CN113427938B - Decalcomania paper and application thereof - Google Patents
Decalcomania paper and application thereof Download PDFInfo
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- CN113427938B CN113427938B CN202110844188.8A CN202110844188A CN113427938B CN 113427938 B CN113427938 B CN 113427938B CN 202110844188 A CN202110844188 A CN 202110844188A CN 113427938 B CN113427938 B CN 113427938B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/175—Transfer using solvent
- B44C1/1758—Decalcomanias applied under pressure only, e.g. provided with a pressure sensitive layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/12—Stencil printing; Silk-screen printing
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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Abstract
The invention discloses a decal paper and application thereof, wherein the decal paper is prepared by the following method: mixing silicon dioxide, clinker, hydroxyapatite and phyllite, then crushing, calcining and sieving to obtain a ground pigment; mixing the base color material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow, printing the mixture on base paper or pretreated base paper, and drying to obtain base color paper; mixing silicon dioxide, clinker and sphalerite, crushing, calcining and sieving to obtain a relief material; and (3) mixing the relief material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow, printing the mixture on bottom colored paper, and drying to obtain the decal paper. The decal paper can be used for automatic decal process of vessels, and has good microwave oven resistance and thermal shock resistance.
Description
Technical Field
The invention belongs to the technical field of ware decalcomania, and particularly relates to a decal paper and application thereof.
Background
The applique transfers beautiful colorful patterns on the stained paper to a blank or glaze of the porcelain in a sticking way. The ceramic applique is a decoration process that patterns are printed on special paper pre-coated with water-soluble glue, and then the paper is soaked in water for wetting and then transferred and attached to the surface of a ceramic article, and is widely applied to articles such as ceramics, metals, woodware, glass, sports equipment and the like. The ceramic applique is composed of base paper, intermediate layer sol and cover oil. Ceramic appliques can be classified into low temperature appliques and high temperature appliques according to the difference in the grill temperature after transfer. Chinese patent CN102416811B provides an over-glaze ceramic decal paper and a production method thereof, comprising the following steps: uniformly coating water-soluble glue on the hard bottom film; forming a pattern on the water-soluble film by using an aqueous binder chromatography printing pigment; after drying, sticking the mulberry paper on the pattern through a glue layer; after drying, the hard backing film is peeled off, and the mulberry paper and the underlying water-soluble film sandwich the pattern to form a whole. The production process of the ceramic decal paper is environment-friendly and energy-saving, and has high production efficiency, but the adhesion and strength of the ceramic decal paper are still to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a decal paper and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
the decal paper is prepared by the following method:
s1, mixing silica, clinker, hydroxyapatite and phyllite according to the mass ratio of (23-27), (10-15), (7-11), (5-7), crushing, sieving with a 600-minus 800-mesh sieve, calcining for 5-7h at the temperature of 1270-1280 ℃ and under the pressure of 33-36MPa, cooling to 22-26 ℃ along with a furnace, crushing, and sieving with a 600-minus 800-mesh sieve to obtain a ground pigment;
s2, mixing the base color material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of (6-9): (0.5-1.5): (0.6-1.2): (3.5-5) at 30-40 ℃, printing the mixture on base paper by a full-automatic reciprocating screen printer in a 200-mesh and 250-mesh screen printing mode, and drying the mixture for 5-8 hours at 40-50 ℃ under the condition that the air pressure is 88-92kPa to obtain the base color paper;
s3, mixing silicon dioxide, clinker and zinc blende according to the mass ratio of (18-22) to (9-12) to (13-17), crushing, sieving with a 600-fold 800-mesh sieve, calcining for 5-7h at 1340-1350 ℃ and under the pressure of 25-28MPa, cooling to 23-28 ℃ along with the furnace, crushing, and sieving with a 600-fold 800-mesh sieve to obtain a relief material;
s4, mixing the relief material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of (7-9): (0.8-1.2): (1.5-2.3): (3.5-4.5), printing on the base color paper by a full-automatic reciprocating screen printer in a 200-mesh 250-mesh screen printing mode, and drying for 8-12h at the temperature of 52-57 ℃ and under the air pressure of 87-92kPa to obtain the decal paper.
Preferably, the decal paper is prepared by the following method:
s1, mixing silica, clinker, hydroxyapatite and phyllite according to the mass ratio of (23-27), (10-15), (7-11), (5-7), crushing, sieving with a 600-minus 800-mesh sieve, calcining for 5-7h at the temperature of 1270-1280 ℃ and under the pressure of 33-36MPa, cooling to 22-26 ℃ along with a furnace, crushing, and sieving with a 600-minus 800-mesh sieve to obtain a ground pigment;
s2, mixing the base color material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of (6-9): (0.5-1.5): (0.6-1.2): (3.5-5) at 30-40 ℃, printing the mixture on the pretreated base paper by a full-automatic reciprocating screen printer in a 200-250 mesh screen printing mode, and drying the mixture for 5-8 hours at 40-50 ℃ under the condition that the air pressure is 88-92kPa to obtain the base color paper;
s3, mixing silicon dioxide, clinker and zinc blende according to the mass ratio of (18-22) to (9-12) to (13-17), crushing, sieving with a 600-fold 800-mesh sieve, calcining for 5-7h at 1340-1350 ℃ and under the pressure of 25-28MPa, cooling to 23-28 ℃ along with the furnace, crushing, and sieving with a 600-fold 800-mesh sieve to obtain a relief material;
s4, mixing the relief material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of (7-9): (0.8-1.2): (1.5-2.3): (3.5-4.5), printing on the base color paper by a full-automatic reciprocating screen printer in a 200-mesh and 250-mesh screen printing manner, and drying for 8-12h at 52-57 ℃ and under the air pressure of 87-92kPa to obtain the decal paper.
The preparation method of the pretreatment base paper comprises the following steps:
mixing silicon dioxide and 10-20wt.% ethanol aqueous solution according to the mass ratio (0.5-2) of 50, and treating for 20-30min by using ultrasonic waves with the power of 300-500W and the frequency of 25-35 kHz; then adding tetra (dimethylsiloxy) silane and stirring for 10-20min at 50-60 ℃ and 100-150 rpm; centrifuging, collecting precipitate, and drying at 80-90 deg.C under 80-90kPa for 2-3h to obtain modified silicon dioxide; uniformly mixing modified silicon dioxide, polyethylene glycol and water according to the mass ratio of (0.5-1) to (3-5) to (50-60), and stirring at 50-60 ℃ and 300rpm for 30-40min to obtain a pretreatment solution; coating the pretreatment solution on the base paper with a coating thickness of 0.1-0.2mm, and drying at 50-60 deg.C under 80-90kPa for 1-2h to obtain the pretreated base paper.
The preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of (4-6): 15-18): 11-13): 8-10): 14-16): 0.5-1.1): 7-10): 1.5-2.3, crushing and passing through a 600-mesh sieve with 800 meshes to obtain mineral powder;
t2 mixing the mineral powder and 60-65wt.% ethanol water solution according to the mass ratio of 1 (5.5-6.3), treating the mixture by ultrasonic waves with the power of 300-340W and the frequency of 32-35kHz for 25-50min, centrifuging the mixture for 3-5min at the rotating speed of 11000-13000rpm, standing the mixture for 20-25h at the temperature of 5-10 ℃, taking the precipitate, and drying the precipitate for 300min at the temperature of 85-90 ℃ under the nitrogen atmosphere with the air pressure of 80-86kPa to obtain a pretreatment material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of (6.5-8.5) to 1 to obtain a mixed material, and jointly treating the mixed material by adopting a sectional type pressure sintering/pulse electric field to obtain the frit.
The synergist is at least one of potassium antimony oxide tartrate and bismuth chloride; preferably, the synergist is a mixture of potassium antimony oxide tartrate and bismuth chloride according to a mass ratio of (1-5) to (1-5); most preferably, the synergist is a mixture of potassium antimony tartrate and bismuth chloride according to a mass ratio of 5: 3.
The sectional type pressure sintering/pulse electric field combined treatment comprises the following steps:
h1 heating: heating from 20-30 ℃ to 800-810 ℃ at a heating rate of 8-10 ℃/min, preserving the heat for 1-2h, then heating to 1190-1210 ℃ at a heating rate of 5-8 ℃/min, preserving the heat for 2-3h, heating to 1400-1410 ℃ at a heating rate of 3-5 ℃/min, preserving the heat for 2-3h, and then heating to 1525-1535 ℃ at a heating rate of 1-2 ℃/min, preserving the heat for 3-4 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature is 20-30 ℃;
h3 applies a pressure of 100-105MPa to the mixed material in the heating process of H1 and applies a pulse electric field with the strength of 22-26kV/cm, the frequency of 38-42kHz and the pulse width of 40-80 mus.
In the prior art, the adhesion degree between the obtained applique and the surface of a ceramic vessel is not high, the phenomena of failure such as cracks, peeling and the like are easy to occur in the processes of applique burning and service in the prior art, and the resistance to thermal shock and a microwave environment is poor, so the invention aims to provide the applique and the process which can resist the thermal shock and have good resistance to the microwave heating environment.
The relative orientation relation of hydroxyl and ester in ethyl lactate enables the base paper and the applique prepared by the specific method of the invention to be more easily separated, improves the mutual wettability of the applique and the attached ceramic ware, enables the contact effect to be better, and prevents the possibility of falling off and peeling off of the applique in the decoration firing process and the subsequent service process. The iron oxide yellow is dispersed into turbid emulsion by using 2, 5-dihydroxyhexane with a symmetrical o-methylhydroxy structure and tetradecyl thioglycolic acid with sulfur element existing in a meta-position relation with carboxyl, so that the operability of the coloring process and the color developing effect and durability of the iron oxide yellow are improved. The frit is prepared by using zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to a specific method, wherein the atomic weight size and the special charge distribution of the zirconia can enhance the energy dispersion uniformity and the atomic lattice distortion degree in an inorganic compound system in which the zirconia is arranged, and the wear resistance and the durability of the obtained ceramic applique are improved. The specific orientation relation of potassium, antimony and oxygen atoms in the antimony potassium oxysulfate tartrate can improve the crystal face compatibility of each crystal form in the frit, relieve cracking caused by thermal shock caused by temperature change in the burning and subsequent service processes, but weaken the smoothness of the prepared ceramic applique to a certain extent; the addition of bismuth chloride can improve the whiteness of zinc oxide in the frit, and impurities can be removed from the zinc oxide when the frit is sintered, so that the brittleness of crystals caused by unnecessary impurities is prevented, and therefore, the combination of potassium antimony tartrate and bismuth chloride as a synergist of the frit can improve the glossiness of the obtained ceramic applique and simultaneously improve the hardness and the service reliability. The frit is obtained by sintering in a sectional heating/cooling manner, so that the phenomena of uneven element diffusion caused by overhigh heating/cooling rate and aging and precipitation possibly occurring along with time increase at normal temperature can be avoided, and the unnecessary precipitation phenomenon can cause brittle fracture of the ceramic applique, so that the service reliability of the ceramic applique is remarkably reduced. Pressurization during sintering can kinetically provide a motive force for further uniform diffusion of elements. Loading the pulsed electric field during sintering can change the charge distribution of the used inorganic compound, promote the diffusion capacity of the inorganic compound during sintering and melting, and thus can obtain ceramic applique with higher hardness and strength.
The decal paper is applied to an automatic ware decal process.
The automatic adhering flower process for utensil includes the following steps:
w1 soaking the decal paper in an ethyl lactate water solution;
w2 removing the base paper of the decal paper and pasting the decal paper on the surface of the vessel;
w3 the ware was subjected to pressure holding and then to decoration firing to obtain a decal ware.
Preferably, the automatic labeling process for the vessel comprises the following steps:
w1 soaking the above decal paper in 16-19 wt.% ethyl lactate water solution at 42-48 deg.C for 50-70 s; the mass ratio of the decal paper to the ethyl lactate aqueous solution is 1 (55-65);
w2 removing the base paper of the decal paper and pasting the decal paper on the surface of the vessel;
w3 maintaining the pressure of the ware for 15-30s under the conditions of 72-77 ℃ and 0.2-0.4MPa of protective gas, and then baking for 5-7h under the conditions of 500-600 ℃ and nitrogen atmosphere to obtain the applique ware.
The vessel is any one of a ceramic vessel and a glass vessel.
The protective gas is at least one of carbon dioxide and nitrogen; preferably, the protective gas is a mixture of carbon dioxide and nitrogen according to a volume ratio of (1-3) to (1-3).
The invention has the beneficial effects that: the method for manufacturing the decal paper is simple and convenient, can be widely used for the automatic decal process of the vessel, and the manufactured decal vessel can effectively resist thermal shock and has good tolerance to a microwave heating environment.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
ceramic ware, purchased from wutong ceramics ltd, honor county, tribute, Sichuan.
Silica, CAS: 7631-86-9, available from sahn chemical technology (shanghai) ltd, cat #: a61708-500g, particle size: 300 meshes.
Hydroxyapatite, CAS: 1306-06-5, available from Sahn chemical technology (Shanghai) Co., Ltd., cat #: 21223, particle size: 300 meshes.
Phyllite, CAS: 1302-66-5, available from rongxing mining ltd, antifebrile county, particle size: 320 meshes.
Yellow iron oxide, CAS: 20344-49-4, available from Sahn chemical technology (Shanghai) Co., Ltd, No.: A16267.
base paper, purchased from Shandong Shenghe paper-plastic packaging company Limited, materials: polyvinyl butyral, cat No.: SH 002.
Blende, CAS: 1314-98-3, available from sahn chemical technology (shanghai) ltd, No.: a49696-500g, particle size: 400 meshes.
Zinc oxide, CAS: 1314-13-2, available from sahn chemical technology (shanghai) ltd, cat #: e0607215000, particle size: 100 nm.
Quartz, CAS: 14808-60-7, available from Sahn chemical technology (Shanghai) Inc., number: 013024, particle size: 100 μm.
Boronatrocalcite, CAS: 1319-33-1, from Zibozizi new materials science, Inc., cat No.: 1393-96-4, particle size: 200 meshes.
Dolomite, CAS: 16389-88-1, purchased from processing plant of di-Lei mineral products in Hubei Shijiazhuang Lingshu county, goods number: 008, particle size: 100 meshes.
Albite, available from deng-bang trading ltd, Liuzhou, K2O content > 99.5%, Fe2O3Content is less than 65%, Na2The content of O: 99.5% of Al2O3The content is as follows: 65% of SiO2The content is as follows: 68%, density: 69g/cm3The Mohs hardness: 6.5.
zirconium oxide, CAS: 1314-23-4, available from sahn chemical technology (shanghai) ltd, cat # n: e0103105000, particle size: 300 meshes.
Mica, CAS: 12001-26-2, which is purchased from a Shunsheng mineral product processing factory in Hubei Shijiazhuang Lingshou county, and has the particle size: 120 meshes.
Potassium antimony tartrate, CAS: 28300-74-5, available from sahn chemical technology (shanghai) ltd, No.: 383376.
tridecyl 3-mercaptopropionate, CAS: 50727-77-0, available from Hangzhou Dayang chemical Co.
Tetrakis (dimethylsiloxy) silane, CAS: 17082-47-2, available from Han hong technology GmbH of Shanghai.
Polyethylene glycol, CAS: 25322-68-3, available from Shanghai Tantake Tech technologies, Inc., MW: 10000.
an automatic decal machine for ceramic, provided by moral precision machines, ltd, guan, model number: DS-351M.
Full-automatic reciprocating type screen printing machine is provided by wenzhou song xu machinery science and technology limited, and the model of machine is MX-1050GT, the operation mode: full-automatic, printing speed is 50m/min, maximum printing area: 1050mm × 750mm, substrate thickness range: 0.05mm, table size: 1100mm × 800 mm.
Example 1
The decal paper is prepared by the following method:
s1, mixing silicon dioxide, fusion cakes, hydroxyapatite and phyllite according to a mass ratio of 25:12:9:6, crushing, sieving by a 800-mesh sieve, calcining for 6 hours at 1280 ℃ under 35MPa, cooling to 25 ℃ along with a furnace, crushing, and sieving by the 800-mesh sieve to obtain a ground pigment;
s2, mixing the base color material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow at the temperature of 35 ℃, printing the mixture on base paper in a 250-mesh screen printing mode by adopting a full-automatic reciprocating screen printer after mixing the base color material with the 2, 5-dihydroxyhexane, the tetradecyl thioglycolic acid and the iron oxide yellow according to the mass ratio of 7:1:1:4, and drying the mixture for 6 hours at the temperature of 50 ℃ under the air pressure of 90kPa to obtain base color paper;
s3, mixing silicon dioxide, clinker and sphalerite according to a mass ratio of 20:11:15, crushing, sieving with a 800-mesh sieve, calcining at 1350 ℃ and a pressure of 27MPa for 6 hours, cooling to 25 ℃ along with a furnace, crushing, and sieving with the 800-mesh sieve to obtain a relief material;
s4, mixing the relief material, 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of 8:1:2:4, printing the mixture on the base color paper in a 250-mesh screen printing mode by using a full-automatic reciprocating screen printer, and then drying the base color paper for 10 hours at the temperature of 55 ℃ and under the air pressure of 90kPa to obtain the decal paper.
The preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of 5:17:12:9:15:1:9:2, crushing and sieving with a 800-mesh sieve to obtain mineral powder;
t2 mixing mineral powder and 65wt.% ethanol water solution in a mass ratio of 1:6, treating with ultrasonic wave with power of 340W and frequency of 35kHz for 40min, centrifuging at 13000rpm for 4min, standing at 10 deg.C for 24h, collecting precipitate, drying at 90 deg.C under 85kPa nitrogen atmosphere for 180min to obtain pretreated material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of 8:1 to obtain a mixed material, and jointly processing the mixed material by adopting a sectional type pressure sintering/pulse electric field to obtain the frit.
The synergist is a mixture of potassium antimony oxide tartrate and bismuth chloride according to the mass ratio of 5: 3.
The sectional type pressure sintering/pulse electric field combined treatment comprises the following steps:
h1 heating: heating from 25 ℃ to 800 ℃ at a heating rate of 10 ℃/min and preserving heat for 1h, then heating to 1200 ℃ at a heating rate of 8 ℃/min and preserving heat for 2h, then heating to 1400 ℃ at a heating rate of 5 ℃/min and preserving heat for 2.5h, and then heating to 1532 ℃ at a heating rate of 2 ℃/min and preserving heat for 3 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature reaches 25 ℃;
h3 applied a pressure of 105MPa to the mixture during the heating process of H1 and applied a pulsed electric field with a strength of 25kV/cm, a frequency of 40kHz and a pulse width of 60 mus.
The automatic adhering flower process for utensil includes the following steps:
w1 soaking the above decal paper in 18 wt.% ethyl lactate water solution at 45 deg.C for 60 s; the mass ratio of the decal paper to the ethyl lactate aqueous solution is 1: 60;
w2 removing the base paper of the decal paper and pasting the decal paper on the surface of the ceramic ware;
w3 adopts a ceramic automatic applique machine, the ceramic ware is kept for 20s under the condition of 75 ℃ and 0.3MPa of protective gas, and then the ceramic ware is baked for 6h under the condition of 600 ℃ and nitrogen atmosphere, thus obtaining the applique ware. The protective gas is a mixture of carbon dioxide and nitrogen according to a volume ratio of 3: 2.
Example 2
Essentially the same as example 1, except that: the synergist is antimony potassium tartrate.
Example 3
Essentially the same as example 1, except that: the synergist is bismuth chloride.
Comparative example 1
Essentially the same as example 1, except that:
the preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of 5:17:12:9:15:1:9:2, crushing and sieving with a 800-mesh sieve to obtain mineral powder;
t2 mixing mineral powder and 65wt.% ethanol water solution in a mass ratio of 1:6, treating with ultrasonic wave with power of 340W and frequency of 35kHz for 40min, centrifuging at 13000rpm for 4min, standing at 10 deg.C for 24h, collecting precipitate, drying at 90 deg.C under 85kPa nitrogen atmosphere for 180min to obtain pretreated material;
t3 the frit is obtained by treating the pretreated material with a combination of segmented pressure sintering and pulsed electric field.
The sectional type pressure sintering/pulse electric field combined treatment comprises the following steps:
h1 heating: heating from 25 ℃ to 800 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, then heating to 1200 ℃ at a heating rate of 8 ℃/min, preserving heat for 2h, heating to 1400 ℃ at a heating rate of 5 ℃/min, preserving heat for 2.5h, then heating to 1532 ℃ at a heating rate of 2 ℃/min, and preserving heat for 3 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature reaches 25 ℃;
h3 the pretreatment material was subjected to a pressure of 105MPa in the heating process of H1 and a pulsed electric field of 25kV/cm in intensity, 40kHz in frequency and 60. mu.s in pulse width was applied.
Comparative example 2
Essentially the same as example 1, except that:
the preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of 5:17:12:9:15:1:9:2, crushing and sieving with a 800-mesh sieve to obtain mineral powder;
t2 mixing mineral powder and 65wt.% ethanol water solution in a mass ratio of 1:6, treating with ultrasonic wave with power of 340W and frequency of 35kHz for 40min, centrifuging at 13000rpm for 4min, standing at 10 deg.C for 24h, collecting precipitate, drying at 90 deg.C under 85kPa nitrogen atmosphere for 180min to obtain pretreated material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of 8:1 to obtain a mixed material, and jointly processing the mixed material by adopting a sectional type pressure sintering/pulse electric field to obtain the frit.
The synergist is a mixture of potassium antimony oxide tartrate and bismuth chloride according to the mass ratio of 5: 3.
The sectional type pressure sintering treatment comprises the following steps:
h1 heating: heating from 25 ℃ to 800 ℃ at a heating rate of 10 ℃/min and preserving heat for 1h, then heating to 1200 ℃ at a heating rate of 8 ℃/min and preserving heat for 2h, then heating to 1400 ℃ at a heating rate of 5 ℃/min and preserving heat for 2.5h, and then heating to 1532 ℃ at a heating rate of 2 ℃/min and preserving heat for 3 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature reaches 25 ℃;
h3 applied a pressure of 105MPa to the mixture during the heating of H1.
Comparative example 3
Essentially the same as example 1, except that:
the preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of 5:17:12:9:15:1:9:2, crushing and sieving with a 800-mesh sieve to obtain mineral powder;
t2 mixing mineral powder and 65wt.% ethanol water solution in a mass ratio of 1:6, treating with ultrasonic wave with power of 340W and frequency of 35kHz for 40min, centrifuging at 13000rpm for 4min, standing at 10 deg.C for 24h, collecting precipitate, drying at 90 deg.C under 85kPa nitrogen atmosphere for 180min to obtain pretreated material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of 8:1 to obtain a mixed material, and jointly processing the mixed material by adopting a pressurized sintering/pulsed electric field to obtain the frit.
The synergist is a mixture of potassium antimony oxide tartrate and bismuth chloride according to the mass ratio of 5: 3.
The pressure sintering/pulse electric field combined treatment comprises the following steps:
h1 heating: heating from 25 ℃ to 1532 ℃ at the heating rate of 2 ℃/min and preserving heat for 3 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature reaches 25 ℃;
h3 applied a pressure of 105MPa to the mixture during the heating process of H1 and applied a pulsed electric field with a strength of 25kV/cm, a frequency of 40kHz and a pulse width of 60 mus.
Comparative example 4
Essentially the same as example 1, except that:
the preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of 5:17:12:9:15:1:9:2, crushing and sieving with a 800-mesh sieve to obtain mineral powder;
t2 mixing mineral powder and 65wt.% ethanol water solution in a mass ratio of 1:6, treating with ultrasonic wave with power of 340W and frequency of 35kHz for 40min, centrifuging at 13000rpm for 4min, standing at 10 deg.C for 24h, collecting precipitate, drying at 90 deg.C under 85kPa nitrogen atmosphere for 180min to obtain pretreated material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of 8:1 to obtain a mixed material, and jointly processing the mixed material by adopting a sectional type pressure sintering/pulse electric field to obtain the frit.
The synergist is a mixture of potassium antimony oxide tartrate and bismuth chloride according to the mass ratio of 5: 3.
The sectional sintering/pulse electric field combined treatment comprises the following steps:
h1 heating: heating from 25 ℃ to 800 ℃ at a heating rate of 10 ℃/min and preserving heat for 1h, then heating to 1200 ℃ at a heating rate of 8 ℃/min and preserving heat for 2h, then heating to 1400 ℃ at a heating rate of 5 ℃/min and preserving heat for 2.5h, and then heating to 1532 ℃ at a heating rate of 2 ℃/min and preserving heat for 3 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature reaches 25 ℃;
H3A pulsed electric field with intensity of 25kV/cm, frequency of 40kHz and pulse width of 60 mus is applied to the mixed material in the heating process of H1.
Comparative example 5
Essentially the same as example 1, except that:
the preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, mica and barium carbonate according to the mass ratio of 5:17:12:9:15:9:2, crushing and sieving with a 800-mesh sieve to obtain mineral powder;
t2 mixing mineral powder and 65wt.% ethanol water solution in a mass ratio of 1:6, treating with ultrasonic wave with power of 340W and frequency of 35kHz for 40min, centrifuging at 13000rpm for 4min, standing at 10 deg.C for 24h, collecting precipitate, drying at 90 deg.C under 85kPa nitrogen atmosphere for 180min to obtain pretreated material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of 8:1 to obtain a mixed material, and jointly processing the mixed material by adopting a sectional type pressure sintering/pulse electric field to obtain the frit.
The synergist is a mixture of potassium antimony oxide tartrate and bismuth chloride according to the mass ratio of 5: 3.
The sectional type pressure sintering/pulse electric field combined treatment comprises the following steps:
h1 heating: heating from 25 ℃ to 800 ℃ at a heating rate of 10 ℃/min and preserving heat for 1h, then heating to 1200 ℃ at a heating rate of 8 ℃/min and preserving heat for 2h, then heating to 1400 ℃ at a heating rate of 5 ℃/min and preserving heat for 2.5h, and then heating to 1532 ℃ at a heating rate of 2 ℃/min and preserving heat for 3 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature reaches 25 ℃;
h3 applied a pressure of 105MPa to the mixture during the heating process of H1 and applied a pulsed electric field with a strength of 25kV/cm, a frequency of 40kHz and a pulse width of 60 mus.
Comparative example 6
Essentially the same as example 1, except that:
the decal paper is prepared by the following method:
s1, mixing silicon dioxide, frit, hydroxyapatite and phyllite according to a mass ratio of 25:12:9:6, crushing, sieving with a 800-mesh sieve, calcining at 1280 ℃ under 35MPa for 6 hours, cooling to 25 ℃ along with a furnace, crushing, and sieving with the 800-mesh sieve to obtain a ground pigment;
s2, mixing the base color material with 2, 5-dihydroxyhexane, tridecyl 3-mercaptopropionate and iron oxide yellow at the temperature of 35 ℃, printing the mixture on base paper in a 250-mesh screen printing mode by adopting a full-automatic reciprocating screen printing machine after mixing the base color material, the 2, 5-dihydroxyhexane, the tridecyl 3-mercaptopropionate and the iron oxide yellow according to the mass ratio of 7:1:1:4, and then drying the mixture for 6 hours at the temperature of 50 ℃ under the air pressure of 90kPa to obtain base color paper;
s3, mixing silicon dioxide, clinker and sphalerite according to a mass ratio of 20:11:15, crushing, sieving with a 800-mesh sieve, calcining at 1350 ℃ and a pressure of 27MPa for 6 hours, cooling to 25 ℃ along with a furnace, crushing, and sieving with the 800-mesh sieve to obtain a relief material;
s4, mixing the relief material, 2, 5-dihydroxyhexane, tridecyl 3-mercaptopropionate and iron oxide yellow according to the mass ratio of 8:1:2:4, printing the mixture on the base color paper in a 250-mesh screen printing mode by using a full-automatic reciprocating screen printer, and drying the base color paper for 10 hours at the temperature of 55 ℃ and under the air pressure of 90kPa to obtain the decal paper.
Example 4
The decal paper is prepared by the following method:
s1, mixing silicon dioxide, frit, hydroxyapatite and phyllite according to a mass ratio of 25:12:9:6, crushing, sieving with a 800-mesh sieve, calcining at 1280 ℃ under 35MPa for 6 hours, cooling to 25 ℃ along with a furnace, crushing, and sieving with the 800-mesh sieve to obtain a ground pigment;
s2, mixing the base color material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow at the temperature of 35 ℃, printing the mixture on pretreated base paper in a 250-mesh screen printing mode by adopting a full-automatic reciprocating screen printer after mixing the base color material, the 2, 5-dihydroxyhexane, the tetradecyl thioglycolic acid and the iron oxide yellow according to the mass ratio of 7:1:1:4, and drying the mixture for 6 hours at the temperature of 50 ℃ under the air pressure of 90kPa to obtain base color paper;
s3, mixing silicon dioxide, clinker and sphalerite according to a mass ratio of 20:11:15, crushing, sieving with a 800-mesh sieve, calcining at 1350 ℃ and a pressure of 27MPa for 6 hours, cooling to 25 ℃ along with a furnace, crushing, and sieving with the 800-mesh sieve to obtain a relief material;
s4, mixing the relief material, 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of 8:1:2:4, printing the mixture on the base color paper in a 250-mesh screen printing mode by using a full-automatic reciprocating screen printer, and then drying the base color paper for 10 hours at the temperature of 55 ℃ and under the air pressure of 90kPa to obtain the decal paper.
The preparation method of the pretreated base paper comprises the following steps:
mixing silicon dioxide with 20wt.% ethanol water solution at a mass ratio of 1:50, and treating with ultrasonic wave with power of 300W and frequency of 25kHz for 30 min; then adding tetra (dimethylsiloxy) silane, and stirring at 55 ℃ and 120rpm for 20 min; centrifuging, collecting precipitate, and drying at 90 deg.C under 85kPa for 2.5h to obtain modified silicon dioxide; uniformly mixing modified silicon dioxide, polyethylene glycol and water in a mass ratio of 0.5:4:55, and stirring at 50 ℃ and 250rpm for 35min to obtain a pretreatment solution; and (3) coating the pretreatment liquid on the base paper, wherein the coating thickness is 0.2mm, and drying for 1.5h at the temperature of 55 ℃ and under the air pressure of 90kPa to obtain the pretreated base paper.
The preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of 5:17:12:9:15:1:9:2, crushing and sieving with a 800-mesh sieve to obtain mineral powder;
t2 mixing mineral powder and 65wt.% ethanol water solution in a mass ratio of 1:6, treating with ultrasonic wave with power of 340W and frequency of 35kHz for 40min, centrifuging at 13000rpm for 4min, standing at 10 deg.C for 24h, collecting precipitate, drying at 90 deg.C under 85kPa nitrogen atmosphere for 180min to obtain pretreated material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of 8:1 to obtain a mixed material, and jointly processing the mixed material by adopting a sectional type pressure sintering/pulse electric field to obtain the frit.
The synergist is a mixture of potassium antimony oxide tartrate and bismuth chloride according to the mass ratio of 5: 3.
The sectional type pressure sintering/pulse electric field combined treatment comprises the following steps:
h1 heating: heating from 25 ℃ to 800 ℃ at a heating rate of 10 ℃/min and preserving heat for 1h, then heating to 1200 ℃ at a heating rate of 8 ℃/min and preserving heat for 2h, then heating to 1400 ℃ at a heating rate of 5 ℃/min and preserving heat for 2.5h, and then heating to 1532 ℃ at a heating rate of 2 ℃/min and preserving heat for 3 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature reaches 25 ℃;
h3 applied a pressure of 105MPa to the mixture during the heating process of H1 and applied a pulsed electric field with a strength of 25kV/cm, a frequency of 40kHz and a pulse width of 60 mus.
The automatic utensil applique technology consists of the following steps:
w1 soaking the above decal paper in 18 wt.% ethyl lactate water solution at 45 deg.C for 60 s; the mass ratio of the decal paper to the ethyl lactate aqueous solution is 1: 60;
w2 removing the base paper of the decal paper and pasting the decal paper on the surface of the ceramic ware;
w3 adopts a ceramic automatic applique machine, the ceramic ware is kept for 20s under the condition of 75 ℃ and 0.3MPa of protective gas, and then the ceramic ware is baked for 6h under the condition of 600 ℃ and nitrogen atmosphere, thus obtaining the applique ware. The protective gas is a mixture of carbon dioxide and nitrogen according to a volume ratio of 3: 2. The decalcomania paper obtained in the example 4 has good decalcomania effect and high decalcomania transfer efficiency in the automatic ware decalcomania process, and the decalcomania transfer rate is 91.6%.
Comparative example 7
The decal paper is prepared by the following method:
s1, mixing silicon dioxide, frit, hydroxyapatite and phyllite according to a mass ratio of 25:12:9:6, crushing, sieving with a 800-mesh sieve, calcining at 1280 ℃ under 35MPa for 6 hours, cooling to 25 ℃ along with a furnace, crushing, and sieving with the 800-mesh sieve to obtain a ground pigment;
s2, mixing the base color material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow at the temperature of 35 ℃, printing the mixture on pretreated base paper in a 250-mesh screen printing mode by adopting a full-automatic reciprocating screen printer after mixing the base color material, the 2, 5-dihydroxyhexane, the tetradecyl thioglycolic acid and the iron oxide yellow according to the mass ratio of 7:1:1:4, and drying the mixture for 6 hours at the temperature of 50 ℃ under the air pressure of 90kPa to obtain base color paper;
s3, mixing silicon dioxide, clinker and sphalerite according to a mass ratio of 20:11:15, crushing, sieving with a 800-mesh sieve, calcining at 1350 ℃ and a pressure of 27MPa for 6 hours, cooling to 25 ℃ along with a furnace, crushing, and sieving with the 800-mesh sieve to obtain a relief material;
s4, mixing the relief material, 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of 8:1:2:4, printing the mixture on the base color paper in a 250-mesh screen printing mode by using a full-automatic reciprocating screen printer, and then drying the base color paper for 10 hours at the temperature of 55 ℃ and under the air pressure of 90kPa to obtain the decal paper.
The preparation method of the pretreated base paper comprises the following steps:
uniformly mixing silicon dioxide, polyethylene glycol and water in a mass ratio of 0.5:4:55, and stirring at 50 ℃ and 250rpm for 35min to obtain a pretreatment solution; and (3) coating the pretreatment liquid on the base paper, wherein the coating thickness is 0.2mm, and drying for 1.5h at the temperature of 55 ℃ and under the air pressure of 90kPa to obtain the pretreated base paper.
The preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of 5:17:12:9:15:1:9:2, crushing and sieving with a 800-mesh sieve to obtain mineral powder;
t2 mixing mineral powder and 65wt.% ethanol water solution in a mass ratio of 1:6, treating with ultrasonic wave with power of 340W and frequency of 35kHz for 40min, centrifuging at 13000rpm for 4min, standing at 10 deg.C for 24h, collecting precipitate, drying at 90 deg.C under 85kPa nitrogen atmosphere for 180min to obtain pretreated material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of 8:1 to obtain a mixed material, and jointly processing the mixed material by adopting a sectional type pressure sintering/pulse electric field to obtain the frit.
The synergist is a mixture of potassium antimony oxide tartrate and bismuth chloride according to the mass ratio of 5: 3.
The sectional type pressure sintering/pulse electric field combined treatment comprises the following steps:
h1 heating: heating from 25 ℃ to 800 ℃ at a heating rate of 10 ℃/min and preserving heat for 1h, then heating to 1200 ℃ at a heating rate of 8 ℃/min and preserving heat for 2h, then heating to 1400 ℃ at a heating rate of 5 ℃/min and preserving heat for 2.5h, and then heating to 1532 ℃ at a heating rate of 2 ℃/min and preserving heat for 3 h;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature reaches 25 ℃;
h3 applied a pressure of 105MPa to the mixture during the heating process of H1 and applied a pulsed electric field with a strength of 25kV/cm, a frequency of 40kHz and a pulse width of 60 mus.
The automatic adhering flower process for utensil includes the following steps:
w1 soaking the above decal paper in 18 wt.% ethyl lactate water solution at 45 deg.C for 60 s; the mass ratio of the decal paper to the ethyl lactate aqueous solution is 1: 60;
w2 removing the base paper of the decal paper and pasting the decal paper on the surface of the ceramic ware;
w3 adopts a ceramic automatic applique machine, the ceramic ware is kept for 20s under the condition of 75 ℃ and 0.3MPa of protective gas, and then the ceramic ware is baked for 6h under the condition of 600 ℃ and nitrogen atmosphere, thus obtaining the applique ware. The protective gas is a mixture of carbon dioxide and nitrogen according to a volume ratio of 3: 2. The decal paper obtained in comparative example 7 had a poorer decal effect in the automatic decal process for vessels than example 4, and had a decal transfer rate of 87.9%.
Test example 1
And (3) testing thermal shock resistance: the thermal shock resistance of the applique on the surface of the applique ware obtained in each example of the invention is tested according to GB/T3298-. 5 samples were taken for each case; coating a methylene blue solution with the concentration of 0.3 wt.% on the surface of the sample, wiping off the dyeing solution after the sample is slightly dried, and observing whether the sample has defects of cracks, damages, falling off and the like by naked eyes under the illumination condition that the distance from the sample is 30cm and the illumination of a light source is 300 lx; starting a heating furnace, and setting the heating temperature to be 200 ℃; vertically putting the sample after heat preservation into water at 20 ℃ within 15s, and keeping for 10min, wherein the water surface is 20mm higher than the sample, and the water temperature is increased by no more than 2 ℃; taking out the sample, wiping the sample with water, coating a methylene blue solution with the concentration of 0.3 wt.% on the surface of the sample, wiping the dyeing solution after the sample is slightly dried, and observing whether the sample has defects of cracks, shedding and the like; after standing for 24h, the test was repeated. The results are shown in Table 1.
TABLE 1 thermal shock resistance of decal ware
Test example 2
And (3) microwave oven resistance test: the microwave oven resistance test was carried out on the decalcomania on the surface of the decalcomania ware obtained in each example of the present invention according to QB/T2456-. 5 samples were taken for each case; immersing a sample in water with the temperature of 20 ℃ for 1h, taking out the sample, wiping the surface of the sample with cloth, quickly placing the sample in the center of a turntable of a microwave oven for microwave heating, and respectively placing a container filled with 125mL of water at two corners of the microwave oven, wherein the container is not contacted with the turntable; the total heating energy is 72000J, the microwave power is 800W, and the heating time is 90 s; taking out the sample after heating, placing the sample on a cement board, and naturally cooling to room temperature; 500mm from the specimen and the specimen was observed from the front. The results are shown in Table 2.
TABLE 2 microwave oven resistance of decal ware
Test example 3
And (3) hardness testing: the hardness of the surface of the applique ware obtained in each example of the invention was measured according to QB/T4780-. Fixing the sample on a sample loading platform, selecting a 200g weight according to the hardness of the sample, keeping the load for 15s, unloading the load after the indentation is finished, rotating a micrometer, recording the reading, obtaining the length of the diagonal line, and obtaining the length of the diagonal line according to the HV (2 P.sin 136 degree/2)/d (1.8544P/d)2The Vickers hardness of each sample was determined. The results are shown in Table 3.
TABLE 3 hardness of the surface of the Applique vessel
Obviously, the thermal shock resistance, the microwave resistance and the hardness of the material in the embodiment 1 are superior to those of other embodiments. The relative orientation relation of hydroxyl and ester in ethyl lactate enables the base paper and the applique prepared by the specific method of the invention to be more easily separated, improves the mutual wettability of the applique and the attached ceramic ware, enables the contact effect to be better, and prevents the possibility of falling off and peeling off of the applique in the decoration firing process and the subsequent service process. The 2, 5-dihydroxyhexane with a symmetrical o-methylhydroxyl structure and the tetradecyl thioglycolic acid with sulfur element existing in a meta-position relation with carboxyl are used for dispersing the iron oxide yellow into turbid whey, so that the operability of a coloring process and the color developing effect and durability of the iron oxide yellow are improved. The frit is prepared by using zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to a specific method, wherein the atomic weight size and the special charge distribution of the zirconia can enhance the energy dispersion uniformity and the atomic lattice distortion degree in an inorganic compound system in which the zirconia is arranged, and the wear resistance, toughness, hardness and durability of the obtained ceramic applique are improved. The specific orientation relation of potassium, antimony and oxygen atoms in the antimony potassium oxysulfate tartrate can improve the crystal face compatibility of each crystal form in the frit, relieve cracking caused by thermal shock caused by temperature change in the burning and subsequent service processes, but weaken the smoothness of the prepared ceramic applique to a certain extent; the addition of bismuth chloride can improve the whiteness of zinc oxide in the frit, and impurities can be removed from the zinc oxide when the frit is sintered, so that the brittleness of crystals caused by unnecessary impurities is prevented, and therefore, the combination of potassium antimony tartrate and bismuth chloride as a synergist of the frit can improve the glossiness of the obtained ceramic applique and simultaneously improve the hardness and the service reliability. The frit is obtained by sintering in a sectional heating/cooling manner, so that the phenomena of uneven element diffusion caused by overhigh heating/cooling rate and aging and precipitation possibly occurring along with time increase at normal temperature can be avoided, and the unnecessary precipitation phenomenon can cause brittle fracture of the ceramic applique, so that the service reliability of the ceramic applique is remarkably reduced. Pressurization during sintering can kinetically provide a motive force for further uniform diffusion of elements. Loading the pulsed electric field during sintering can change the charge distribution of the used inorganic compound, promote the diffusion capacity of the inorganic compound during sintering and melting, and thus can obtain ceramic applique with higher hardness and strength.
Claims (5)
1. The decal paper is characterized by being prepared by the following method:
s1, mixing silica, clinker, hydroxyapatite and phyllite according to the mass ratio of (23-27), (10-15), (7-11), (5-7), crushing, sieving with a 600-minus 800-mesh sieve, calcining for 5-7h at the temperature of 1270-1280 ℃ and under the pressure of 33-36MPa, cooling to 22-26 ℃ along with a furnace, crushing, and sieving with a 600-minus 800-mesh sieve to obtain a ground pigment;
s2, mixing the base color material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of (6-9): (0.5-1.5): (0.6-1.2): 3.5-5) at 30-40 ℃, printing the mixture on base paper or pretreated base paper in a 200-mesh 250-mesh screen printing mode, and drying the mixture for 5-8 hours at 40-50 ℃ under the air pressure of 88-92kPa to obtain base color paper;
s3, mixing silicon dioxide, clinker and zinc blende according to the mass ratio of (18-22) to (9-12) to (13-17), crushing, sieving with a 600-fold 800-mesh sieve, calcining for 5-7h at 1340-1350 ℃ and under the pressure of 25-28MPa, cooling to 23-28 ℃ along with the furnace, crushing, and sieving with a 600-fold 800-mesh sieve to obtain a relief material;
s4, mixing the relief material with 2, 5-dihydroxyhexane, tetradecyl thioglycolic acid and iron oxide yellow according to the mass ratio of (7-9): (0.8-1.2): (1.5-2.3): (3.5-4.5), printing on the base color paper in a 200-mesh 250-mesh screen printing mode, and then drying for 8-12h at the temperature of 52-57 ℃ and under the air pressure of 87-92kPa to obtain the decal paper;
the preparation method of the frit comprises the following steps:
t1 mixing zinc oxide, quartz, ascharite, dolomite, albite, zirconia, mica and barium carbonate according to the mass ratio of (4-6): 15-18): 11-13): 8-10): 14-16): 0.5-1.1): 7-10): 1.5-2.3, crushing and passing through a 600-mesh sieve with 800 meshes to obtain mineral powder;
t2 mixing the mineral powder and 60-65wt.% ethanol water solution according to the mass ratio of 1 (5.5-6.3), treating the mixture by ultrasonic waves with the power of 300-340W and the frequency of 32-35kHz for 25-50min, centrifuging the mixture for 3-5min at the rotating speed of 11000-13000rpm, standing the mixture for 20-25h at the temperature of 5-10 ℃, taking the precipitate, and drying the precipitate for 300min at the temperature of 85-90 ℃ under the nitrogen atmosphere with the air pressure of 80-86kPa to obtain a pretreatment material;
t3, uniformly mixing the pretreatment material and the synergist according to the mass ratio of (6.5-8.5) to 1 to obtain a mixed material, and jointly treating the mixed material by adopting a sectional type pressure sintering/pulse electric field to obtain the frit.
2. The decal paper according to claim 1, wherein said pretreated base paper is prepared by:
mixing silicon dioxide with 10-20wt.% ethanol water solution at a mass ratio of 0.5-2: 50, and treating with ultrasonic wave with power of 300-500W and frequency of 25-35kHz for 20-30 min; then adding tetra (dimethylsiloxy) silane to stir for 10-20min at 50-60 ℃ and 100-150 rpm; centrifuging, collecting precipitate, and drying at 80-90 deg.C under 80-90kPa for 2-3h to obtain modified silicon dioxide; uniformly mixing modified silicon dioxide, polyethylene glycol and water according to the mass ratio of (0.5-1) to (3-5) to (50-60), and stirring at 50-60 ℃ and 300rpm for 30-40min to obtain a pretreatment solution; coating the pretreatment solution on the base paper with a coating thickness of 0.1-0.2mm, and drying at 50-60 deg.C under 80-90kPa for 1-2h to obtain the pretreated base paper.
3. The decal paper according to claim 1, wherein said synergist is at least one of potassium antimony tartrate and bismuth chloride.
4. The decal paper according to claim 1, wherein said segmented pressure sintering/pulsed electric field combined treatment consists of the steps of:
h1 heating: heating from 20-30 ℃ to 800-;
h2 cooling: closing a heat source, and cooling along with the furnace until the temperature is 20-30 ℃;
h3 applies a pressure of 100-105MPa to the mixed material in the heating process of H1 and applies a pulse electric field with the strength of 22-26kV/cm, the frequency of 38-42kHz and the pulse width of 40-80 mus.
5. Use of a decal according to any one of claims 1 to 4 in an automatic process for the decal of a vessel.
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