CN115093752B - Metal ink for ceramic tiles - Google Patents
Metal ink for ceramic tiles Download PDFInfo
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- CN115093752B CN115093752B CN202210655760.0A CN202210655760A CN115093752B CN 115093752 B CN115093752 B CN 115093752B CN 202210655760 A CN202210655760 A CN 202210655760A CN 115093752 B CN115093752 B CN 115093752B
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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
- 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
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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
- 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
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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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
- 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
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
The invention discloses metal ink for ceramic tiles, which comprises the following raw materials in parts by weight: 45-55 parts of glaze powder base material, 10-20 parts of pigment, 5-9 parts of fiber composite modifier, 3-6 parts of modified nano alumina, 4-10 parts of sodium tripolyphosphate, 1-3 parts of methylcellulose, 1-2 parts of coupling agent and 35-45 parts of solvent. According to the metal ink disclosed by the invention, the glaze powder base material and the pigment are matched, the raw materials such as sodium tripolyphosphate, methyl cellulose and a coupling agent are added as the auxiliary agents, so that the dispersion capacity of the ink is enhanced, the printing effect is improved after the ink is sintered later, the wear-resistant stability of a product can be enhanced by the added fiber composite modifier, the reinforcing and enhancing effects can be achieved by the modified nano-alumina, and the wear-resistant stability is further enhanced.
Description
Technical Field
The invention relates to the technical field of ceramic tiles, in particular to metal ink for ceramic tiles.
Background
The ceramic tile is made of refractory metal oxide and semi-metal oxide, and through grinding, mixing, pressing, glazing and sintering, and is one kind of ceramic, stone, etc. with acid and alkali resistance. The raw materials are mostly mixed by clay and quartz sand after high temperature compression, and the like, and the high-hardness ceramic material has high hardness. Compared with the traditional decoration means for ceramic tile production, the ink-jet printing technology has the following advantages: (1) The energy is saved, the emission is reduced, the intermediate procedures of tabletting, screening, engraving and the like in batch production are eliminated, the production cycle is shortened, the production efficiency is greatly improved, and the loss in the production process is reduced; (2) The printing process is completely controlled by a computer, complex pattern decoration can be performed in the production process, the precision and the repeatability of the pattern are improved, the mechanization degree and the production efficiency of the decoration process can be greatly improved, and the customization of small batches of even single-piece products can be completed; (3) The non-contact type printing can be performed on the concave-convex surface, so that the decoration of some special-shaped products is easy, and the decoration effect is greatly enriched.
The printing layer formed by the existing metal ink through ink jet has poor wear resistance and is easy to wear and lose, and based on the wear resistance, the invention further improves the processing.
Disclosure of Invention
In view of the drawbacks of the prior art, an object of the present invention is to provide a metallic ink for ceramic tiles, so as to solve the problems set forth in the background art.
The invention solves the technical problems by adopting the following technical scheme:
the invention provides a metal ink for ceramic tiles, which comprises the following raw materials in parts by weight:
45-55 parts of glaze powder base material, 10-20 parts of pigment, 5-9 parts of fiber composite modifier, 3-6 parts of modified nano alumina, 4-10 parts of sodium tripolyphosphate, 1-3 parts of methylcellulose, 1-2 parts of coupling agent and 35-45 parts of solvent.
Preferably, the metal ink for the ceramic tile comprises the following raw materials in parts by weight:
50 parts of glaze powder backing material, 15 parts of pigment, 7 parts of fiber composite modifier, 4.5 parts of modified nano-alumina, 7 parts of sodium tripolyphosphate, 2 parts of methylcellulose, 1.5 parts of coupling agent and 40 parts of solvent.
Preferably, the glaze powder base material comprises the following raw materials in parts by weight: 1-5 parts of zirconia, 1-4 parts of potassium oxide, 1-2 parts of titanium dioxide, 0.1-0.7 part of vanadium pentoxide and 0.1-0.6 part of zinc oxide.
Preferably, the preparation method of the fiber composite modifier comprises the following steps:
s101: reacting palygorskite fiber for 15-25min at 75-85 ℃, cooling to room temperature, then sending into 1-3% lanthanum sulfate aqueous solution by mass fraction, stirring and dispersing for 15-25min, and stirring at a speed of 1000-1500r/min to obtain pre-modified palygorskite fiber;
s102: adding 10-20 parts of carbon nano tube into 35-45 parts of modified liquid, stirring and mixing fully to prepare modified carbon nano tube liquid;
s103: mixing the pre-modified palygorskite fiber and the modified carbon nanotube liquid according to the weight ratio of 1:4, performing ultrasonic dispersion treatment, wherein the ultrasonic power is 300-500W, the ultrasonic time is 15-25min, and washing and drying to obtain the fiber composite modified body.
The inventor finds that the wear-resistant retention rate of the product is obviously reduced from 99.9% to 93.2% without adding the fiber composite modifier, and the reduction rate is lower than that of the product without adding the fiber composite modifier because the fiber is singly added, so that raw materials of the product are easily agglomerated, and the wear-resistant stability of the product is affected;
the preparation method of the fiber composite modified body is different from the preparation method of the fiber composite modified body without adding the carbon nano tube and the modification liquid, and the wear resistance stability of the product is reduced, so that the preparation method of the fiber composite modified body has uniqueness, and the preparation effect is obvious by adopting other methods.
Preferably, the stirring and mixing speed in the step S102 is 500-700r/min, and stirring is carried out for 30-40min.
Preferably, the preparation method of the modified liquid comprises the following steps: 5-10 parts of tetradecyl trimethyl ammonium bromide, 1-3 parts of N-octyl diaminoethyl glycine hydrochloride, 4-7 parts of sodium alginate, 1-3 parts of silane coupling agent KH570 and 10-15 parts of glycolic acid aqueous solution are fully mixed to prepare a modified liquid.
Preferably, the mass fraction of the aqueous solution of the hydroxy acetic acid is 5-10%.
Preferably, the modification method of the modified nano alumina comprises the following steps:
s111: the nano alumina is sent into an ethanol solvent with the concentration of 2-5 times to prepare nano alumina suspension;
s112: adding hypochlorous acid aqueous solution with the total amount of 1-5% into the nano alumina suspension of S111, standing for 1-2h at the standing temperature of 55 ℃, then washing with water and drying to obtain active nano alumina;
s113:10-20 parts of active nano alumina is added into 35-45 parts of chitosan modified solution, ultrasonic dispersion is sufficient, ultrasonic power is 100-300W, ultrasonic time is 15-25min, ultrasonic treatment is finished, and the modified nano alumina is obtained through water washing and drying.
The inventor finds that the modified nano alumina and the fiber composite modifier have the advantages that the nano alumina and the fiber composite modifier are coordinated and mutually adopted, the product performance is also obviously reduced, and the interface performance of the product is possibly influenced due to the fact that the nano alumina also influences the dispersibility of raw materials of the product, so that the wear-resistant stability of the product is influenced;
in addition, the modification of nano alumina has characteristics, and the modification by adopting other methods is not obvious as the improvement effect of the invention.
Preferably, the chitosan modified solution is prepared by stirring and mixing 10-20 parts of chitosan, 5-10 parts of acetic acid, 1-3 parts of stearic acid and 1-2 parts of sodium silicate according to parts by weight.
Preferably, the coupling agent is silane coupling agent KH560, and the solvent is one or more of ethanol, isopropanol and butyl acetate; the pigment is one of red brown, orange and cobalt blue.
Compared with the prior art, the invention has the following beneficial effects:
according to the metal ink disclosed by the invention, the glaze powder base material and the pigment are matched, the raw materials such as sodium tripolyphosphate, methyl cellulose and a coupling agent are added as auxiliary agents, so that the dispersion capacity of the ink is enhanced, the printing effect is improved after the ink is sintered later, the wear-resistant stability of a product can be enhanced by the added fiber composite modifier, the reinforcing and enhancing effects can be achieved by the modified nano alumina, and the wear-resistant stability is further enhanced;
in the preparation of the fiber composite modified body, the activity is improved by pre-improving the palygorskite fiber in a lanthanum sulfate aqueous solution, and the carbon nano tube in the carbon nano tube liquid is further improved by forming modified liquid by using carbon nano tube, namely, tetradecyl trimethyl ammonium bromide, N-octyl diaminoethyl glycine hydrochloride, sodium alginate and the like, so that the palygorskite fiber is better improved, the fiber dispersion is improved, and the agglomeration in the fiber re-sintering is avoided, and the effect of a product is influenced;
in addition, after the nano aluminum oxide is modified, the interfacial force is improved, and meanwhile, the dispersing force is improved and is dispersed in the product, so that the further filling and compacting effects are achieved, the stability of the product is enhanced, and the wear-resisting stability effect of the product is improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The metal ink for the ceramic tile comprises the following raw materials in parts by weight:
45-55 parts of glaze powder base material, 10-20 parts of pigment, 5-9 parts of fiber composite modifier, 3-6 parts of modified nano alumina, 4-10 parts of sodium tripolyphosphate, 1-3 parts of methylcellulose, 1-2 parts of coupling agent and 35-45 parts of solvent.
The metal ink for the ceramic tile of the embodiment comprises the following raw materials in parts by weight:
50 parts of glaze powder backing material, 15 parts of pigment, 7 parts of fiber composite modifier, 4.5 parts of modified nano-alumina, 7 parts of sodium tripolyphosphate, 2 parts of methylcellulose, 1.5 parts of coupling agent and 40 parts of solvent.
The glaze powder base material of the embodiment comprises the following raw materials in parts by weight: 1-5 parts of zirconia, 1-4 parts of potassium oxide, 1-2 parts of titanium dioxide, 0.1-0.7 part of vanadium pentoxide and 0.1-0.6 part of zinc oxide.
The preparation method of the fiber composite modified body of the embodiment comprises the following steps:
s101: reacting palygorskite fiber for 15-25min at 75-85 ℃, cooling to room temperature, then sending into 1-3% lanthanum sulfate aqueous solution by mass fraction, stirring and dispersing for 15-25min, and stirring at a speed of 1000-1500r/min to obtain pre-modified palygorskite fiber;
s102: adding 10-20 parts of carbon nano tube into 35-45 parts of modified liquid, stirring and mixing fully to prepare modified carbon nano tube liquid;
s103: mixing the pre-modified palygorskite fiber and the modified carbon nanotube liquid according to the weight ratio of 1:4, performing ultrasonic dispersion treatment, wherein the ultrasonic power is 300-500W, the ultrasonic time is 15-25min, and washing and drying to obtain the fiber composite modified body.
In the step S102 of this embodiment, the stirring and mixing speed is 500-700r/min, and stirring is performed for 30-40min.
The preparation method of the modified liquid in the embodiment comprises the following steps: 5-10 parts of tetradecyl trimethyl ammonium bromide, 1-3 parts of N-octyl diaminoethyl glycine hydrochloride, 4-7 parts of sodium alginate, 1-3 parts of silane coupling agent KH570 and 10-15 parts of glycolic acid aqueous solution are fully mixed to prepare a modified liquid.
The mass fraction of the aqueous solution of hydroxy acetic acid in this example is 5-10%.
The modification method of the modified nano alumina of the embodiment comprises the following steps:
s111: the nano alumina is sent into an ethanol solvent with the concentration of 2-5 times to prepare nano alumina suspension;
s112: adding hypochlorous acid aqueous solution with the total amount of 1-5% into the nano alumina suspension of S111, standing for 1-2h at the standing temperature of 55 ℃, then washing with water and drying to obtain active nano alumina;
s113:10-20 parts of active nano alumina is added into 35-45 parts of chitosan modified solution, ultrasonic dispersion is sufficient, ultrasonic power is 100-300W, ultrasonic time is 15-25min, ultrasonic treatment is finished, and the modified nano alumina is obtained through water washing and drying.
The chitosan modified solution of the embodiment is prepared by mixing 10-20 parts of chitosan, 5-10 parts of acetic acid, 1-3 parts of stearic acid and 1-2 parts of sodium silicate according to parts by weight.
The coupling agent of the embodiment is a silane coupling agent KH560, and the solvent is one or more of ethanol, isopropanol and butyl acetate; the pigment is one of red brown, orange and cobalt blue.
Example 1.
The metal ink for the ceramic tile comprises the following raw materials in parts by weight:
45 parts of glaze powder base material, 10 parts of pigment, 5 parts of fiber composite modifier, 3 parts of modified nano-alumina, 4 parts of sodium tripolyphosphate, 1 part of methylcellulose, 1 part of coupling agent and 35 parts of solvent.
The glaze powder base material of the embodiment comprises the following raw materials in parts by weight: 1 part of zirconia, 1 part of potassium oxide, 1 part of titanium dioxide, 0.1 part of vanadium pentoxide and 0.1 part of zinc oxide.
The preparation method of the fiber composite modified body of the embodiment comprises the following steps:
s101: reacting the palygorskite fiber for 15min at 75 ℃, cooling to room temperature, then sending into a lanthanum sulfate aqueous solution with the mass fraction of 1% for stirring and dispersing for 15min, wherein the stirring speed is 1000r/min, and obtaining the pre-modified palygorskite fiber;
s102: adding 10 parts of carbon nano tubes into 35 parts of modified liquid, and stirring and mixing fully to prepare modified carbon nano tube liquid;
s103: mixing the pre-modified palygorskite fiber and the modified carbon nanotube liquid according to the weight ratio of 1:4, performing ultrasonic dispersion treatment, wherein the ultrasonic power is 300W, the ultrasonic time is 15min, and washing and drying to obtain the fiber composite modified body.
In the step S102 of this example, the stirring and mixing speed was 500r/min, and stirring was performed for 30min.
The preparation method of the modified liquid in the embodiment comprises the following steps: 5 parts of tetradecyltrimethylammonium bromide, 1 part of N-octyl diaminoethyl glycine hydrochloride, 4 parts of sodium alginate, 1 part of a silane coupling agent KH570 and 10 parts of a glycolic acid aqueous solution are fully mixed to prepare a modified liquid.
The mass fraction of the aqueous solution of hydroxyacetic acid in this example was 5%.
The modification method of the modified nano alumina of the embodiment comprises the following steps:
s111: the nano alumina is sent into an ethanol solvent with the concentration of 2 times to prepare nano alumina suspension;
s112: adding 1% hypochlorous acid aqueous solution into the nano alumina suspension of S111, standing for 1h at 55 ℃, washing with water, and drying to obtain active nano alumina;
s113: adding 10 parts of active nano alumina into 35 parts of chitosan modified solution, fully dispersing by ultrasonic, enabling the ultrasonic power to be 100W, enabling the ultrasonic time to be 15min, ending ultrasonic, washing by water, and drying to obtain the modified nano alumina.
The chitosan modified solution of the embodiment is prepared by mixing 10 parts of chitosan, 5 parts of acetic acid, 1 part of stearic acid and 1 part of sodium silicate according to the weight parts.
The coupling agent of the embodiment is silane coupling agent KH560, and the solvent is ethanol; the pigment is reddish brown.
Example 2.
The metal ink for the ceramic tile comprises the following raw materials in parts by weight:
55 parts of glaze powder backing material, 20 parts of pigment, 9 parts of fiber composite modifier, 6 parts of modified nano-alumina, 10 parts of sodium tripolyphosphate, 3 parts of methylcellulose, 2 parts of coupling agent and 45 parts of solvent.
The glaze powder base material of the embodiment comprises the following raw materials in parts by weight: 5 parts of zirconia, 4 parts of potassium oxide, 2 parts of titanium dioxide, 0.7 part of vanadium pentoxide and 0.6 part of zinc oxide.
The preparation method of the fiber composite modified body of the embodiment comprises the following steps:
s101: reacting the palygorskite fiber for 25min at 85 ℃, cooling to room temperature, then sending into a lanthanum sulfate aqueous solution with the mass fraction of 3%, stirring and dispersing for 25min, wherein the stirring speed is 1500r/min, and obtaining the pre-modified palygorskite fiber;
s102: adding 20 parts of carbon nano tubes into 45 parts of modified liquid, and stirring and mixing fully to prepare modified carbon nano tube liquid;
s103: mixing the pre-modified palygorskite fiber and the modified carbon nanotube liquid according to the weight ratio of 1:4, performing ultrasonic dispersion treatment, wherein the ultrasonic power is 500W, the ultrasonic time is 25min, and washing and drying to obtain the fiber composite modified body.
In the step S102 of this embodiment, the stirring and mixing speed was 700r/min, and stirring was performed for 40min.
The preparation method of the modified liquid in the embodiment comprises the following steps: 10 parts of tetradecyl trimethyl ammonium bromide, 3 parts of N-octyl diaminoethyl glycine hydrochloride, 7 parts of sodium alginate, 3 parts of a silane coupling agent KH570 and 15 parts of a glycolic acid aqueous solution are fully mixed to prepare a modified liquid.
The mass fraction of the aqueous solution of hydroxyacetic acid in this example was 10%.
The modification method of the modified nano alumina of the embodiment comprises the following steps:
s111: the nano alumina is sent into ethanol solvent with the concentration of 5 times to prepare nano alumina suspension;
s112: adding 5% hypochlorous acid aqueous solution into the nano alumina suspension of S111, standing for 2h at 55 ℃, washing with water, and drying to obtain active nano alumina;
s113: adding 20 parts of active nano alumina into 45 parts of chitosan modified solution, fully dispersing by ultrasonic, setting the ultrasonic power at 300W, setting the ultrasonic time at 25min, finishing ultrasonic treatment, washing with water, and drying to obtain the modified nano alumina.
The chitosan modified solution of the embodiment is prepared by stirring and mixing 20 parts of chitosan, 10 parts of acetic acid, 3 parts of stearic acid and 2 parts of sodium silicate according to parts by weight.
The coupling agent of the embodiment is silane coupling agent KH560, and the solvent is isopropanol; the pigment is reddish brown.
Example 3.
The metal ink for the ceramic tile comprises the following raw materials in parts by weight:
50 parts of glaze powder backing material, 15 parts of pigment, 7 parts of fiber composite modifier, 4.5 parts of modified nano-alumina, 7 parts of sodium tripolyphosphate, 2 parts of methylcellulose, 1.5 parts of coupling agent and 40 parts of solvent.
The glaze powder base material of the embodiment comprises the following raw materials in parts by weight: 3 parts of zirconia, 2.5 parts of potassium oxide, 1.5 parts of titanium dioxide, 0.4 part of vanadium pentoxide and 0.35 part of zinc oxide.
The preparation method of the fiber composite modified body of the embodiment comprises the following steps:
s101: reacting the palygorskite fiber for 20min at 80 ℃, cooling to room temperature, then sending into a 2% lanthanum sulfate aqueous solution by mass fraction, stirring and dispersing for 20min, wherein the stirring speed is 1250r/min, and obtaining the pre-modified palygorskite fiber;
s102: adding 15 parts of carbon nano tubes into 40 parts of modified liquid, and stirring and mixing fully to prepare modified carbon nano tube liquid;
s103: mixing the pre-modified palygorskite fiber and the modified carbon nanotube liquid according to the weight ratio of 1:4, performing ultrasonic dispersion treatment, wherein the ultrasonic power is 400W, the ultrasonic time is 20min, and washing and drying to obtain the fiber composite modified body.
In the step S102 of this example, the stirring and mixing speed was 600r/min and stirring was carried out for 35min.
The preparation method of the modified liquid in the embodiment comprises the following steps: 7.5 parts of tetradecyl trimethyl ammonium bromide, 2 parts of N-octyl diaminoethyl glycine hydrochloride, 5 parts of sodium alginate, 2 parts of a silane coupling agent KH570 and 12.5 parts of a glycolic acid aqueous solution are fully mixed to prepare a modified liquid.
The mass fraction of the aqueous solution of hydroxy acetic acid in this example is 5-10%.
The modification method of the modified nano alumina of the embodiment comprises the following steps:
s111: the nano alumina is sent into an ethanol solvent with the concentration of 2-5 times to prepare nano alumina suspension;
s112: adding 3% hypochlorous acid aqueous solution into the nano alumina suspension of S111, standing for 1.5h at 55 ℃, washing with water, and drying to obtain active nano alumina;
s113:15 parts of active nano alumina is added into 40 parts of chitosan modified solution, ultrasonic dispersion is complete, ultrasonic power is 200W, ultrasonic time is 20min, ultrasonic treatment is finished, and the modified nano alumina is obtained after washing and drying.
The chitosan modified solution of the embodiment is prepared by mixing 15 parts of chitosan, 7.5 parts of acetic acid, 2 parts of stearic acid and 1.5 parts of sodium silicate according to the weight parts.
The coupling agent of the embodiment is silane coupling agent KH560, and the solvent is butyl acetate; the pigment is reddish brown.
Comparative example 1.
The difference from example 3 is that the fiber composite modifier was not added.
Comparative example 2.
The difference from example 3 is that the fiber composite modifier is replaced with palygorskite fiber.
Comparative example 3.
Unlike example 3, carbon nanotubes were not added to the method for producing the fiber composite modifier.
Comparative example 4.
The difference from example 3 is the preparation method of the modified liquid;
the preparation method of the modified liquid comprises the following steps: 7.5 parts of sodium dodecyl sulfate, 2 parts of phosphoric acid, 5 parts of sodium oxalate and 2 parts of sodium lignin sulfonate are fully mixed to prepare a modified liquid.
Comparative example 5.
The difference from example 3 is that no modified nano alumina was added.
Comparative example 6.
The difference from example 3 is that the modified nano-alumina is replaced with nano-alumina.
Comparative example 7.
The difference from example 3 is the modification method of the modified nano alumina;
the modification method of the modified nano alumina comprises the following steps:
s111: the nano alumina is sent into an ethanol solvent with the concentration of 2-5 times to prepare nano alumina suspension;
s112: adding oxalic acid accounting for 3 percent of the total amount, 1-3 parts of gamma-aminopropyl triethoxysilane and 5 percent of chitosan aqueous solution into the nano alumina suspension of the S111, stirring and mixing fully, washing with water and drying to obtain the modified nano alumina.
To comparatively illustrate the properties of the different products, the following properties of the products obtained in examples and comparative examples were tested;
the products of examples 1-3 and comparative examples 1-7 were sprayed onto tile surfaces, then sintered at 1200 ℃ for 45-55min, then cooled to room temperature, and tested:
the abrasion resistance test standard is as follows: selecting an abrasive with Mohs hardness of 4, and rubbing the abrasive on the ceramic tile for 1000 times, wherein the retention rate is maintained;
the products of examples 1-3 and comparative examples 1-7 were tested for performance as follows:
as can be seen from comparative examples 1 to 4, example 3; the product of the invention is not added with a fiber composite modifier, the wear-resistant retention rate of the product is obviously reduced from 99.9 to 93.2%, the fiber composite modifier is replaced by palygorskite fiber, the reduction rate is lower than that of the product without adding the fiber composite modifier, and the product raw material agglomeration is easy to be caused due to the independent addition of the fiber, but the wear-resistant stability of the product is affected;
the preparation method of the fiber composite modified body is different from the preparation method of the fiber composite modified body without adding the carbon nano tube and the modification liquid, and the wear resistance stability of the product is reduced, so that the preparation method of the fiber composite modified body has uniqueness, and the preparation effect is obvious by adopting other methods as compared with the preparation method of the invention;
from the comparison examples 5 and 1, the modified nano alumina and the fiber composite modifier have the coordination and interaction effects, and can play a role in reinforcing and enhancing the wear resistance stability of the product;
as can be seen from comparative examples 5 to 7, the product performance is also significantly reduced by adopting the nano alumina, and the product interface performance is possibly influenced by the nano alumina, so that the dispersibility of the raw materials of the product is reduced, and the wear resistance stability of the product is influenced;
in addition, the modification of nano alumina has characteristics, and the modification by adopting other methods is not obvious as the improvement effect of the invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (2)
1. The metal ink for the ceramic tile is characterized by comprising the following raw materials in parts by weight:
45-55 parts of glaze powder base material, 10-20 parts of pigment, 5-9 parts of fiber composite modifier, 3-6 parts of modified nano alumina, 4-10 parts of sodium tripolyphosphate, 1-3 parts of methyl cellulose, 1-2 parts of coupling agent and 35-45 parts of solvent;
the glaze powder base material comprises the following raw materials in parts by weight: 1-5 parts of zirconia, 1-4 parts of potassium oxide, 1-2 parts of titanium dioxide, 0.1-0.7 part of vanadium pentoxide and 0.1-0.6 part of zinc oxide;
the preparation method of the fiber composite modifier comprises the following steps:
s101: reacting palygorskite fiber for 15-25min at 75-85 ℃, cooling to room temperature, then sending into 1-3% lanthanum sulfate aqueous solution by mass fraction, stirring and dispersing for 15-25min, and stirring at a speed of 1000-1500r/min to obtain pre-modified palygorskite fiber;
s102: adding 10-20 parts of carbon nano tube into 35-45 parts of modified liquid, stirring and mixing fully to prepare modified carbon nano tube liquid;
s103: mixing the pre-modified palygorskite fiber and the modified carbon nanotube liquid according to the weight ratio of 1:4, performing ultrasonic dispersion treatment, wherein the ultrasonic power is 300-500W, the ultrasonic time is 15-25min, and washing and drying to obtain a fiber composite modified body;
the rotation speed of stirring and mixing in the step S102 is 500-700r/min, and stirring is carried out for 30-40min;
the preparation method of the modified liquid comprises the following steps: fully mixing 5-10 parts of tetradecyl trimethyl ammonium bromide, 1-3 parts of N-octyl diaminoethyl glycine hydrochloride, 4-7 parts of sodium alginate, 1-3 parts of silane coupling agent KH570 and 10-15 parts of glycolic acid aqueous solution to prepare a modified liquid;
the mass fraction of the hydroxy acetic acid aqueous solution is 5-10%;
the modification method of the modified nano alumina comprises the following steps:
s111: the nano alumina is sent into an ethanol solvent with the concentration of 2-5 times to prepare nano alumina suspension;
s112: adding hypochlorous acid aqueous solution with the total amount of 1-5% into the nano alumina suspension of S111, standing for 1-2h at the standing temperature of 55 ℃, then washing with water and drying to obtain active nano alumina;
s113: adding 10-20 parts of active nano alumina into 35-45 parts of chitosan modified solution, fully dispersing by ultrasonic, wherein the ultrasonic power is 100-300W, the ultrasonic time is 15-25min, and washing and drying to obtain modified nano alumina;
the chitosan modified solution is prepared by stirring and mixing 10-20 parts of chitosan, 5-10 parts of acetic acid, 1-3 parts of stearic acid and 1-2 parts of sodium silicate according to parts by weight;
the coupling agent is silane coupling agent KH560, and the solvent is one or more of ethanol, isopropanol and butyl acetate; the pigment is one of red brown, orange and cobalt blue.
2. The metal ink for ceramic tiles according to claim 1, wherein the metal ink for ceramic tiles comprises the following raw materials in parts by weight:
50 parts of glaze powder backing material, 15 parts of pigment, 7 parts of fiber composite modifier, 4.5 parts of modified nano-alumina, 7 parts of sodium tripolyphosphate, 2 parts of methylcellulose, 1.5 parts of coupling agent and 40 parts of solvent.
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