CN109485380A - A kind of the 3D printing ceramic material and Method of printing of rapid shaping - Google Patents
A kind of the 3D printing ceramic material and Method of printing of rapid shaping Download PDFInfo
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- CN109485380A CN109485380A CN201810037272.7A CN201810037272A CN109485380A CN 109485380 A CN109485380 A CN 109485380A CN 201810037272 A CN201810037272 A CN 201810037272A CN 109485380 A CN109485380 A CN 109485380A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/1305—Organic additives
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/131—Inorganic additives
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/405—Iron group metals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
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- Inorganic Chemistry (AREA)
- Producing Shaped Articles From Materials (AREA)
Abstract
The invention discloses the 3D printing ceramic material and Method of printing of a kind of rapid shaping, the ceramic material is made of the raw material of following parts by weight: the wooden Mount Tai china clay, and 30-40 parts, clay: 10-15 parts, aluminium oxide: 18-25 parts, 10-18 parts of zirconium oxide, iron powder: 2-10 parts, auxiliary agent: 25-33 parts；Method of printing, comprising the following steps: (1) the wooden Mount Tai china clay, clay, aluminium oxide, zirconium oxide and auxiliary agent are uniformly mixed, are passed through nitrogen to exclude air, added iron powder and stirred in logical nitrogen, until iron powder obtains the ceramic material after mixing evenly；(2) ceramic material is placed in 3D printer hopper, Yang Nong Du≤10ppm in the hopper；(3) starting 3D printer printing ceramics just base, then postmenstruation processing and polishing, obtains final ceramic product.Technical solution of the present invention realizes rapid shaping at normal temperatures and pressures, shortens molding cycle, save the cost, and process conditions are simple, it is easy to accomplish, it can large-scale application.
Description
Technical field
The present invention relates to the 3D printing techniques of ceramic material, more particularly, to a kind of 3D printing ceramic material of rapid shaping
And Method of printing.
Background technique
3D printing technique is a kind of entity rapid prototyping & manufacturing technology, it is using discrete -- accumulation principle combines calculating
The advantage of the multinomial technology such as machine graphics process, digital information and control, ray machine power technology and material technology passes through successively different
The accumulation of figure ultimately forms a three-dimension object.With the development and application of 3D printing technique, material becomes limitation 3D printing
One of the key factor of technology future trend, to a certain extent, the development of material decide that can 3D printing have widely
Using.3D printing material mainly includes high molecular material, metal material, inorganic non-metallic material and food material etc. at present.
The raw material that ceramic 3D printing technique uses is ceramic powders or ceramic slurries, and forming technique and technique, at present
It is divided into two kinds of forming methods of straight forming and indirect forming, straight forming uses selective laser sintering and moulding, directly obtains pottery
Porcelain products, shaping speed is fast, and precision is high, but energy consumption is high, and the requirement to material and printer is high, thus with high costs, is unfavorable for
The large-scale promotion and use of 3D printing；Indirect forming coats ceramic particle as carrier using high molecular material, is printing
Shi Jinhang is heated, and carries out molding bonded after melt polymer material, then made pottery by subsequent techniques such as degreasing, plastic removal, sintering
Porcelain products, condition of molding is mild, and cost is relatively low, but subsequent technique is complicated, and molding cycle is long, and precision is poor.
For example, disclosed a kind of nano ceramic material and its 3D printing molding side for 3D printing on Chinese patent
Method, Publication No. CN105130402A, will using inorganic clay as binder using the high-ductility and caking property of inorganic clay
Nano-ceramic particle is mixed with inorganic clay, obtains the nano ceramic material for 3D printing, then form by 3D printing, simultaneously
Using laser sintered, by laser rapid heating and cooling characteristic, inorganic clay is sintered to form nanoscale ceramic crystalline grain,
And nano ceramics product is formed with nano-ceramic particle.
Disclosed 3D printing titanium oxide ceramics material and preparation method thereof, Publication No. on Chinese patent
CN106699111A, the preparation method include: 1) by kaolin, diatomite, titanium oxide, boric acid, sucrose, molybdenum trioxide, nanometer
Aluminium, glass fibre and water are mixed, and are then calcined so that calcined product is made；2) by Kynoar, methylcellulose,
Silane coupling agent is mixed with calcined product base-material is made；3) base-material is ground so that 3D printing titanium oxide ceramics is made
Material.
Summary of the invention
The present invention is that above-mentioned existing ceramic 3D printing technique laser sintering and moulding energy consumption is high, is unfavorable for 3D printing in order to overcome
Popularization and use or molding bonded complex process, the long problem of molding cycle provides a kind of 3D printing ceramics of rapid shaping
Material and Method of printing, without laser sintered, using molding bonded, under normal condition can rapid curing, simple process molding week
Phase is short, effectively improves ceramic 3D printing efficiency.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of 3D printing ceramic material of rapid shaping, is made of the raw material of following parts by weight:
30-40 parts of the wooden Mount Tai china clay
10-15 parts of clay
18-25 parts of aluminium oxide
10-18 parts of zirconium oxide
2-10 parts of iron powder
25-33 parts of auxiliary agent.
Preferably, the auxiliary agent includes 10-15 parts and binder 15-18 parts of size.
Preferably, the binder is selected from one or more of polyethylene glycol, polyvinyl alcohol, carragheen.
Preferably, the size is sodium chloride solution or Klorvess Liquid, the sodium chloride solution or potassium chloride are molten
The concentration of liquid is 0.1-2M.
It is made preferably, the size is dissolved in the water boiled by sodium chloride or potassium chloride.After boiling is boiled again
Solution is prepared, the air in water can be removed, to reduce the oxygen content in solution.
Preferably, the clay is selected from one or more of kaolin or montmorillonite, Jing≤10 the iron powder Li are micro-
Rice.
Using technical solution of the present invention, high-purity iron powder is added in ceramic raw material, ceramic raw material in the presence of water and oxygen
Inside occurs oxidation reaction and releases amount of heat, and temperature increases, and accelerates the volatilization of binder to realize rapid curing.In addition,
It is that a small amount of sodium chloride or potassium chloride are added in solution to accelerate the oxidation rate of iron powder in water, improves thermal discharge, the wooden Mount Tai china clay is inhaled
Receiving portions heat reduces heat loss so that heat is stored in inside ceramic material, and the utilization oxidation reaction of maximal efficiency generates
Heat accelerate the solidification of ceramic material, simple process is not necessarily to laser formation, realizes rapid shaping at normal temperatures and pressures, contract
Short molding cycle, save the cost.
A kind of Method of printing of the 3D printing ceramic material of rapid shaping, comprising the following steps:
(1) the wooden Mount Tai china clay, clay, aluminium oxide, zirconium oxide and auxiliary agent are uniformly mixed, are passed through nitrogen to exclude air, add
Iron powder is stirred in logical nitrogen, until iron powder obtains the ceramic material after mixing evenly；
(2) ceramic material is placed in 3D printer hopper, Yang Nong Du≤10ppm in the hopper；
(3) starting 3D printer printing ceramics just base, then postmenstruation processing and polishing, obtains final ceramic product.Iron will first be removed
The unexpected raw material of powder is uniformly mixed, and being passed through nitrogen is saturated nitrogen in solution to exclude air, after avoiding iron powder from being added with
Oxygen fast reaction, causes thermal loss.Then iron powder is added and is stirred evenly, is placed into 3D printer hopper, the mistake
Since iron powder is inevitably with a small amount of oxygen haptoreaction heat release, solution temperature risen journey, is conducive to binder in water molten
Solution, to improve caking property.The base at the beginning of ceramic material prints from 3D printer hopper and to form ceramics, ceramics just base exposure
In air, the porosity of ceramic raw material enters to oxygen provides condition inside porcelain body, release greatly to react with iron powder
Calorimetric amount promotes the volatilization of binder, accelerates solidification, it is all to shorten molding so that the internal and external temperature of the first base of ceramics improves rapidly
Phase, process conditions are simple, it is easy to accomplish, it can large-scale application.
Preferably, the auxiliary agent includes 10-15 parts and binder 15-18 parts of size, the binder is selected from poly- second
One or more of glycol, polyvinyl alcohol, carragheen, the size are sodium chloride solution or Klorvess Liquid, the chlorine
The concentration for changing sodium solution or Klorvess Liquid is 0.1-2M；Clay is selected from one or more of kaolin or montmorillonite, described
Jing≤10 micron iron powder Li.
Preferably, the amount for being passed through nitrogen makes ceramic material temperature be 60-96 DEG C in step (1).Iron powder meets water and oxygen
Oxidation reaction occurs and releases thermal energy, the oxygen content in ceramic material is controlled by controlling the intake of nitrogen, to realize control
Oxygenerating reaction rate controls the temperature of ceramic material at 60-96 DEG C, to improve the solubility of binder in water, improves slurry
The mobility and adhesive property of material.
Preferably, starting 3D printer prints ceramic just base in the Yang Nong ppm atmosphere of Du≤1000.Oxygen concentration is bigger,
The oxidation rate of iron powder is faster, and the temperature for being more conducive to the first base of ceramics increases, thus the volatilization of speed adhesive, further quickly
Solidification improves the efficiency of 3D printing to shorten short molding cycle.
Therefore, the invention has the following beneficial effects: (1) to realize rapid shaping at normal temperatures and pressures, shortens molding cycle,
Save the cost；(2) process conditions are simple, it is easy to accomplish, it can large-scale application；(3) solubility of binder in water is improved,
Improve the mobility and adhesive property of slurry.
Specific embodiment
The present invention will be further described With reference to embodiment.Agents useful for same of the present invention is conventional reagent
Or commercial products.
Embodiment 1:
A kind of Method of printing of the 3D printing ceramic material of rapid shaping, comprising the following steps:
(1) by 30 parts of the wooden Mount Tai china clay, 10 parts of kaolin, 18 parts of aluminium oxide, 10 parts of zirconium oxide, the sodium chloride solution that concentration is 0.1M
10 parts and 15 parts of polyethylene glycol are uniformly mixed, and are passed through high pure nitrogen to exclude air, add 2 parts of iron powder that partial size is 8 microns,
It is stirred in logical nitrogen, adjusting nitrogen, which is passed through rate, makes system temperature reach 60 DEG C, until iron powder obtains the pottery after mixing evenly
Ceramic material；
(2) ceramic material is placed in 3D printer hopper, oxygen concentration is 8ppm in the hopper；
(3) starting 3D printer prints ceramics just base, and 1h, then postmenstruation processing and polishing are stood in air, obtains final ceramics
Product.
Embodiment 2:
A kind of Method of printing of the 3D printing ceramic material of rapid shaping, comprising the following steps:
(1) by 40 parts of the wooden Mount Tai china clay, 15 parts of kaolin, 25 parts of aluminium oxide, 18 parts of zirconium oxide, the Klorvess Liquid 15 that concentration is 2M
Part is uniformly mixed with 18 parts of polyvinyl alcohol, is passed through high pure nitrogen to exclude air, adds 10 parts of iron powder that partial size is 10 microns,
It is stirred in logical nitrogen, adjusting nitrogen, which is passed through rate, makes system temperature reach 96 DEG C, until iron powder obtains the pottery after mixing evenly
Ceramic material；
(2) ceramic material is placed in 3D printer hopper, oxygen concentration is 10ppm in the hopper；
(3) starting 3D printer prints ceramics just base in the case where oxygen concentration is 1500 ppm, stands 10min and completes solidification process, then
Postmenstruation processing and polishing, obtain final ceramic product.
Embodiment 3:
A kind of Method of printing of the 3D printing ceramic material of rapid shaping, comprising the following steps:
(1) by 35 parts of the wooden Mount Tai china clay, 13 parts of montmorillonite, 21 parts of aluminium oxide, 14 parts of zirconium oxide, the Klorvess Liquid 13 that concentration is 1M
Part is uniformly mixed with 16 parts of carragheen, is passed through high pure nitrogen to exclude air, adds 6 parts of iron powder that partial size is 5 microns, Bian Tong
The stirring of nitrogen side, adjusting nitrogen, which is passed through rate, makes system temperature reach 80 DEG C, until iron powder obtains the ceramic material after mixing evenly
Material；
(2) ceramic material is placed in 3D printer hopper, oxygen concentration is 5ppm in the hopper；
(3) starting 3D printer prints ceramics just base in the case where oxygen concentration is 1100 ppm, stands 35min molding and completes, then after
Phase processing and polishing, obtain final ceramic product.
Embodiment 4:
A kind of Method of printing of the 3D printing ceramic material of rapid shaping, comprising the following steps:
(1) by 34 parts of the wooden Mount Tai china clay, 14 parts of kaolin, 20 parts of aluminium oxide, 15 parts of zirconium oxide, the Klorvess Liquid that concentration is 1.4M
13 parts and polyvinyl alcohol and carragheen are uniformly mixed for 17 parts totally, are passed through high pure nitrogen to exclude air, and adding partial size is 6 micro-
4 parts of iron powder of rice are stirred in logical nitrogen, and adjusting nitrogen, which is passed through rate, makes system temperature reach 85 DEG C, until iron powder stirs evenly
After obtain the ceramic material；
(2) ceramic material is placed in 3D printer hopper, oxygen concentration is 6ppm in the hopper；
(3) starting 3D printer prints ceramics just base in the case where oxygen concentration is 1300 ppm, stands 20min molding and completes, then after
Phase processing and polishing, obtain final ceramic product.
Claims (10)
1. a kind of 3D printing ceramic material of rapid shaping, which is characterized in that be made of the raw material of following parts by weight:
30-40 parts of the wooden Mount Tai china clay
10-15 parts of clay
18-25 parts of aluminium oxide
10-18 parts of zirconium oxide
2-10 parts of iron powder
25-33 parts of auxiliary agent.
2. a kind of 3D printing ceramic material of rapid shaping according to claim 1, which is characterized in that the auxiliary agent includes
10-15 parts and binder 15-18 parts of size.
3. a kind of 3D printing ceramic material of rapid shaping according to claim 2, which is characterized in that the binder choosing
From one or more of polyethylene glycol, polyvinyl alcohol, carragheen.
4. a kind of 3D printing ceramic material of rapid shaping according to claim 2, which is characterized in that the size is
The concentration of sodium chloride solution or Klorvess Liquid, the sodium chloride solution or Klorvess Liquid is 0.1-2M.
5. a kind of 3D printing ceramic material of rapid shaping according to claim 4, which is characterized in that the size by
Sodium chloride or potassium chloride, which are dissolved in the water boiled, to be made.
6. a kind of 3D printing ceramic material of rapid shaping described in -5 any one according to claim 1, which is characterized in that institute
It states clay and is selected from one or more of kaolin or montmorillonite, Jing≤10 micron the iron powder Li.
7. a kind of Method of printing of the 3D printing ceramic material of rapid shaping according to claim 1, which is characterized in that packet
Include following steps:
(1) the wooden Mount Tai china clay, clay, aluminium oxide, zirconium oxide and auxiliary agent are uniformly mixed, are passed through nitrogen to exclude air, add
Iron powder is stirred in logical nitrogen, until iron powder obtains the ceramic material after mixing evenly；
(2) ceramic material is placed in 3D printer hopper, Yang Nong Du≤10ppm in the hopper；
(3) starting 3D printer printing ceramics just base, then postmenstruation processing and polishing, obtains final ceramic product.
8. a kind of Method of printing of the 3D printing ceramic material of rapid shaping according to claim 7, which is characterized in that institute
Stating auxiliary agent includes 10-15 parts and binder 15-18 parts of size, and the binder is selected from polyethylene glycol, polyvinyl alcohol, carragheen
One or more of, the size is sodium chloride solution or Klorvess Liquid, the sodium chloride solution or Klorvess Liquid
Concentration be 0.1-2M；Clay is selected from one or more of kaolin or montmorillonite, Jing≤10 micron the iron powder Li.
9. a kind of Method of printing of the 3D printing ceramic material of rapid shaping according to claim 7 or 8, feature exist
In in step (1), the amount for being passed through nitrogen makes ceramic material temperature be 60-96 DEG C.
10. a kind of Method of printing of the 3D printing ceramic material of rapid shaping according to claim 7 or 8, feature exist
In starting 3D printer prints ceramic just base in the Yang Nong ppm atmosphere of Du≤1000.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810037272.7A CN109485380A (en) | 2018-01-15 | 2018-01-15 | A kind of the 3D printing ceramic material and Method of printing of rapid shaping |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810037272.7A CN109485380A (en) | 2018-01-15 | 2018-01-15 | A kind of the 3D printing ceramic material and Method of printing of rapid shaping |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0208849A1 (en) * | 1985-07-18 | 1987-01-21 | KIRIBAI CHEMICAL INDUSTRY Co., Ltd. | Exothermic composition |
| CN104651605A (en) * | 2015-02-06 | 2015-05-27 | 唐竹胜 | Preparation method of cold-bonded pellets |
| CN105130402A (en) * | 2015-06-30 | 2015-12-09 | 成都新柯力化工科技有限公司 | Nanometer ceramic material used for 3D printing and 3D printing molding method thereof |
| CN106167855A (en) * | 2016-08-08 | 2016-11-30 | 方喜 | A kind of cleaning method of smelting of lead containing sludge |
| WO2017011456A1 (en) * | 2015-07-16 | 2017-01-19 | Velo3D, Inc. | Material-fall three-dimensional printing |
-
2018
- 2018-01-15 CN CN201810037272.7A patent/CN109485380A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0208849A1 (en) * | 1985-07-18 | 1987-01-21 | KIRIBAI CHEMICAL INDUSTRY Co., Ltd. | Exothermic composition |
| CN104651605A (en) * | 2015-02-06 | 2015-05-27 | 唐竹胜 | Preparation method of cold-bonded pellets |
| CN105130402A (en) * | 2015-06-30 | 2015-12-09 | 成都新柯力化工科技有限公司 | Nanometer ceramic material used for 3D printing and 3D printing molding method thereof |
| WO2017011456A1 (en) * | 2015-07-16 | 2017-01-19 | Velo3D, Inc. | Material-fall three-dimensional printing |
| CN106167855A (en) * | 2016-08-08 | 2016-11-30 | 方喜 | A kind of cleaning method of smelting of lead containing sludge |
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Application publication date: 20190319 |