CN115385672B - Opalescent porcelain powder and preparation method thereof - Google Patents

Opalescent porcelain powder and preparation method thereof Download PDF

Info

Publication number
CN115385672B
CN115385672B CN202211144166.1A CN202211144166A CN115385672B CN 115385672 B CN115385672 B CN 115385672B CN 202211144166 A CN202211144166 A CN 202211144166A CN 115385672 B CN115385672 B CN 115385672B
Authority
CN
China
Prior art keywords
percent
opalescent
porcelain
powder
nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202211144166.1A
Other languages
Chinese (zh)
Other versions
CN115385672A (en
Inventor
李蛟
鄢新章
刘谋山
郑杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Besmile Biotechnology Co ltd
Original Assignee
Chengdu Besmile Biotechnology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chengdu Besmile Biotechnology Co ltd filed Critical Chengdu Besmile Biotechnology Co ltd
Priority to CN202211144166.1A priority Critical patent/CN115385672B/en
Publication of CN115385672A publication Critical patent/CN115385672A/en
Application granted granted Critical
Publication of CN115385672B publication Critical patent/CN115385672B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C12/00Powdered glass; Bead compositions
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201Alkali metal oxides or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203Lithium oxide or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208Calcium oxide or oxide-forming salts thereof, e.g. lime
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/36Glass starting materials for making ceramics, e.g. silica glass
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646Optical properties

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

The invention relates to the technical field of ceramic materials, in particular to opalescent porcelain powder and a preparation method thereof. The specific technical scheme is as follows: the opalescent porcelain powder comprises the following components in percentage by weight: 10.1 to 20 percent of micro-nano leucite crystal, 79 to 89.9 percent of vitreous base powder and 0.01 to 0.1 percent of inorganic pigment. The invention solves the problem that the milky effect of the porcelain powder is uncontrollable in the prior art.

Description

Opalescent porcelain powder and preparation method thereof
Technical Field
The invention relates to the technical field of ceramic materials, in particular to opalescent porcelain powder and a preparation method thereof.
Background
The design idea of opalescent effect porcelain is to carry out color mixing according to different color requirements on the premise of meeting the performances of various porcelain powders. The imported emulsion porcelain powder has excellent aesthetic effect and physical and chemical properties, but has high price; the price of the dairy porcelain powder produced by domestic manufacturers is relatively low, but the performance of the dairy porcelain powder is inferior to that of imported dairy porcelain powder in aesthetic effect and physical and chemical properties, and the dairy porcelain powder has not been widely accepted by the market.
The prior common porcelain powder with main types such as intrinsic porcelain, enamel porcelain, transparent porcelain and the like has defects in gloss and translucency compared with natural teeth, the natural teeth have good milky gloss and high translucency at cut ends and adjacent parts of the teeth, and the opalescent effect porcelain can supplement the problems of poor aesthetic effect, low translucency and the like of the porcelain powder with main types such as the intrinsic porcelain, the enamel porcelain, the transparent porcelain and the like after being used, so that the opalescent effect porcelain becomes one of the main types of zirconia porcelain powder more and more.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides opalescent porcelain powder and a preparation method thereof, and solves the problem that the opalescent effect of porcelain powder in the prior art is uncontrollable.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the invention discloses opalescent porcelain powder which comprises the following components in percentage by weight: 10.1 to 20 percent of micro-nano leucite crystal, 79 to 89.9 percent of vitreous base powder and 0.01 to 0.1 percent of inorganic pigment.
Preferably, the micro-nano garnet crystal comprises, in weight percent: 45% -65% of SiO 2 10 to 30 percent of Al 2 O 3 10-30% of K 2 O, 1-10% Na 2 O, 0.1-5% TiO 2 0.1 to 5 percent of Li 2 0.1 to 5 percent of O and 0.1 to 5 percent of SnO 2
Preferably, the vitreous base powder comprises, in weight percent: 60% -70% of SiO 2 10 to 20 percent of alumina and 8 to 24 percent of K 2 O, 1-10% Na 2 O, 0.1 to 5 percent of CaO, 0.1 to 5 percent of BaO and 0.1 to 5 percent of TiO 2 ZrO 0.1% -5% 2 0.1 to 5 percent of Li 2 O、0.1%~5%SnO 2 2-10% of B 2 O 3 MgO in 0.1-5 wt% and MgO in 0.01-2%F wt% 4 Si、0.01%~2%P 2 O 5 0.01 to 1 percent of ZnO and 0.01 to 1 percent of Y 2 O 3
Preferably, the inorganic pigment is at least one of erbium chloride, manganese chloride, praseodymium chloride and ferric chloride.
Correspondingly, the preparation method of the opalescent porcelain powder comprises the following steps: solid-phase sintering the leucite crystal, and then ball milling, drying and sieving the leucite crystal to obtain the micro-nano leucite crystal; melting, opacifying and grinding the vitreous base powder and the inorganic pigment to obtain the vitreous base powder; mixing the micro-nano leucite crystals and the vitreous base powder, and then sintering, grinding and spray drying to obtain the opalescent effect porcelain powder.
Preferably, the preparation process of the vitreous base powder comprises the following steps:
(1) 8 to 24 percent of K 2 O, 1-10% Na 2 O, 0.1 to 5 percent of BaO and 0.1 to 5 percent of TiO 2 ZrO 0.1% -5% 2 0.1 to 5 percent of Li 2 O、0.1%~5%SnO 2 2-10% of B 2 O 3 MgO in 0.1-5 wt% and MgO in 0.01-2%P wt% 2 O 5 0.01 to 1 percent of ZnO and 0.01 to 1 percent of Y 2 O 3 Uniformly mixing to obtain a mixture;
(2) Will be 0.01% -2%F 4 Dissolving Si in 50-70% ethanol to obtain emulsion for later use;
(3) Mixing 10-20% of alumina, 0.1-5% of CaO and inorganic pigment, heating to 1200-1600 ℃ at 4-10 ℃/min, preserving heat for 1-3 h, cooling, pulverizing, mixing with 60-70% of SiO 2 Mixing to obtain adsorbent for use;
(4) Uniformly mixing the prepared adsorbent and emulsion, standing for 1-3 h, adding the mixture, uniformly mixing, heating to 1500-1600 ℃ at 4-10 ℃/min, preserving heat for 1-3 h, preserving heat, solidifying molten glass after the heat preservation is finished, preserving heat for 3-5 h at 500-800 ℃, rapidly placing into cold water for water quenching, crushing, grinding and sieving with a 18-mesh sieve to obtain the vitreous base powder.
Preferably, the alumina comprises alpha alumina and gamma alumina, and the mass ratio is 8-9:1-2.
Preferably, the vitreous base powder and the micro-nano leucite crystal are uniformly mixed according to the mass ratio of 79-90:10-20, then the temperature is raised to 850-1100 ℃ at 5-8 ℃/min, the heat is preserved for 30-90 min, after the heat preservation is finished, the mixture is put into water for cold quenching, crushed and then screened by a 18-mesh sieve, and the opalescent effect porcelain base powder is obtained.
Preferably, the opalescent effect porcelain base powder comprises the following components in parts by mass: (10-100): ball milling is carried out for 0.5 to 5 hours under the condition of (10 to 100), and the opalescent effect porcelain powder is obtained by spray drying.
Preferably, the preparation process of the micro-nano leucite crystal comprises the following steps: uniformly mixing leucite crystals, heating to 1200-1400 ℃ at a speed of 7-12 ℃/min, preserving heat for 1-3 h, cooling to room temperature, crushing, grinding, sieving with a 18-mesh sieve, and mixing the materials with distilled water according to the mass ratio of (80-200): (10-50): ball milling for 1-24 h under the condition of (10-50), drying, and sieving with a 200-mesh sieve to obtain the micro-nano leucite crystal.
The invention has the following beneficial effects:
according to the invention, alpha alumina and gamma alumina are added into the vitreous base powder, calcium oxide is combined to prepare the adsorbent with micropores, silicon tetrafluoride is dissolved in ethanol and is adsorbed by the adsorbent, and other components of the vitreous base powder are combined to sinter, so that silicon tetrafluoride is successfully added to prepare the vitreous base powder. And the opalescent porcelain powder with controllable opalescence effect is prepared by combining phosphorus pentoxide and controlling the contents of silicon tetrafluoride and phosphorus pentoxide. Moreover, the ceramic material has the advantages of good natural opalescence effect, good permeability, high strength, high corrosion resistance and the like after sintering; in industrial preparation, the cost is lower, and each preparation method is simple and easy to operate, so that commercialization of the opalescent porcelain powder can be effectively realized.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. 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 technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.
In the invention, the proportion of opal porcelain powder, micro-nano leucite crystal and vitreous base powder are calculated according to mass percent, so the percentages in the proportion table disclosed by the invention are defined according to the percentages of the components in the respective formulas. The percentage of manganese chloride as disclosed in table 4 was selected based on its proportion in opalescent porcelain powder.
1. The invention discloses opalescent porcelain powder which comprises the following components in percentage by weight: 10.1 to 20 percent of micro-nano leucite crystal, 79 to 89.9 percent of vitreous base powder and 0.01 to 0.1 percent of inorganic pigment.
Wherein, according to weight percent, the micro-nano leucite crystal comprises: 45% -65% of SiO 2 10 to 30 percent of Al 2 O 3 10-30% of K 2 O, 1-10% Na 2 O、0.1 to 5 percent of TiO 2 0.1 to 5 percent of Li 2 0.1 to 5 percent of O and 0.1 to 5 percent of SnO 2
The vitreous base powder comprises: 60% -70% of SiO 2 10 to 20 percent of alumina and 8 to 24 percent of K 2 O, 1-10% Na 2 O, 0.1 to 5 percent of CaO, 0.1 to 5 percent of BaO and 0.1 to 5 percent of TiO 2 ZrO 0.1% -5% 2 0.1 to 5 percent of Li 2 O、0.1%~5%SnO 2 2-10% of B 2 O 3 MgO in 0.1-5 wt% and MgO in 0.01-2%F wt% 4 Si、0.01%~2%P 2 O 5 0.01 to 1 percent of ZnO and 0.01 to 1 percent of Y 2 O 3
The inorganic pigment is at least one of erbium chloride, manganese chloride, praseodymium chloride and ferric chloride.
According to the invention, phosphide and fluoride are added into the formula of the porcelain powder at the same time, so that the glass has a milky effect, if fluoride is added singly, the opacifying effect of fluoride on the glass is not strong, and a large amount of fluoride is added to generate the opacifying effect, and when more fluoride is added, the strength of the finally produced porcelain powder is influenced to a certain extent; the emulsion effect is too strong and is not easy to control when phosphide is added alone, and the emulsion effect can be quickly formed by emulsion after the phosphide is poured out, so that the problem of uneven emulsion of the glass (the inside of the glass can be quickly milky) is generated. Therefore, the invention can make the milky effect more uniform in a controllable range on the basis of the expected milky effect by adjusting the proportion of the fluoride and the phosphide on the basis.
2. The invention also discloses a preparation method of the opalescent porcelain powder, which comprises the following steps:
(1) Preparation of micro-nano leucite crystal
Weighing the components of the micro-nano leucite crystal according to the formula 1, uniformly mixing, heating to 1200-1400 ℃ at 7-12 ℃/min, preserving heat for 1-3 h, cooling to room temperature, crushing, grinding, sieving with a 18-mesh sieve, and mixing with the following components in percentage by mass (80-200): (10-50): ball milling is carried out for 1 to 24 hours under the condition of (10 to 50),drying and sieving with a 200-mesh sieve to obtain micro-nano leucite crystals. The micro-nano leucite crystal prepared by the invention has controllable components and shape, higher thermal expansion coefficient, and is generally (22-30) multiplied by 10 -6 And (K) the ceramic powder prepared by the method has the advantages of continuously adjustable thermal expansion coefficients, ceramic powder with different thermal expansion coefficients can be prepared according to specific requirements in actual operation, and meanwhile, the white garnet crystal also has the refractive index close to that of stone glass, so that the transparency required by the ceramic powder is not influenced by strong diffuse scattering.
(2) Preparation of vitreous base powder
1) 8 to 24 percent of K 2 O, 1-10% Na 2 O, 0.1 to 5 percent of BaO and 0.1 to 5 percent of TiO 2 ZrO 0.1% -5% 2 0.1 to 5 percent of Li 2 O、0.1%~5%SnO 2 2-10% of B 2 O 3 MgO in 0.1-5 wt% and MgO in 0.01-2%P wt% 2 O 5 0.01 to 1 percent of ZnO and 0.01 to 1 percent of Y 2 O 3 Uniformly mixing to obtain a mixture;
2) Will be 0.01 to 2%F 4 Dissolving Si in 50-70% ethanol to obtain emulsion (i.e. silicon tetrafluoride ethanol solution) for later use; wherein the mass fraction of the silicon tetrafluoride ethanol solution is 10-30%, and the dissolution time is 1-4 h. Due to F 4 Si is gas and can not be directly added into the material, so that the Si is dissolved in ethanol, and is mixed with the mixture for high-temperature sintering after being adsorbed by the adsorbent, so that not only is the opacifying effect more uniform, but also F is solved 4 Si is scattered into the air to cause harm to human body. The ethanol may be in excess to completely dissolve F 4 Si is the right.
3) Mixing 10-20% of alumina, 0.1-5% of CaO and inorganic pigment, heating to 1200-1600 ℃ at 4-10 ℃/min, preserving heat for 1-3 h, cooling, pulverizing, mixing with 60-70% of SiO 2 Mixing to obtain adsorbent for use; wherein the alumina comprises alpha alumina and gamma alumina, and the mass ratio is 8-9:1-2. It should be noted that: calcium oxide and alpha alumina form calcium aluminum crystal form in high temperature sintering, so as to obtain stable structureIs a micro-pore of (a). The added gamma alumina can take account of two factors of material strength and stability, and when the gamma alumina is higher than 800 ℃, crystal form change occurs, and simultaneously volume shrinkage is accompanied, so that in the sintering process, more open pores can be formed due to crystal form transformation shrinkage of the gamma alumina, and the obtained open pores have smaller pore diameters, uniform distribution and good pore structure, thereby being beneficial to adsorbing emulsion.
4) Uniformly mixing the prepared adsorbent and emulsion, and standing for 1-3 h; then adding the mixture, uniformly mixing, heating to 1500-1600 ℃ at 4-10 ℃/min, preserving heat for 1-3 h, after the heat preservation is finished, solidifying the molten glass, preserving heat for 3-5 h at 500-800 ℃, rapidly putting into cold water for water quenching, crushing, grinding and sieving with a 18-mesh sieve to obtain the vitreous base powder. It should be noted that: upon water quenching, the vitreous base powder exhibits a milky effect.
(3) Preparation of opalescent effect porcelain powder
Uniformly mixing vitreous base powder and micro-nano leucite crystals according to the mass ratio of 79-90:10-20, heating to 850-1100 ℃ at 5-8 ℃/min, preserving heat for 30-90 min, putting into water for cold quenching after the heat preservation is finished, and sieving with a 18-mesh sieve after crushing to obtain opalescent effect porcelain base powder. The opalescent effect porcelain base powder comprises the following components in percentage by mass (80-200): (10-100): ball milling is carried out for 0.5 to 5 hours under the condition of (10 to 100), and the opalescent effect porcelain powder is obtained by spray drying. The ceramic powder prepared by mixing the white pomegranate crystals and the vitreous base powder has the characteristic of continuously adjustable thermal expansion coefficient, and meanwhile, the opalescent ceramic powder matched with the thermal expansion coefficient of the zirconia full ceramic bottom crown can be prepared.
The invention is further illustrated below in conjunction with specific examples.
Examples
The preparation process was carried out according to method 2 described above.
1. Preparation of micro-nano leucite crystal
According to the proportion shown in the following table 1, the temperature is raised to 1350 ℃ at a heating rate of 10 ℃/min, then the mixture is kept for 2 hours, crushed, ground and screened by a 18-mesh sieve, ball milling is carried out for 8 hours under the condition that the mass ratio of balls, materials and distilled water is 100:30:30, and the mixture is dried and screened by a 200-mesh sieve, thus obtaining the micro-nano leucite crystal.
TABLE 1 proportion of micro-nano-sized leucite crystals (%)
Group of SiO 2 Al 2 O 3 K 2 O Na 2 O TiO 2 Li 2 O SnO 2
Group 1 45 29 13 6 2.5 2.5 2
Group 2 49 25 13 6 2.5 2.5 2
Group 3 59 15 13 6 2.5 2.5 2
Group 4 64 10 13 6 2.5 2.5 2
2. Preparation of vitreous base powder
The proportions of the mixtures are shown in Table 2 below. Before preparing the porcelain powder, the components were weighed according to the proportions shown in the following table.
TABLE 2 formulation of vitreous base powder (%)
Figure BDA0003854933130000071
3. Preparation of the emulsion
The proportions are shown in Table 3 below.
TABLE 3 emulsion formulation (%)
Group of F 4 Si Mass fraction of ethanol Mass fraction of silicon tetrafluoride ethanol solution
Group A1 0.01 65 10
Group A2 0.5 65 10
Group A3 1 65 20
Group A4 2 65 30
4. Preparation of adsorbents
The proportions are shown in Table 4 below. Heating to 1400 ℃ at 8 ℃/min, preserving heat for 2h, cooling, pulverizing, mixing with SiO 2 Mixing to obtain the adsorbent. The control group is common alumina.
Table 4 proportion of adsorbents (%)
Figure BDA0003854933130000072
/>
Figure BDA0003854933130000081
5. Adsorption effect of adsorbent on emulsion
And (3) uniformly mixing the adsorbent and the emulsion, and standing for 2 hours. The results are shown in Table 5 below. As a result, the adsorption effect was evaluated by the content of the siliconoxide tetrafluoride solution in the remaining emulsion. The result shows that after the alpha alumina, the gamma alumina and the calcium oxide are sintered at high temperature, a plurality of micropores are formed, and the adsorption of emulsion can be increased, so that the content of silicon tetrafluoride in the preparation process of the emulsion porcelain powder is controlled.
TABLE 5 adsorption Effect of adsorbents
Figure BDA0003854933130000082
/>
Figure BDA0003854933130000091
6. The adsorbents of the adsorption emulsion of table 5 were mixed with the mixture, and each group of table 5 was mixed in accordance with table 2 to obtain 36 groups of vitreous base powders (for example, group a of table 2, based on alumina, alpha alumina and gamma alumina were mixed with the other components of group a in three proportions of table 4, so that there were three experiments for the proportions shown in group a, and the total of 36 experiments for the whole table 2). After the temperature is raised to 1580 ℃ at 5 ℃ per minute, the glass is kept for 2 hours, after the molten glass is solidified after the temperature is kept, the molten glass is quickly put into cold water for water quenching after the temperature is kept for 4 hours at 650 ℃, at this time, the effect of milky white is achieved on all groups of glass, and the milky white degree is different. And then crushing and grinding the water quenched glass, and sieving the crushed and ground glass with a 18-mesh sieve to obtain the vitreous base powder. In contrast, in comparative example 1, the glass paper base powder was obtained directly according to the above sintering parameters in accordance with the proportions shown in Table 2 without preparing an emulsion. Comparative example 2 is the same as the preparation method of the present invention. The results show that the glass prepared in comparative example 1, when quenched with water, had a problem of uneven glass opacification (rapid milky white inside the glass). The glass prepared in comparative example 2 had a poor opacifying effect on the glass when quenched with water.
7. Preparation of opalescent effect porcelain powder
7.1, uniformly mixing the vitreous base powder and the micro-nano leucite crystal according to the mass ratio of 89:10.95 (89% of the vitreous base powder, 10.95% of the micro-nano leucite crystal and 0.05% of the inorganic pigment according to the mass percentage), heating to 1000 ℃ at 5 ℃/min, preserving heat for 50min, putting into water for quenching after the heat preservation is finished, and sieving with a 18-mesh sieve after crushing to obtain the opalescent effect porcelain base powder. The opalescent effect porcelain base powder is prepared from the following components in percentage by mass: 30: ball milling is carried out for 3 hours under the condition of 30, and the opalescent effect porcelain powder is obtained by spray drying. The test of the three-point flexural strength and the thermal expansion coefficient was carried out according to the method of GB 30367-2013 "dental ceramic Material". The results are shown in Table 6 below, wherein the vitreous base powders prepared in the proportions shown in the groups B6+A3+i were selected, and the respective proportions shown in Table 1 were mixed to prepare the emulsion porcelain powders, and the thermal expansion coefficients and the three-point flexural strength were measured.
Table 6 Performance display of porcelain powders of each group
Figure BDA0003854933130000101
7.2 selecting group B6+A3+i+group 2 of Table 6, preparing opalescent effect porcelain powder according to the method of 7.1, performing chemical solubility test according to the method in YY 0716-2009 "dental ceramics", and preparing 10 samples and 6 samples respectively for chemical solubility test and facing porcelain strength test. The results are shown in Table 7 below.
Table 7 Performance display of porcelain powders
Figure BDA0003854933130000111
8. Influence of the content and proportion of silicon tetrafluoride and phosphorus pentoxide on the thermal expansion coefficient and three-point bending strength of the porcelain powder. The proportion of micro-nano-sized leucite crystals was as set 1 in table 1 and the adsorbents were prepared as set B6 in table 5. The results are shown in Table 8 below.
TABLE 8 influence of the contents and proportions of silicon tetrafluoride and phosphorus pentoxide on the properties of porcelain powders
Figure BDA0003854933130000112
/>
Figure BDA0003854933130000121
9. Mode of addition for silicon tetrafluoride
(1) The silicon tetrafluoride is directly pressed and condensed into liquid, and when the vitreous base powder is sintered, the silicon tetrafluoride liquid is added after the sintering of the vitreous base powder is completed, and as a result, the problem that the silicon tetrafluoride volatilizes due to the fact that milky white color only appears on part of glass and is very uneven is found.
(2) In the process of sintering the vitreous base powder, sintering is performed in an atmosphere containing silicon tetrafluoride gas. The results show that after sintering is completed, a large amount of silicon tetrafluoride gas is still present as a gas, while the water quenched glass has only a slight opalescence on the surface and no or too much opalescence inside.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (8)

1. A preparation method of opalescent porcelain powder is characterized in that: the method comprises the following steps: solid-phase sintering the leucite crystal, and then ball milling, drying and sieving the leucite crystal to obtain the micro-nano leucite crystal; melting, opacifying and grinding the vitreous base powder and the inorganic pigment to obtain pigment-containing vitreous base powder; mixing micro-nano leucite crystals and vitreous base powder containing pigment, and then sintering, grinding and spray drying to obtain opalescent effect ceramic powder;
the preparation process of the vitreous base powder containing pigment comprises the following steps:
(1) 8 to 24 percent of K 2 O, 1-10% Na 2 O, 0.1 to 5 percent of BaO and 0.1 to 5 percent of TiO 2 ZrO 0.1% -5% 2 0.1 to 5 percent of Li 2 O、0.1%~5%SnO 2 2-10% of B 2 O 3 MgO in 0.1-5 wt% and MgO in 0.01-2%P wt% 2 O 5 0.01 to 1 percent of ZnO and 0.01 to 1 percent of Y 2 O 3 Uniformly mixing to obtain a mixture;
(2) Will be 0.01% -2%F 4 Dissolving Si in 50-70% ethanol to obtain emulsion for later use;
(3) Mixing 10-20% of alumina, 0.1-5% of CaO and inorganic pigment, heating to 1200-1600 ℃ at 4-10 ℃/min, preserving heat for 1-3 h, cooling, pulverizing, mixing with 60-70% of SiO 2 Mixing to obtain adsorbent for use;
(4) Uniformly mixing the prepared adsorbent and emulsion, standing for 1-3 h, adding the mixture, uniformly mixing, heating to 1500-1600 ℃ at 4-10 ℃/min, preserving heat for 1-3 h, preserving heat, solidifying molten glass after the heat preservation is finished, preserving heat for 3-5 h at 500-800 ℃, rapidly placing into cold water for water quenching, crushing, grinding and sieving with a 18-mesh sieve to obtain vitreous base powder containing pigment;
wherein, the opalescent effect porcelain powder comprises the following raw materials in percentage by weight: 10.1 to 20 percent of micro-nano leucite crystal, 79 to 89.9 percent of vitreous basic powder containing pigment and 0.01 to 0.1 percent of inorganic pigment;
the vitreous base powder containing pigment comprises the following components in percentage by weight: 60% -70% of SiO 2 10 to 20 percent of alumina and 8 to 24 percent of K 2 O, 1-10% Na 2 O, 0.1 to 5 percent of CaO, 0.1 to 5 percent of BaO and 0.1 to 5 percent of TiO 2 ZrO 0.1% -5% 2 、0.1%~5% Li 2 O、0.1%~5%SnO 2 2-10% of B 2 O 3 MgO in 0.1-5 wt% and MgO in 0.01-2%F wt% 4 Si、0.01%~2%P 2 O 5 0.01 to 1 percent of ZnO and 0.01 to 1 percent of Y 2 O 3
2. The method for preparing opalescent porcelain powder according to claim 1, which is characterized in that: the alumina comprises alpha alumina and gamma alumina, and the mass ratio is 8-9:1-2.
3. The method for preparing opalescent porcelain powder according to claim 1, which is characterized in that: uniformly mixing the vitreous base powder containing the pigment and the micro-nano leucite crystal, heating to 850-1100 ℃ at 5-8 ℃/min, preserving heat for 30-90 min, putting into water for cold quenching after preserving heat, crushing, and sieving with a 18-mesh sieve to obtain the opalescent effect porcelain base powder.
4. A method for preparing opalescent porcelain powder according to claim 3, which is characterized in that: the opalescent effect porcelain base powder comprises the following components in parts by mass: (10-100): ball milling is carried out for 0.5 to 5 hours under the condition of (10 to 100), and the opalescent effect porcelain powder is obtained by spray drying.
5. The method for preparing opalescent porcelain powder according to claim 1, which is characterized in that: the preparation process of the micro-nano leucite crystal comprises the following steps: uniformly mixing leucite crystal raw materials, heating to 1200-1400 ℃ at a speed of 7-12 ℃/min, preserving heat for 1-3 h, cooling to room temperature, crushing, grinding, sieving with a 18-mesh sieve, and mixing the materials with distilled water according to the mass ratio of (80-200): (10-50): ball milling for 1-24 h under the condition of (10-50), drying, and sieving with a 200-mesh sieve to obtain the micro-nano leucite crystal.
6. An opalescent porcelain powder produced by the production method of claim 1.
7. According to the weightsA opalescent porcelain powder as defined in claim 6 wherein: the micro-nano leucite crystal comprises the following components in percentage by weight: 45% -65% of SiO 2 10 to 30 percent of Al 2 O 3 10-30% of K 2 O, 1-10% Na 2 O, 0.1-5% TiO 2 0.1 to 5 percent of Li 2 0.1 to 5 percent of O and 0.1 to 5 percent of SnO 2
8. The opalescent porcelain powder of claim 6 wherein: the inorganic pigment is at least one of erbium chloride, manganese chloride, praseodymium chloride and ferric chloride.
CN202211144166.1A 2022-09-20 2022-09-20 Opalescent porcelain powder and preparation method thereof Active CN115385672B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211144166.1A CN115385672B (en) 2022-09-20 2022-09-20 Opalescent porcelain powder and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211144166.1A CN115385672B (en) 2022-09-20 2022-09-20 Opalescent porcelain powder and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115385672A CN115385672A (en) 2022-11-25
CN115385672B true CN115385672B (en) 2023-04-28

Family

ID=84126763

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211144166.1A Active CN115385672B (en) 2022-09-20 2022-09-20 Opalescent porcelain powder and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115385672B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE603476C (en) * 1931-10-23 1934-10-03 Beryllium Dev Corp Separation of metals or metalloids forming water-soluble double fluorides from their compounds, in particular oxide or silicate ores containing foreign metals
CN101234851B (en) * 2008-03-04 2010-11-17 浙江大学 Method for preparing fluorine phosphorus composite opacifying glass
CN101244889A (en) * 2008-03-19 2008-08-20 山东轻工业学院 Non-fluorin environment protection opacifiedglass material and method for manufacturing same
CN109363952B (en) * 2018-11-29 2021-08-17 成都贝施美生物科技有限公司 Porcelain powder and preparation method thereof

Also Published As

Publication number Publication date
CN115385672A (en) 2022-11-25

Similar Documents

Publication Publication Date Title
CN109363952B (en) Porcelain powder and preparation method thereof
CN102503122B (en) Leadless, cadmium-free and strontium-free glass and manufacture process thereof
CN101768016A (en) Enamel color ceramic glaze and production process and application thereof
CN106477877B (en) Extra-high refraction high density environment-friendly type cameo glass of one kind and preparation method thereof
CN101875567A (en) Exquisite glaze, exquisite ceramic and preparation process of exquisite ceramic
CN110078371B (en) Low-melting glass composition with excellent water resistance
CN109095778B (en) Microcrystalline glass ceramic tile and preparation method thereof
CN109095775A (en) A kind of clear frit and preparation method thereof suitable for high-strength ceramic whiteware
CN105174724A (en) Preparation method of lithium base glass ceramic used for dental restoration bodies
CN113087389A (en) Method for preparing lithium silicate glass or lithium silicate glass ceramic body with different light transmittances
JPS62158134A (en) Preparation of colored frit and artificial stone
CN103910489A (en) Glass used as dental veneering porcelain, preparation method and application thereof
CN101050059B (en) Covering layer without lead, cadmium of pigment without lead on ceramic glaze, and preparation method
CN113666640B (en) Mesoporous antibacterial frit, preparation method thereof and preparation method of antibacterial ceramic tile
CN115385672B (en) Opalescent porcelain powder and preparation method thereof
CN101857463B (en) Ceramic glaze and preparation method thereof
CN113149438B (en) Tooth glaze composition, method for forming tooth glaze and denture prosthesis
CN109180006A (en) A kind of low-temperature co-burning ceramic material and preparation method thereof
CN108706880A (en) A kind of red glaze of corrosion resistant an ancient unit of weight and preparation method thereof
CN115028364B (en) Glass ceramic, preparation method thereof and dental restoration material
CN112358182A (en) Antibacterial and deodorant Jun porcelain glaze and preparation method thereof
CN107417104A (en) A kind of pottery moon white glaze and preparation method thereof
JP3088074B2 (en) Manufacturing method of paint for ceramics
CN110713345B (en) Enamel color material, preparation method and application in repairing enamel cultural relics painted on porcelain body
CN114477773A (en) Pyrochlore phase-lithium disilicate glass ceramic, preparation method thereof and dental prosthesis

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant