Ceramic ink prepared from chromium ore powder and preparation method thereof

Abstract

The invention relates to the field of ceramic pigments and ceramic ink, and discloses ceramic ink prepared from chromium ore powder and a preparation method of the ceramic ink. The dark reddish brown pigment comprises the following components in percentage by weight: 35-50% of Fe2O3, 10-50% of Cr2O3, 1-50% of ZnO, 0-10% of NiO and 1-20% of chromium ore powder. Wherein the chromium ore powder comprises the following components in percentage by weight: 35 to 50 percent of Fe2O3, 10 to 70 percent of Cr2O3, 1 to 30 percent of Al2O3 and 0 to 30 percent of MgO. Particularly, the natural color material needs to be calcined twice at the high temperature of 1330-1360 DEG C, so that the color development effect and the glaze effect of the natural color material are better. The ink prepared from the dark reddish brown pigment has the advantages of bright color development, high adaptability, better glaze effect and lower cost.

Description

Technical field

[0001] The present invention relates to the field of ceramic colorants and ceramic inks, and in particular to a ceramic ink prepared by utilizing chromium ore powder and a preparation method thereof. [Background Technology]

[0002] After years of development, ceramic inkjet printing technology has replaced traditional screen and roller printing techniques, earning it the nickname "the third revolution" in ceramic printing technology. In recent years, the emergence of various ceramic tiles imitating wood grain, marble, and rock slabs has continuously increased the demand for inkjet technology. Furthermore, with the recent decline in the real estate industry, ceramic manufacturers have been increasingly demanding stricter control over tile production costs while also demanding superior decorative effects. As one of the primary colors for ceramic inkjet printing, reddish-brown ceramic ink is of undeniable importance. Currently, reddish-brown ceramic inks still have some drawbacks. For one thing, glaze defects are prone to appearing on some antique and polished tiles. Furthermore, ceramic companies are also seeking to further control costs. These factors necessitate a reddish-brown ink with enhanced decorative effects and lower costs.

[0003] Chinese patent CN115572494A describes a reddish-brown ceramic colorant, its preparation method, and its use in ceramic inkjet printing inks. This patent employs a method of pre-firing a mixture of Fe2O3 and ZnO, followed by mixing and firing with Cr2O3, ZnO, and V2O5. The dark reddish-brown colorant prepared using this method suffers from unsatisfactory cost and, on the other hand, its glaze decorative effect is still flawed. Chinese patent CN108997786A describes a red pigment and its preparation method, whose main components are Li2O, Na2O, K2O, Al2O3, B2O3, ZnO, CuO, and SiO2. This patented process is complex and requires sintering to form a frit, which is not conducive to preparing ceramic inks. Furthermore, its color development is mediocre and cannot meet the current needs of inkjet printing. [Summary of the invention]

[0004] The present invention aims to reduce costs and increase efficiency for current ceramic enterprises while improving glaze effects. It aims to improve the defects of antique tiles such as reddish brown becoming shiny at low temperatures and white spots on fully polished reddish brown after firing, so as to reduce costs for ceramic enterprises while improving product quality.

[0005] The invention discloses a ceramic ink prepared by using chromium ore powder. The ceramic ink is composed of the following components in weight percentage: 25-55% of a dark red-brown colorant, 2-10% of a hyperdispersant, and 40-60% of a solvent; wherein the dark red-brown colorant is composed of the following components in weight percentage: 5-50% of Fe2O3, 10-50% of Cr2O3, 1-50% of ZnO, 0-10% of NiO, and 1-20% of chromium ore powder; wherein the chromium ore powder is composed of the following components in weight percentage: 5-50% of Fe2O3, 10-70% of Cr2O3, 1-30% of Al2O3, and 0-30% of MgO.

[0006] The invention discloses a preparation method of a dark reddish brown pigment. The dark reddish brown pigment comprises the following components: 5-50% of Fe2O3, 10-50% of Cr2O3, 1-50% of ZnO, 0-10% of NiO and 1-20% of chromium ore powder. The ingredients are evenly mixed and then calcined at a high temperature of 1330-1360°C.

[0007] Preferably, the dark reddish brown colorant needs to be calcined twice at 1330-1360°C.

[0008] Preferably, the dark reddish brown colorant must be pulverized after each high-temperature calcination before the next calcination, and the pulverization process is performed to a D50 of less than 10 μm. More preferably, the pulverization process is performed to a D50 of less than 5 μm.

[0009] Preferably, the chromium ore powder comprises: Fe2O3 5-50%, Cr2O3 10-70%, Al2O3 1-30%, MgO 0-30%, and the fineness of the chromium ore powder is required to pass through a standard sieve of 400 mesh, and more preferably, can pass through a standard sieve of 600 mesh.

[0010] The hyperdispersant is one or a mixture of polyester hyperdispersants, polyurethane hyperdispersants, polyamide hyperdispersants, and polyacrylate hyperdispersants, such as Lubrizol-13940, Lubrizol-J980, Lubrizol-J1280, S35, Lamberti 1028, Lamberti 1087, CH-6, CH-30, AD1310, HP1068, HP1064, and HP1062.

[0011] Preferably, the solvent is isopropyl laurate, isooctyl cocoate, isooctyl palmitate, isooctyl myristate, methyl oleate, butyl oleate, methyl laurate, low polarity alkane solvent ToTal 25-28H, 28-32H, 30-35H, 30-36H, 30-38H, 35-40H, or a mixture thereof.

[0012] A method for preparing ceramic ink comprises the following steps:

[0013] Step 1: Mix the dark reddish brown pigment raw materials evenly, put them into a bowl and burn them at a temperature of 1330-1360℃;

[0014] Step 2: After the dark reddish-brown pigment is sintered, it is cooled to room temperature and pulverized until its D50 is less than 10 μm;

[0015] Step 3: After the dark reddish-brown pigment is crushed, it is placed in a bowl and fired again at a temperature of 1330-1360°C.

[0016] Step 4: After the dark reddish brown pigment is sintered twice, it is cooled to room temperature and pulverized until its D50 is less than 10 μm;

[0017] Step 5: Mixing the solvent and the hyperdispersant to prepare a dispersion;

[0018] Step 6: Add the dark reddish brown pigment to the dispersion and grind it using a horizontal sand mill;

[0019] Step 7: Grind with 0.3-0.4mm zirconium beads until the ink reaches a certain particle size and viscosity;

[0020] Step 8: Add a certain proportion of solvent to the ground ink slurry to adjust it to the required solid content and viscosity, and then filter it through multiple stages to obtain dark red-brown ceramic ink.

[0021] Preferably, in step seven, a sand mill is used to grind the ink until the particle size D50 is less than 400 nm, a particle size analyzer is used, the viscosity at 40°C is less than 200 cp, a viscometer is used, and a Cobetter glass fiber filter is used for filtration, and the filtration weight is greater than 200 grams.

[0022] Preferably, in step eight, after the prepared ink is prepared, it is filtered through multiple stages of 1 μm filter elements, and after filtration, it is packaged to obtain a dark reddish-brown ceramic ink.

[0023] Compared with the existing technology, the present invention has the following advantages:

[0024] The dark reddish-brown colorant prepared from chromium ore powder and the ceramic ink prepared therefrom of the present invention have one of the characteristics that chromium ore powder can be used as a raw material, which can greatly reduce the formulation cost of the colorant. Secondly, the preparation process is mature and simple, and can be achieved based on the existing production conditions of the colorant enterprise. Through a large number of experiments, in order to improve the colorant for preparation into ceramic ink for application on the surface of ceramic tiles so that it has a better glaze effect, the firing temperature of the general inorganic colorant is increased from about 1200°C to 1330-1360°C, thereby improving the adaptability temperature range of the colorant, and further performing a secondary firing on the colorant, thereby better improving the temperature resistance and burn-out performance of the colorant, so that the ceramic ink prepared therefrom is not easy to appear low in temperature in antique tiles and thus easy to burn out. At the same time, when applied to glazed tiles, its color is purer, and the glaze surface is not easy to have defects such as prickly heat and polishing white spots. The dark reddish-brown ceramic ink prepared by the present invention can better reduce costs and increase efficiency for ceramic enterprises. [Specific implementation method]

[0025] Example 1: The dark reddish-brown ceramic ink of Example 1 was prepared according to the following formula. The dark reddish-brown colorant consisted of the following components in weight percentage: Fe2O3 30%, Cr2O3 30%, ZnO2 9%, NiO 1%, and chromium ore powder 10%.

[0026] The components of chromium ore powder are:

[0027] Fe2O329%, Cr2O346%, Al2O315%, MgO 10%.

[0028] The ink prepared therefrom consists of the following components in percentage by weight:

[0029] Dark reddish brown pigment 25-50%, Lamberti 10283-6%, 2-ethylhexyl cocoate 10-70%,

[0030] Isooctyl palmitate 1-30%, isopropyl laurate 1-20%;

[0031] Example 1 A dark reddish brown pigment is composed of the following components in weight percentage: Fe2O3 30%, Cr2O3 30%, ZnO 29%, NiO 1%, and chromium ore powder 10%. After the ingredients are uniformly mixed, they are calcined at a high temperature of 1350°C.

[0032] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 10 μm.

[0033] The dark reddish-brown pigment is crushed and put back into the sagger, and needs to be calcined again at a high temperature of 1350℃.

[0034] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 5μm.

[0035] Prepare high-temperature resistant dark red-brown ink according to the above formula: mix 10286% of hyperdispersant Lamberti and 44% of 2-ethylhexyl cocoate, stir evenly, add to the grinding equipment, and start the sand mill while stirring.

[0036] The sand mill was a NETZSCH Labstar horizontal sand mill, using 0.3-0.4mm zirconium beads with an 85% fill rate. The grinding speed was set at 3000 rpm. After starting the sand mill, the prepared dark reddish-brown colorant (50%) was slowly added to the mixing tank and circulated. The sand mill was used to grind the ink to a particle size of D50 = 470-490nm. The particle size instrument used was OMEC, the viscosity at 40°C was <100cp, and the viscometer was a Brookfield. A Cobetter 1μm glass fiber filter was used for filtration. When the filtrate exceeded 200g, the grinding was complete.

[0037] After the ink is ground and qualified, add appropriate amount of solvent (isooctyl cocoate, isopropyl laurate, isooctyl palmitate) to control the performance parameters of the ink. The solid content of the ink is controlled at 40%, the viscosity at 40°C is controlled between 16-18cp, and the surface tension is controlled at 25-40mN / m.

[0038] The prepared ink is filtered through a multi-stage 1 μm filter element and packaged to obtain a finished dark red-brown ink.

[0039] Example 2

[0040] The dark reddish-brown ceramic ink of Example 2 was prepared according to the following formula. The dark reddish-brown colorant consisted of the following components in weight percentage: Fe2O3 28%, Cr2O3 29%, ZnO 29%, NiO 2%, and chromium ore powder 12%.

[0041] The components of the chromium ore powder are: Fe2O3 32%, Cr2O3 50%, Al2O3 10%, and MgO 8%.

[0042] The prepared ink consists of the following components in percentage by weight: 25-50% of dark reddish brown colorant, 3-6% of Lamberti 1028, 10-70% of isooctyl cocoate, 1-30% of isooctyl palmitate, and 1-20% of isopropyl laurate.

[0043] The remaining steps of Example 2 are the same as those of Example 1.

[0044] Example 3

[0045] The dark reddish brown ceramic ink of Example 3 was prepared according to the following formula. The dark reddish brown colorant consisted of the following components in weight percentage: Fe2O3 27%, Cr2O3 27%, ZnO 29%, NiO 2%, and chromium ore powder 15%.

[0046] The components of the chromium ore powder are: Fe2O3 30%, Cr2O3 55%, Al2O3 10%, and MgO 5%.

[0047] The prepared ink is composed of the following components in weight percentage: 25-50% dark red-brown colorant, 3-6% Lamberti 1028, 10-70% isooctyl cocoate, 1-30% isooctyl palmitate, and 1-20% isopropyl laurate;

[0048] The remaining steps of Example 3 are the same as those of Example 1.

[0049] In order to better illustrate the present invention, a comparative example is given below.

[0050] In the comparative example, oxides of the same composition were used to replace the chromium ore powder, and the chromium ore powder fired once and twice was compared with the example.

[0051] Comparative Example 1

[0052] A reddish-brown ceramic ink of Comparative Example 1 was prepared according to the following formula. The dark reddish-brown pigment consisted of the following components in weight percentage: Fe2O3 32.9%, Cr2O3 34.6%, ZnO 29%, NiO 1%, Al2O3 1.5%, and MgO 1%;

[0053] The ink prepared therefrom consists of the following components in percentage by weight:

[0054] Dark reddish brown pigment 25-50%, Lamberti 10283-6%, 2-ethylhexyl cocoate 10-70%, 2-ethylhexyl palmitate 1-30%, and 1-20% isopropyl laurate;

[0055] Comparative Example 1: A dark reddish brown pigment is composed of the following components in weight percentage: Fe2O3 32.9%, Cr2O3 34.6%, ZnO 29%, NiO 1%, Al2O3 1.5%, and MgO 1%. After the ingredients are uniformly mixed, they are calcined at a high temperature of 1350°C.

[0056] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 5 μm.

[0057] In Comparative Example 1, the dark reddish-brown pigment was not subjected to secondary high-temperature calcination, and the ink preparation process was the same as in Example 1.

[0058] Comparative Example 2

[0059] The reddish-brown ceramic ink of Comparative Example 2 was prepared according to the following formula. The dark reddish-brown pigment consisted of the following components in weight percentage: Fe2O3 32.9%, Cr2O3 34.6%, ZnO 29%, NiO 1%, Al2O3 1.5%, and MgO 1%;

[0060] The prepared ink is composed of the following components in weight percentage: 25-50% dark red-brown colorant, 3-6% Lamberti 1028, 10-70% isooctyl cocoate, 1-30% isooctyl palmitate, and 1-20% isopropyl laurate;

[0061] Comparative Example 2: A dark reddish brown pigment is composed of the following components in weight percentage: Fe2O3 32.9%, Cr2O3 34.6%, ZnO 29%, NiO 1%, Al2O3 1.5%, and MgO 1%. After the ingredients are uniformly mixed, they are calcined at a high temperature of 1350°C.

[0062] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 10 μm.

[0063] The dark reddish-brown pigment is crushed and put back into the sagger, and needs to be calcined again at a high temperature of 1350℃.

[0064] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 5 μm.

[0065] The ink preparation process of Comparative Example 2 is the same as that of Example 1.

[0066] Comparative Example 3

[0067] The reddish-brown ceramic ink of comparative example 3 was prepared according to the following formula. The dark reddish-brown colorant consisted of the following components in weight percentage: Fe2O3 31.84%, Cr2O3 35%, ZnO 29%, NiO 2%, Al2O3 1.2%, and MgO 0.96%.

[0068] The ink prepared therefrom consists of the following components in percentage by weight:

[0069] Dark reddish brown pigment 25-50%, Lamberti 10283-6%, 2-ethylhexyl cocoate 10-70%, 2-ethylhexyl palmitate 1-30%, and 1-20% isopropyl laurate;

[0070] Comparative Example 3: A dark reddish brown pigment is composed of the following components in weight percentage: Fe2O3 31.84%, Cr2O3 35%, ZnO 29%, NiO 2%, Al2O3 1.2%, and MgO 0.96%. After the ingredients are uniformly mixed, they are calcined at a high temperature of 1350°C.

[0071] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 5 μm.

[0072] The dark reddish-brown pigment of Comparative Example 3 was not subjected to secondary high-temperature calcination, and the ink preparation process was the same as that of Example 1.

[0073] Comparative Example 4

[0074] The reddish-brown ceramic ink of comparative example 4 was prepared according to the following formula. The dark reddish-brown colorant consisted of the following components in weight percentage: Fe2O3 31.84%, Cr2O3 35%, ZnO 29%, NiO 2%, Al2O3 1.2%, and MgO 0.96%.

[0075] The prepared ink is composed of the following components in weight percentage: 25-50% dark red-brown colorant, 3-6% Lamberti 1028, 10-70% isooctyl cocoate, 1-30% isooctyl palmitate, and 1-20% isopropyl laurate;

[0076] Comparative Example 4: A dark reddish brown pigment is composed of the following components in weight percentage: Fe2O3 31.84%, Cr2O3 35%, ZnO 29%, NiO 2%, Al2O3 1.2%, and MgO 0.96%. After the ingredients are uniformly mixed, they are calcined at a high temperature of 1350°C.

[0077] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 10 μm.

[0078] The dark reddish-brown pigment is crushed and put back into the sagger, and needs to be calcined again at a high temperature of 1350℃.

[0079] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 5 μm.

[0080] The ink preparation process of Comparative Example 4 is the same as that of Example 1.

[0081] Comparative Example 5

[0082] The reddish-brown ceramic ink of comparative example 5 was prepared according to the following formula. The dark reddish-brown colorant consisted of the following components in weight percentage: Fe2O3 31.5%, Cr2O3 35.25%, ZnO 29%, NiO2%, Al2O3 1.5%, and MgO 0.75%.

[0083] The ink prepared therefrom consists of the following components in percentage by weight:

[0084] Dark reddish brown pigment 25-50%, Lamberti 10283-6%, 2-ethylhexyl coconut oil 10-70%, 2-ethylhexyl palmitate 1-30%,

[0085] Isopropyl laurate 1-20%,

[0086] Comparative Example 5: A dark reddish brown pigment is composed of the following components in weight percentage: Fe2O3 31.5%, Cr2O3 35.25%, ZnO 29%, NiO 2%, Al2O3 1.5%, and MgO 0.75%. After the ingredients are uniformly mixed, they are calcined at a high temperature of 1350°C.

[0087] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 5 μm.

[0088] The dark reddish-brown pigment of Comparative Example 5 was not subjected to secondary high-temperature calcination, and the ink preparation process was the same as that of Example 1.

[0089] Comparative Example 6

[0090] The reddish-brown ceramic ink of Comparative Example 6 was prepared according to the following formula. The dark reddish-brown colorant consisted of the following components in percentage by weight:

[0091] The component composition in percentage is: Fe2O3 31.5%, Cr2O3 35.25%, ZnO 29%, NiO 2%, Al2O3 1.5%, MgO 0.75%.

[0092] The prepared ink is composed of the following components in weight percentage: 25-50% dark red-brown colorant, 3-6% Lamberti 1028, 10-70% isooctyl cocoate, 1-30% isooctyl palmitate, and 1-20% isopropyl laurate;

[0093] Comparative Example 6: A dark reddish brown pigment is composed of the following components in weight percentage: Fe2O3 31.5%, Cr2O3 35.25%, ZnO 29%, NiO 2%, Al2O3 1.5%, and MgO 0.75%. After the ingredients are uniformly mixed, they are calcined at a high temperature of 1350°C.

[0094] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 10 μm.

[0095] The dark reddish-brown pigment is crushed and put back into the sagger, and needs to be calcined again at a high temperature of 1350℃.

[0096] The dark reddish brown pigment is calcined at high temperature, cooled to room temperature, and then pulverized until the particle size D50 is less than 5 μm.

[0097] The ink preparation process of Comparative Example 6 is the same as that of Example 1.

[0098] The inks prepared in the examples of the present invention and the comparative examples were sintered at 1150°C using a screen scraper to compare their color and glaze effects.

[0099]

[0100]

[0101]

[0102] The experimental results of the embodiments and comparative examples show that the dark reddish-brown colorant prepared with chromium ore powder and the colorant prepared with the same proportion of oxide raw materials achieve very similar effects. At the same time, the process of firing the colorant twice can improve the effect of the colorant prepared into ink and its use in tiles, improve the color saturation, and improve the glaze effect.

[0103] The above description is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, various changes, modifications, substitutions and variations can be made to these embodiments without departing from the technical principles of the present invention. These changes, modifications, substitutions and variations should also be regarded as the scope of protection of the present invention.

Claims

1. A ceramic ink prepared using chromium ore powder, characterized in that: The invention is composed of the following components in weight percentage: 25-55% of dark red-brown colorant, 2-10% of hyperdispersant, and 40-60% of solvent; wherein the dark red-brown colorant is composed of the following components in weight percentage: 5-50% of Fe2O3, 10-50% of Cr2O3, 1-50% of ZnO, 0-10% of NiO, and 1-20% of chromium ore powder; wherein the chromium ore powder is composed of the following components in weight percentage: 5-50% of Fe2O3, 10-70% of Cr2O3, 1-30% of Al2O3, and 0-30% of MgO.

2. A method for preparing the dark reddish-brown colorant according to claim 1, characterized in that: The dark reddish brown colorant comprises the following components: Fe2O3 5-50%, Cr2O3 10-50%, ZnO 1-50%, NiO 0-10%, and chromium ore powder 1-20%. The ingredients are evenly mixed and then calcined at a high temperature of 1330-1360°C.

3. The method for preparing the dark reddish brown colorant according to claim 2, wherein: The dark reddish brown colorant needs to be calcined twice at 1330-1360°C.

4. The method for preparing the dark reddish brown colorant according to claim 3, wherein: After each high-temperature calcination, the dark reddish-brown colorant must be pulverized until D50 is less than 10 μm before the next calcination.

5. The ceramic ink according to claim 1, characterized in that The components of the chromium ore powder are: Fe2O3 5-50%, Cr2O3 10-70%, Al2O3 1-30%, MgO 0-30%, and the fineness of the chromium ore powder is required to pass through a standard sieve of 400 mesh.

6. The ceramic ink according to claim 1, characterized in that The hyperdispersant is one or a mixture of polyester hyperdispersant, polyurethane hyperdispersant, polyamide hyperdispersant, and polyacrylate hyperdispersant.

7. The ceramic ink according to claim 1, characterized in that The solvent is one or a mixture of isopropyl laurate, isooctyl cocoate, isooctyl palmitate, myristate, methyl oleate, butyl oleate, methyl laurate, low polarity alkane solvent ToTal 25-28H, 28-32H, 30-35H, 30-36H, 30-38H, 35-40H.

8. A method for preparing the ceramic ink according to claim 1, characterized in that: The following steps are involved: Step 1: Mix the dark reddish brown pigment raw materials evenly, put them into a bowl and burn them at a temperature of 1330-1360℃; Step 2: After the dark reddish-brown pigment is sintered, it is cooled to room temperature and pulverized until its D50 is less than 10 μm; Step 3: After the dark reddish-brown pigment is crushed, it is placed in a bowl and fired again at a temperature of 1330-1360°C. Step 4: After the dark reddish brown pigment is sintered twice, it is cooled to room temperature and pulverized until its D50 is less than 10 μm; Step 5: Mixing the solvent and the hyperdispersant to prepare a dispersion; Step 6: Add the dark reddish brown pigment to the dispersion and grind it using a horizontal sand mill; Step 7: Grind with 0.3-0.4mm zirconium beads until the ink reaches a certain particle size and viscosity; Step 8: Add a certain proportion of solvent to the ground ink slurry to adjust it to the required solid content and viscosity, and then filter it through multiple stages to obtain dark red-brown ceramic ink.

9. The method for preparing ceramic ink according to claim 8, wherein: In the step seven, a sand mill is used to grind the ink until the particle size D50 is less than 400 nm, a particle size instrument is used, the viscosity at 40°C is less than 200 cp, a viscometer is used, and a Cobetter glass fiber filter is used for filtration, and the filtration weight is greater than 200 grams.

10. The method for preparing ceramic ink according to claim 8, wherein: In the step eight, after the prepared ink is prepared, it is filtered through a multi-stage 1 μm filter element, and after filtration, it is packaged to obtain a dark reddish-brown ceramic ink.

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