same conditions as in example 4 except that: na in composite mineralizer2CO3NaF and Sb2O3The mass ratio of (1): 1: 1.
comparative example 9
The comparative example was conducted under the same conditions as in example 4 except that: na in composite mineralizer2CO3NaF and Sb2O3The mass ratio of (A) to (B) is 2:1: 1.
the examples 20 to 21 and the comparative examples 8 to 9 were subjected to the performance test, and the specific test results are shown in the following table 5:
TABLE 5
| Mineralizing agent | L | a | b | △E | |
| Example 4 | Na2CO3：NaF：Sb2O3＝2：1：1 | 32.61 | 1.15 | -0.61 | 0.48 |
| Example 20 | Na2CO3：NaF：Sb2O3＝1.5：1：1 | 32.53 | 1.32 | -0.58 | 0.58 |
| Example 21 | Na2CO3：NaF：Sb2O3＝2.5：1：1 | 32.58 | 1.35 | -0.55 | 0.64 |
| Comparative example 8 | Na2CO3：NaF：Sb2O3＝1：1：1 | 32.47 | 1.37 | -0.57 | 0.61 |
| Comparative example 9 | Na2CO3：NaF：Sb2O3＝3：1：1 | 32.59 | 1.42 | -0.54 | 0.70 |
The above examples and comparative examples show that the present solution uses Na in the composite mineralizer2CO3NaF and Sb2O3Has the best color development effect when the mass ratio of (1) to (2) is 1:1, and is compounded with Na in a mineralizer2CO3NaF and Sb2O3At other mass ratio, the coloring effect is reduced, and Na is preferably used as the mass ratio2CO3NaF and Sb2O3＝2:1:1。
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (9)
1. The black pigment for ceramics is characterized by being prepared by roasting the following raw materials in percentage by mass: cold/hot rolled iron oxide65% -79% of skin and Cr2O320-35% and 1-2% of ternary composite mineralizer.
2. The black colorant for ceramics according to claim 1, wherein the ternary complex mineralizer comprises Na2CO3NaF and Sb2O3。
3. A black colorant for ceramics according to claim 2, wherein said Na is2CO3The NaF and the Sb2O3The mass ratio of (1.5-2.5): 1: 1.
4. a process for producing a black colorant for ceramics according to any one of claims 2 to 3, comprising the steps of:
(1) respectively weighing cold-rolled/hot-rolled iron scale and Cr according to mass percentage2O3、Na2CO3NaF and Sb2O3；
(2) Adding water into cold-rolled/hot-rolled iron scale and sodium tripolyphosphate, mixing and ball-milling in ball-milling equipment, and drying.
(3) The cold-rolled/hot-rolled iron scale and Cr dried in the step (2)2O3、Na2CO3NaF and Sb2O3And uniformly mixing in a stirring device, roasting, and finely grinding to obtain the black pigment for ceramics.
5. The process for preparing a black pigment for ceramics according to claim 4, wherein the firing temperature is 1000 ℃ to 1030 ℃ and the firing time is 4 to 5 hours.
6. The process for preparing a black pigment for ceramics according to claim 4, wherein the drying temperature is 190 ℃ to 210 ℃ and the drying time is 2 to 3 hours.
7. The process for preparing a black colorant for ceramics according to claim 4, wherein the fineness of the cold-rolled/hot-rolled scale after drying is 1.9 to 2.7 μm.
8. The process according to claim 4, wherein the black pigment for ceramics has a particle size of 3 to 7 μm after the fine grinding.
9. A ceramic tile made using the ceramic of any one of claims 1-3 with a black pigment.
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| US20020073895A1 (en) * | 1999-04-26 | 2002-06-20 | Barnes Raymond E. | Continuous calcination of mixed metal oxides |
| CN1528703A (en) * | 2003-10-14 | 2004-09-15 | 廖红卫 | Ceramic glass pigment produced by using ferrochrome alloy as raw material and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020073895A1 (en) * | 1999-04-26 | 2002-06-20 | Barnes Raymond E. | Continuous calcination of mixed metal oxides |
| CN1528703A (en) * | 2003-10-14 | 2004-09-15 | 廖红卫 | Ceramic glass pigment produced by using ferrochrome alloy as raw material and production method thereof |
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| 张启富等编著: "《现代钢带连续热镀锌》", 31 January 2007, 北京：冶金工业出版社 * |
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Effective date of registration: 20231030 Address after: 528000 one of shop 8, block 1, No. 771, Genghe Avenue, Genghe Town, Gaoming District, Foshan City, Guangdong Province Patentee after: Foshan zhongtianrong environmental protection new material technology Co.,Ltd. Address before: Huang Miao Gang" (F1), (F2) of Likeng village committee of niande village, Leping Town, Sanshui District, Foshan City, Guangdong Province Patentee before: Foshan Sanshui Tianyu Ceramic Pigment Co.,Ltd. Patentee before: Foshan zhongtianrong environmental protection new material technology Co.,Ltd. |