CN107189385A - A kind of graphene 3D printing material of high intensity - Google Patents
A kind of graphene 3D printing material of high intensity Download PDFInfo
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- CN107189385A CN107189385A CN201710534553.9A CN201710534553A CN107189385A CN 107189385 A CN107189385 A CN 107189385A CN 201710534553 A CN201710534553 A CN 201710534553A CN 107189385 A CN107189385 A CN 107189385A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a kind of graphene 3D printing material with high intensity, belong to 3D printing technical field of material, the graphene 3D printing material with high intensity is in units of parts by weight, including following raw material：8 25 parts of modified graphene, 3 15 parts of nano titanium oxide, 2 10 parts of nano-calcium carbonate, 35 39 parts of PLA, 18 23 parts of epoxy acrylate, 2 10 parts of crosslinking agent, 0.5 1 parts of stabilizer, 0.5 1.2 parts of toughener.The material energy rapid shaping of the present invention, the characteristics of with high intensity, high tensile, the product high-impact printed by 3D printing technique, high intensity, while cost is low, and it is environmentally friendly, influence will not be produced on the health of people after formed product and during later stage use.
Description
Technical field
The invention belongs to 3D printing technical field of material, and in particular to a kind of graphene 3D with high intensity is beaten
Print material.
Background technology
With the appearance of 3D printing commodity, 3D printing technique is also gradually understood by people.3D printing technique belongs to quick
One kind in forming technique, it is a kind of based on mathematical model file, and material can be bonded with powdery metal or plastics etc.
Material, come the technology of constructed object by way of successively printing.Past, it was often used in fields such as Making mold, industrial designs
Modeling, is now increasingly used for the direct manufacture of some products.The available raw material of 3D printing includes resin, metal and ceramics
Powder etc., the product that different material is prepared by 3D printing is in footwear, architectural engineering, automobile, Aero-Space, medical treatment, military, soil
Wood engineering, gun and other field have all been applied.
Extensive concern is constantly subjected in recent years as the printed material of the core component of 3D printing.It progressively have developed pottery
The different species such as porcelain, photosensitive resin, metal alloy, biological tissue, composite and plastics.According to printed material shape
Difference, can be divided into thread, powdered and liquid material.It let us say that the difference of the species of printed material is just determined
The species and performance of 3D printer.Material is an important factor for restricting 3D printing.Material engineering does not catch up with industry hair
Exhibition, large forgings can not be molded, and the factor such as poor mechanical property governs the development of 3D technology.How raising 3D printing material is broken through
Expect feature, reduction 3D printing cost, the problems such as improving the mechanical property of 3D printing material is extremely urgent.
Graphene is a kind of dimensional thinlayer material for being stripped out, being made up of carbon atom from graphite material, with excellent
Mechanics and thermodynamic property, it is considered to be it is a kind of following to meet before engineering plastics field has tremendous expansion potentiality and application
The material of scape.But plastics 3D printing at present has that low intensity, tensile strength be small and bending strength with material, because
This, research and development are a kind of to have high intensity, while having the graphene 3D printing material of high tenacity and tensile strength significant.
Chinese patent CN106633717A discloses a kind of preparation side of the graphene 3D printing material with high anti-intensity
Method, including graphene, waste plastic, PLA, six PA 800Ks, epoxy acrylate, specific synthetics and Starch synthesis agent,
Graphene 3D printing tensile strength of material that it is made is big, intensity is high, but the material complex manufacturing technology, and proportioning has
Machine material is high, and not degradable, the product printed has certain pollution to environment.
The content of the invention
To solve the above problems, the present invention improves a kind of graphene 3D printing material with high intensity, using the present invention
The graphene 3D printing strength of materials that is made is high, tensile strength is high, at the same 3D printing come out product high intensity, high-impact, tool
There are wide market prospects.
To solve above technical problem, the present invention uses following technical scheme：
A kind of graphene 3D printing material of high intensity, it is characterised in that the printed material by following parts by weight original
Material is obtained by mixing：
Above-mentioned each component summation should be 100 parts by weight.
Preferably, described modified graphene is made up of graphene oxide, ammoniacal liquor, polypropylene glycol glycidol ether, its
The mass ratio of middle graphene oxide and the polypropylene glycol glycidol ether is 90:2-4, the mass concentration of the ammoniacal liquor is
30%.
Preferably, 20-100 nanometers of the nano titanium oxide average grain diameter.
Preferably, the crosslinking agent is one kind in benzoyl peroxide and tetraalkyl butyl acrylate.
Preferably, described stabilizer is one or two kinds of compoundings such as stabilizer 1096,168.
Preferably, the toughener is propyl trimethoxy silicane.
A kind of specific preparation method of high strength graphite alkene 3D printing material of the present invention is as follows：
S1：In proportion by modified graphene, nano titanium oxide, nano-calcium carbonate, PLA, epoxy acrylate, increasing
Tough dose and stabilizer are well mixed manually after fully drying；
S2：The compound that S1 is obtained is crushed in the case where temperature is -90-110 DEG C, is added crosslinking agent and is well mixed, will mix
Homogeneous mixture is put into screw extruding forming machine, in 150-200 DEG C of temperature, under rotating speed is 100-120r/min, through extruding silk
Bar, is made graphene 3D printing material.
The present invention has following beneficial effect：
(1) the graphene 3D printing material energy rapid shaping that the present invention is made, the spy with high intensity, high tensile
Point, the product high-impact printed by 3D printing technique, high intensity.
(2) what prepared by the present invention have high intensity, the cost of material is low for the graphene 3D printing of high tensile, and to environment
Close friend, influence will not be produced after formed product and during later stage use on the health of people.
Embodiment
For ease of more fully understanding the present invention, it is illustrated by following examples, these embodiments belong to the present invention's
Protection domain, but do not limit the scope of the invention.
In embodiment, the graphene 3D printing material with high intensity, in units of parts by weight, including following original
Material：8-25 parts of modified graphene, 3-15 parts of nano titanium oxide, 2-10 parts of nano-calcium carbonate, 35-39 parts of PLA, epoxy third
18-23 parts of olefin(e) acid ester, 2-10 parts of crosslinking agent, 0.5-1 parts of stabilizer, 0.5-1.2 parts of toughener.
Described modified graphene is made up of graphene oxide, ammoniacal liquor, polypropylene glycol glycidol ether, wherein graphite oxide
The mass ratio of alkene and the polypropylene glycol glycidol ether is 90:2-4, optimal proportion is 90：3, the mass concentration of the ammoniacal liquor,
27-32%.Specifically, in embodiments of the present invention, the modified graphene as graphene 3D printing material matrix material,
With mechanical property especially, therefore, it is possible to assign the mechanical strength that 3D printed materials are excellent.But, graphene is difficult to and it
His material, particularly PLA and epoxy acrylate carry out compound use.Therefore graphene provided in an embodiment of the present invention is
Modified graphene, by the processing of polypropylene glycol glycidol ether, the polypropylene glycol glycidol ether is coated on the graphite
Alkene surface, so as to form the modified graphene for having preferable respond with PLA and epoxy acrylate, the present invention is implemented
In example, the modified graphene obtained after ammoniacal liquor, the processing of polypropylene glycol glycidol ether not only contributes to graphene and other
Compatibility between material, moreover, improving the intensity of graphene, and then enhances product performance.
It should be noted that the ammoniacal liquor mass concentration is 27-32%, if ammonia concn is too high, graphene is reduced
Degree is excessive, is unfavorable for being combined with the polypropylene glycol glycidol ether, polypropylene glycol glycidol ether is to graphene coated energy
Power is poor；If ammonia concn is too low, make modified graphene and PLA and epoxy acrylic to graphene reducing degree not enough
The binding ability of ester is poor, and then can reduce the stability of graphene 3D printing material.
In the present invention, described crosslinking agent refers to that those can be in intermolecular bridging action of line style, so that multiple lines
Type molecule is mutually bonded the material for being cross-linked into network structure, and specifically those promote or regulation polymer molecule interchain is covalent
Key or the material of ionic bond formation.The crosslinking agent includes but is not limited to：In benzoyl peroxide or tetraalkyl butyl acrylate
One or two kinds of compoundings, such as benzoyl peroxide or tetraalkyl butyl acrylate compounding use, then benzoyl peroxide and four
The ratio of alkyl butyl acrylate preferably 20:6, stabilizer of the present invention refer to those can increase solution, colloid, solid,
The chemical substance of the stability of mixture, preferably composite thermal stabilizer, it is multiple by the one or two such as stabilizer 1096,168
Match somebody with somebody, total addition level is 0.5-1 parts of amount of the mixture.
The nano-calcium carbonate and nano titanium oxide in the present invention, play a part of rigid ion enhancing, toughness reinforcing simultaneously,
Sand and rubble in the similar concrete of mechanism.20-100 nanometers of nano titanium oxide average grain diameter, optimum grain-diameter is 50-80
Nanometer.The average grain diameter of nano-calcium carbonate is 500-9000 nanometers.Nano-calcium carbonate and nano titanium oxide are worked in coordination, and are increased
The strong intensity of the new 3D printing material so that the characteristics of graphene 3D printing material prepared by the present invention has high intensity.
Embodiment 1
In embodiment, the graphene 3D printing material with high intensity, in units of parts by weight, including following original
Material：20 parts of modified graphene, 10 parts of nano silicon, 5 parts of nano-calcium carbonate, 35 parts of PLA, 20 parts of epoxy acrylate,
8 parts of benzoyl peroxide, 10960.9 parts of stabilizer, 1.1 parts of toughener.
Modified graphene is made up of graphene, ammoniacal liquor, polypropylene glycol glycidol ether, wherein graphene oxide and described poly-
The mass ratio of propylene glycol glycidyl ether is 90:3, ammonia concn is 30%.
The specific method that the present embodiment prepares high strength graphite alkene 3D printing material is as follows：
S1：By the modified graphene of above-mentioned parts by weight, nano titanium oxide, nano-calcium carbonate, PLA, epoxy acrylic
Ester, toughener and stabilizer are well mixed manually after fully drying；
S2：The compound that S1 is obtained is crushed in the case where temperature is -90-110 DEG C, is added 8 parts of crosslinking agents and is well mixed, will be mixed
Close homogeneous mixture to be put into screw extruding forming machine, in 150-200 DEG C of temperature, under rotating speed is 100-120r/min, through extruding
Strand, is made graphene 3D printing material.
Embodiment 2
In embodiment, the graphene 3D printing material with high intensity, in units of parts by weight, including following original
Material：18 parts of modified graphene, 12 parts of nano silicon, 8 parts of nano-calcium carbonate, 38 parts of PLA, 17 parts of epoxy acrylate,
5 parts of tetraalkyl butyl acrylate, 1680.8 parts of stabilizer, 1.2 parts of toughener.
Modified graphene is made up of graphene, ammoniacal liquor, polypropylene glycol glycidol ether, wherein graphene oxide and described poly-
The mass ratio of propylene glycol glycidyl ether is 90:3, ammonia concn is 28%.
Graphene 3D printing material preparation method and embodiment 1 are identical.
The test result of the graphene 3D printing material prepared in the various embodiments described above is as follows：
As seen from the above table, by the graphene 3D printing material for preparing of the present invention have high tensile, elongation at break and
High notch impact strength, the product that is come out by 3D printing is high-quality, high intensity, high-impact.
Above content is it cannot be assumed that present invention specific implementation is confined to these explanations, for technical field of the present invention
Those of ordinary skill for, under the premise of present inventive concept is not departed from, some simple deduction or replace can also be made, all should
Belong to the scope of patent protection for claims determination that the present invention is submitted.
Claims (6)
1. a kind of graphene 3D printing material of high intensity, it is characterised in that the printed material by following parts by weight raw material
It is obtained by mixing：
Above-mentioned each component summation should be 100 parts by weight.
2. graphene 3D printing material according to claim 1, it is characterised in that：Described modified graphene is by oxidation stone
Black alkene, ammoniacal liquor, polypropylene glycol glycidol ether are made, wherein the quality of graphene oxide and the polypropylene glycol glycidol ether
Than for 90:2-4, the mass concentration of the ammoniacal liquor is 27-32%.
3. graphene 3D printing material according to claim 1, it is characterised in that：The nano titanium oxide average grain diameter
20-100 nanometers.
4. graphene 3D printing material according to claim 1, it is characterised in that：The crosslinking agent is benzoyl peroxide
With one kind in tetraalkyl butyl acrylate.
5. graphene 3D printing material according to claim 1, it is characterised in that：Described stabilizer is stabilizer
1096th, 168 one or two kinds of compoundings.
6. the preparation method of the graphene 3D printing material according to claim any one of 1-5, it is characterised in that:Including with
Lower step
S1：In proportion by modified graphene, nano titanium oxide, nano-calcium carbonate, PLA, epoxy acrylate, toughener
And stabilizer fully dry after be well mixed manually；
S2：The compound that S1 is obtained is crushed in the case where temperature is -90-110 DEG C, is added crosslinking agent and is well mixed, will be well mixed
Mixture is put into screw extruding forming machine, in 150-200 DEG C of temperature, under rotating speed is 100-120r/min, through extruding strand, system
Obtain graphene 3D printing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710534553.9A CN107189385A (en) | 2017-07-03 | 2017-07-03 | A kind of graphene 3D printing material of high intensity |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107931530A (en) * | 2017-11-27 | 2018-04-20 | 四川共享铸造有限公司 | A kind of sand mold riser runner and preparation method |
| CN107999752A (en) * | 2017-11-29 | 2018-05-08 | 吉林云亭石墨烯技术股份有限公司 | A kind of preparation and application of graphene 3D printing alloy material |
| CN109535662A (en) * | 2018-11-16 | 2019-03-29 | 福州万象三维电子科技有限公司 | A kind of 3D printing material and preparation method thereof |
| CN109608841A (en) * | 2018-12-12 | 2019-04-12 | 广安长明高端产业技术研究院 | A kind of preparation method and product of MXene enhancing polylactic acid 3D printing material |
| CN110157185A (en) * | 2018-04-12 | 2019-08-23 | 济南开发区星火科学技术研究院 | A kind of graphene 3D printing material with high intensity |
| CN110316725A (en) * | 2019-07-23 | 2019-10-11 | 浙江大学 | A kind of high-density high-strength graphene frame material and preparation method thereof |
| CN110698855A (en) * | 2019-10-08 | 2020-01-17 | 浙江乾欣科技有限公司 | 3D printing material and preparation method thereof |
| CN115286739A (en) * | 2022-01-24 | 2022-11-04 | 衢州学院 | Preparation method of nanochitin composite 3d printing conductive material |
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| CN106633717A (en) * | 2016-11-17 | 2017-05-10 | 广西筑梦三体科技有限公司 | Graphene 3D (three-dimensional) print material with high impact strength |
| CN106751587A (en) * | 2016-12-28 | 2017-05-31 | 深圳市明鑫高分子技术有限公司 | Graphene 3D printing material and preparation method thereof |
| CN106751616A (en) * | 2016-12-21 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of plasticizing polylactic acid material for 3D printing and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106633717A (en) * | 2016-11-17 | 2017-05-10 | 广西筑梦三体科技有限公司 | Graphene 3D (three-dimensional) print material with high impact strength |
| CN106751616A (en) * | 2016-12-21 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of plasticizing polylactic acid material for 3D printing and preparation method thereof |
| CN106751587A (en) * | 2016-12-28 | 2017-05-31 | 深圳市明鑫高分子技术有限公司 | Graphene 3D printing material and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107931530A (en) * | 2017-11-27 | 2018-04-20 | 四川共享铸造有限公司 | A kind of sand mold riser runner and preparation method |
| CN107999752A (en) * | 2017-11-29 | 2018-05-08 | 吉林云亭石墨烯技术股份有限公司 | A kind of preparation and application of graphene 3D printing alloy material |
| CN110157185A (en) * | 2018-04-12 | 2019-08-23 | 济南开发区星火科学技术研究院 | A kind of graphene 3D printing material with high intensity |
| CN109535662A (en) * | 2018-11-16 | 2019-03-29 | 福州万象三维电子科技有限公司 | A kind of 3D printing material and preparation method thereof |
| CN109535662B (en) * | 2018-11-16 | 2021-03-19 | 福州万象三维电子科技有限公司 | 3D printing material and preparation method thereof |
| CN109608841A (en) * | 2018-12-12 | 2019-04-12 | 广安长明高端产业技术研究院 | A kind of preparation method and product of MXene enhancing polylactic acid 3D printing material |
| CN110316725A (en) * | 2019-07-23 | 2019-10-11 | 浙江大学 | A kind of high-density high-strength graphene frame material and preparation method thereof |
| CN110698855A (en) * | 2019-10-08 | 2020-01-17 | 浙江乾欣科技有限公司 | 3D printing material and preparation method thereof |
| CN115286739A (en) * | 2022-01-24 | 2022-11-04 | 衢州学院 | Preparation method of nanochitin composite 3d printing conductive material |
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