CN105503146B - Clay material for laser sintering 3D printing and preparation method thereof - Google Patents
Clay material for laser sintering 3D printing and preparation method thereof Download PDFInfo
- Publication number
- CN105503146B CN105503146B CN201510980943.XA CN201510980943A CN105503146B CN 105503146 B CN105503146 B CN 105503146B CN 201510980943 A CN201510980943 A CN 201510980943A CN 105503146 B CN105503146 B CN 105503146B
- Authority
- CN
- China
- Prior art keywords
- clay
- parts
- printing
- laser sintering
- weight
- 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
Links
Classifications
-
- 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
- C04B33/13—Compounding ingredients
- C04B33/131—Inorganic additives
-
- 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
- C04B33/13—Compounding ingredients
- C04B33/1305—Organic additives
-
- 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
-
- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Producing Shaped Articles From Materials (AREA)
Abstract
The invention relates to a clay material for laser sintering 3D printing and a preparation method thereof, which aims to obtain the clay material suitable for a laser sintering 3D printing forming technology, the clay is modified, an inorganic sol solution is used for adsorbing the clay, and a spherical powdery clay material is obtained through emulsification coating.
Description
Technical Field
The invention relates to a 3D printing material and a preparation method thereof, in particular to a clay material for laser sintering 3D printing and a preparation method thereof.
Background
The 3D printing technology, also known as additive manufacturing technology, is a new technology in the field of rapid prototyping, and is a technology for constructing an object by using a bondable material, such as powdered metal or plastic, and printing layer by layer on the basis of a digital model file. With the development and application of 3D printing technology, the development of materials determines whether 3D printing can be applied more widely, and materials become one of the key factors that limit the future trend of 3D printing technology. At present, 3D printing materials mainly include engineering plastics, photosensitive resins, rubber materials, metal materials, ceramic materials, and the like, and besides, food materials such as color gypsum materials, artificial bone powder, cell biological raw materials, wood materials, granulated sugar, and the like are also applied in the field of 3D printing.
The clay is one of the earliest inorganic materials applied to human beings, has the advantages of rich stock and low cost, is still the most inorganic material applied in human life, and can be used for firing ceramic materials, building construction, road paving and the like, and can also be used for industries, such as filler in high polymer materials, treatment of waste water, metal smelting and the like. With the development of 3D printing technology, various materials are applied to 3D printing, the use method of the traditional materials is changed, and a new idea is provided for the use method of clay due to the appearance of the 3D printing technology. When a ceramic product is formed by using a 3D printing technology, the 3D printing material used by people is ceramic powder formed by firing clay, and then the ceramic product is obtained by a direct or indirect method, but the preparation method of the ceramic powder is complex and high in cost, and the development and application of the 3D printing technology on ceramic forming are seriously hindered. The clay has excellent viscosity and plasticity, can be directly molded into a ceramic blank and then sintered to obtain the ceramic, but due to the defects of the process and the technology, the molded ceramic blank has the defects of simple structure, poor size precision and the like, so the application of the clay and the product thereof in life is seriously limited, if the 3D printing technology is used for the clay and then the ceramic is molded, the defects can be completely perfected and solved, and therefore, the application of the clay in 3D printing molding has important significance and market value for the application of the clay and the product thereof in life.
The clay material which is not subjected to modification treatment is not suitable for 3D printing forming, the clay with high plasticity has poor mechanical property and is not beneficial to supporting and forming in the forming process, the clay with good mechanical property has poor caking property and plasticity and is not beneficial to caking and extrusion in the forming process, therefore, the clay needs to be subjected to modification treatment to obtain the clay material suitable for the laser sintering 3D printing technology, and the clay is a precondition for the fact that the clay can be used for the 3D printing technology.
Disclosure of Invention
The invention provides a clay material for laser sintering 3D printing and a preparation method thereof, aiming at expanding the application range of a 3D printing technology in life, enabling the clay material to be used for a laser sintering 3D printing forming technology and modifying the clay.
The invention relates to a clay material for laser sintering 3D printing, which is characterized in that the clay material is a spherical powdery clay mixture with the diameter of 90-100 mu m for laser sintering 3D printing molding technology, and is prepared from the following raw materials:
50-65 parts of clay, namely, clay,
150 portions of solvent and 200 portions of solvent,
5-15 parts of a dispersing agent,
5-10 parts of an emulsifying agent,
wherein the clay is one or two of kaolin and montmorillonite with the fineness of 800-; the solvent is one or two of a silica sol solution and an aluminum sol solution; the dispersing agent is one or more of water glass, sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate; the emulsifier is one or more of alkyl ammonium salt, alkyl phosphate, fatty alcohol sulfate and alkyl sulfonate.
The clay material for laser sintering 3D printing is obtained by the following preparation method, and is characterized by comprising the following specific steps:
1. adding 50-65 parts by weight of clay, 150-200 parts by weight of solvent and 5-15 parts by weight of dispersant into a planetary ball mill for mixing, dispersing and grinding for 1-2 hours to obtain a mixed solution A;
2. adding 5-10 parts by weight of emulsifier into the mixture A obtained in the step 1, and carrying out ultrasonic oscillation and high-speed stirring at the speed of 500-700r/min for emulsification treatment for 20-30min to obtain a mixed solution B;
3. and (3) carrying out spray drying on the mixed solution B obtained in the step (2) by using a spray dryer to obtain the spherical powdery clay material for the laser sintering 3D printing forming technology.
The aperture of the spray dryer in the specific preparation method of the clay material for laser sintering 3D printing is 100-130 μm.
In order to obtain the clay material suitable for the laser sintering 3D printing forming technology, the clay is subjected to modification treatment: the method comprises the steps of adsorbing clay around sol ions by utilizing the adsorbability and the charge property of inorganic sol, dispersing the sol ions into a water-in-oil vesicle structure through the isolation and emulsification of an emulsifier, and finally drying through a spray drying technology to obtain the spherical powdery clay material. The clay material obtained by the modification method has the advantages of good fluidity, good mechanical property and high precision, is suitable for the laser sintering 3D printing and forming technology, promotes the popularization and application of the 3D printing and forming technology, and has wide market prospect.
The invention has the outstanding characteristics and beneficial effects that:
1. according to the invention, in order to use the clay in the 3D printing technology, the clay is subjected to modification treatment, so that the clay material suitable for the laser sintering 3D printing forming technology is obtained.
2. The invention provides a method for modifying clay, and the clay material with good fluidity, good chemical property and high precision is prepared.
3. The product prepared by the method has the advantages of good dimensional accuracy, simple and reliable method and low cost.
The performance indexes of the clay material of the invention are as follows:
| name (R) | Appearance of the product | Shape of | Particle size | Water content |
| Clay material | Off-white powder | Spherical shape | 90-100μm | ≤4% |
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
1. Adding 50 parts by weight of kaolin with the fineness of 2000 meshes, 150 parts by weight of silica sol solution and 5 parts by weight of water glass into a planetary ball mill for mixing, dispersing and grinding for 2 hours to obtain a mixed solution A;
2. adding 10 parts by weight of ammonium alkyl sulfate into the mixture A obtained in the step 1, and carrying out ultrasonic oscillation and high-speed stirring at a speed of 500r/min for emulsification treatment for 20-30min to obtain a mixed solution B;
3. and (3) carrying out spray drying on the mixed solution B obtained in the step (2) by using a spray dryer to obtain the spherical powdery clay material for the laser sintering 3D printing forming technology.
Example 2
1. Adding 65 parts by weight of 800-mesh montmorillonite, 200 parts by weight of alumina sol solution and 15 parts by weight of sodium tripolyphosphate into a planetary ball mill, mixing, dispersing and grinding for 1 hour to obtain a mixed solution A;
2. adding 5 parts by weight of sodium alkyl phosphate into the mixture A obtained in the step 1, and carrying out ultrasonic oscillation and high-speed stirring at a speed of 700r/min for emulsification treatment for 20min to obtain a mixed solution B;
3. and (3) carrying out spray drying on the mixed solution B obtained in the step (2) by using a spray dryer to obtain the spherical powdery clay material for the laser sintering 3D printing forming technology.
Example 3
1. Adding 60 parts by weight of kaolin with the fineness of 1200 meshes, 200 parts by weight of silica sol solution and 10 parts by weight of sodium hexametaphosphate into a planetary ball mill for mixing, dispersing and grinding for 2 hours to obtain a mixed solution A;
2. adding 8 parts by weight of fatty alcohol sodium sulfate into the mixture A obtained in the step 1, and carrying out ultrasonic oscillation and high-speed stirring at a speed of 600r/min for emulsification treatment for 30min to obtain a mixed solution B;
3. and (3) carrying out spray drying on the mixed solution B obtained in the step (2) by using a spray dryer to obtain the spherical powdery clay material for the laser sintering 3D printing forming technology.
Example 4
1. Adding 60 parts by weight of montmorillonite with fineness of 1200 meshes, 150 parts by weight of alumina sol solution and 8 parts by weight of sodium pyrophosphate into a planetary ball mill, mixing, dispersing and grinding for 1.5 hours to obtain a mixed solution A;
2. adding 6 parts by weight of sodium alkyl sulfonate into the mixture A obtained in the step 1, and carrying out ultrasonic oscillation and high-speed stirring at a speed of 650r/min for emulsification treatment for 20min to obtain a mixed solution B;
3. and (3) carrying out spray drying on the mixed solution B obtained in the step (2) by using a spray dryer to obtain the spherical powdery clay material for the laser sintering 3D printing forming technology.
Example 5
1. Adding 55 parts by weight of kaolin with the fineness of 1500 meshes, 180 parts by weight of silica sol solution and 15 parts by weight of sodium hexametaphosphate into a planetary ball mill, and mixing, dispersing and grinding for 2 hours to obtain a mixed solution A;
2. adding 9 parts by weight of aluminum alkyl phosphate into the mixture A obtained in the step 1, and performing ultrasonic oscillation and high-speed stirring at a speed of 600r/min for emulsification treatment for 25min to obtain a mixed solution B;
3. and (3) carrying out spray drying on the mixed solution B obtained in the step (2) by using a spray dryer to obtain the spherical powdery clay material for the laser sintering 3D printing forming technology.
Claims (1)
1. The clay material for laser sintering 3D printing is characterized in that the clay material is a spherical powdery clay mixture with the diameter of 90-100 mu m and used for laser sintering 3D printing and molding technology, and is prepared from the following raw materials:
50-65 parts of clay, namely, clay,
150 portions of solvent and 200 portions of solvent,
5-15 parts of a dispersing agent,
5-10 parts of an emulsifying agent,
wherein the clay is one or two of kaolin and montmorillonite with the fineness of 800-; the solvent is one or two of a silica sol solution and an aluminum sol solution; the dispersing agent is one or more of water glass, sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate; the emulsifier is one or more of alkyl ammonium salt, alkyl phosphate, fatty alcohol sulfate and alkyl sulfonate; the clay material for laser sintering 3D printing is prepared by the following preparation method, and is characterized by comprising the following specific steps:
(1) adding 50-65 parts by weight of clay, 150-200 parts by weight of solvent and 5-15 parts by weight of dispersant into a planetary ball mill for mixing, dispersing and grinding for 1-2 hours to obtain a mixed solution A;
(2) adding 5-10 parts by weight of emulsifier into the mixture A obtained in the step 1, and carrying out ultrasonic oscillation and high-speed stirring at the speed of 500-700r/min for emulsification treatment for 20-30min to obtain a mixed solution B;
(3) spray drying the mixed solution B obtained in the step 2 by using a spray dryer to obtain a spherical powdery clay material for the laser sintering 3D printing forming technology; the aperture of the spray dryer is 100-130 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510980943.XA CN105503146B (en) | 2015-12-24 | 2015-12-24 | Clay material for laser sintering 3D printing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510980943.XA CN105503146B (en) | 2015-12-24 | 2015-12-24 | Clay material for laser sintering 3D printing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105503146A CN105503146A (en) | 2016-04-20 |
| CN105503146B true CN105503146B (en) | 2020-09-29 |
Family
ID=55711525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510980943.XA Active CN105503146B (en) | 2015-12-24 | 2015-12-24 | Clay material for laser sintering 3D printing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105503146B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242507B (en) * | 2016-08-27 | 2022-05-17 | 景德镇陶瓷大学 | Clay mud for directly-formed 3D ceramic printing and preparation method and application thereof |
| WO2019000349A1 (en) * | 2017-06-29 | 2019-01-03 | 黄玉倩 | Silica gel clay preparation technique |
| CN107512898A (en) * | 2017-08-14 | 2017-12-26 | 河海大学常州校区 | A kind of 3D printing clay material and preparation method thereof |
| CN108069704A (en) * | 2018-01-10 | 2018-05-25 | 苏州拜博机电科技有限公司 | A kind of preparation method of 3D printing ceramic slurry |
| CN108484131B (en) * | 2018-02-02 | 2020-10-16 | 航天特种材料及工艺技术研究所 | Alumina ceramic slurry suitable for 3D printing, preparation method and application |
| CN108484110A (en) * | 2018-06-25 | 2018-09-04 | 福州大学 | A kind of formula for ceramic 3D printing pug |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013043908A1 (en) * | 2011-09-20 | 2013-03-28 | The Regents Of The University Of California | 3d printing powder compositions and methods of use |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104446392A (en) * | 2014-12-01 | 2015-03-25 | 青岛麦特瑞欧新材料技术有限公司 | Calcium-doped inorganic nanocomposite material for 3D printing and preparation method of calcium-doped inorganic nanocomposite material |
| CN104526838B (en) * | 2014-12-30 | 2017-01-11 | 宁波伏尔肯陶瓷科技有限公司 | Method for 3D ceramic printing forming |
| CN105174907A (en) * | 2015-06-30 | 2015-12-23 | 成都新柯力化工科技有限公司 | 3D printing clay material and preparation method thereof |
-
2015
- 2015-12-24 CN CN201510980943.XA patent/CN105503146B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013043908A1 (en) * | 2011-09-20 | 2013-03-28 | The Regents Of The University Of California | 3d printing powder compositions and methods of use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105503146A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105503146B (en) | Clay material for laser sintering 3D printing and preparation method thereof | |
| CN104744000B (en) | A kind of 3D printing gypsum material and preparation method thereof | |
| CN105174907A (en) | 3D printing clay material and preparation method thereof | |
| CN105645923A (en) | Filamentous clay material for 3D printing and preparation method thereof | |
| CN105503147B (en) | A kind of clay material and preparation method thereof for 3D printing | |
| CN106830987B (en) | Artificial culture stone using stone waste slurry as raw material and preparation method thereof | |
| CN105481329A (en) | 3D printing gypsum ink and preparation method thereof | |
| CN102936127A (en) | Light hollow ceramsite and production method thereof | |
| CN102343415A (en) | Casting coated sand suitable for selective laser sintering forming and manufacturing method thereof | |
| CN105645840A (en) | Ceramic material for 3D printing and manufacturing method thereof | |
| CN105565820B (en) | A kind of 3D printing ceramic material clay based binder and its application | |
| CN111377699A (en) | Gypsum powder for 3D printing | |
| CN108383465A (en) | A kind of extruded type 3D printing gypsum based composite cementing material and preparation method thereof | |
| CN105619572A (en) | 3D printing forming method of ceramic material | |
| CN105060859A (en) | Remains bone ash treatment method and product thereof | |
| CN100427435C (en) | Method for preparing porous ceramic using modified starch | |
| CN106587780A (en) | Method for preparing and printing aluminosilicate polymer composite material for 3D (three-dimensional) printing | |
| CN111635156A (en) | Preparation method of 3D printing building material aggregate | |
| CN103029506B (en) | Processing method for ceramic-imitated sculpture | |
| CN106348745A (en) | Preparation method for rapidly forming YAG transparent ceramic powder material by 3DP (three-dimensional printing) technology | |
| CN112500111B (en) | Method for preparing phosphorus-removing biological filter material by using autoclaved aerated concrete block waste | |
| CN107721435B (en) | Ceramic product made of waste ceramic material and manufacturing method thereof | |
| CN108530028A (en) | A kind of ceramic powder and ceramic sanitary appliance production technology for 3D printing sanitary ware | |
| CN101774799B (en) | Ceramic scrap product and preparation method thereof | |
| CN103819135A (en) | Artificial stone and production process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200831 Address after: Taizhou City, Zhejiang province Luqiao District 318050 peak River Street No. 9, Mei Ting Lu Applicant after: Xu Enming Address before: Qingyang District of Chengdu City, Sichuan province 610091 Dragon Industrial Port East Road 4 Applicant before: CHENGDU NEW KELI CHEMICAL SCIENCE Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |