CN104672755A - Nano composite material for melt deposition type 3D printers and preparation method thereof - Google Patents
Nano composite material for melt deposition type 3D printers and preparation method thereof Download PDFInfo
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- CN104672755A CN104672755A CN201510058246.9A CN201510058246A CN104672755A CN 104672755 A CN104672755 A CN 104672755A CN 201510058246 A CN201510058246 A CN 201510058246A CN 104672755 A CN104672755 A CN 104672755A
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Abstract
The invention relates to a montmorillonite/ABS (Acrylonitrile Butadiene Styrene) nano composite material for melt deposition type 3D printers and a preparation method thereof. The montmorillonite/ABS nano composite material for melt deposition type 3D printers is obtained from 100 weight parts of ABS and 0.1-100 weight parts of organic modified montmorillonite by high-speed mixing and double-screw extrusion granulation. The material for melt deposition type 3D printers is obtained on the basis of a melt blending method, has the advantages of low production cost, simple preparation process, wide applicability, excellent mechanical property and the like, and can be widely applied to exiting melt deposition type 3D printers.
Description
Technical field
The present invention relates to a kind of fusion sediment type 3D printer polynite/ABS nano composite material and preparation method thereof, especially a kind of method being prepared high-performance fusion sediment type 3D printing ABS by nano imvite, belongs to chemical technology field.
Background technology
Acrylonitrile-butadiene-styrene (ABS) (ABS) is the general thermoplastic engineering plastic grown up the forties in 20th century.Its particulate material is a kind of micro-yellow solid.Have certain toughness, density is about 1.04 ~ 1.06g/cm
3.Corrosion resistance is stronger, can use in the environment of acid, alkali, salt.Also organic solvent can be insoluble in a certain extent.And there is the excellent properties such as surface hardness is high, tough and tensile, low-temperature impact resistance is good, creep resistant is good, good stability of the dimension, molding shrinkage are little.
In recent years, computer aided design (CAD) (Computer-aided Design, CAD) and rapid shaping technique (Rapid prototyping, RP) obtained and developed rapidly.These technology make designer can rapidly from concept development to entity.At present, rapid shaping technique has numerous species, and often kind of technology has unique benefit and limitation.Fusion sediment method (Fused Deposition Modeling, FDM) is wherein a kind of forming method.FDM technique Fused Deposition Modeling technique is succeeded in developing in 1988 by American scholar Scott Crump.The printed material of FDM generally selects thermoplastic material.The material of fusing first by heat fused, then from shower nozzle along part section profile with fill orbiting motion, is extruded, material quick solidification by material in shower nozzle simultaneously, and with the condensation of materials of surrounding, and then shaping.
At present, 3D prints mainly exists following bottleneck problem: 1) with subtract compared with material manufacture or injection moulding manufacture, due to the problem that bonding strength between existing in print procedure is layer by layer not high, cause increasing the goods that material manufacturing technology is often difficult to obtain traditional manufacturing process that can match in excellence or beauty in mechanical property; 2) do not need mould owing to increasing material manufacturing processed, it is very responsive to the thermal expansivity of material; And 3D is printed, due to violent cooling meat, the precision of high thermal expansivity often grievous injury resulting product.In recent ten years, laminated inorganic matter nano material because of itself institute have uniqueness quantum size effect, small-size effect, surface effects etc., the better thermostability of polymer materials, ageing resistance, barrier properties for gases, good flame retardant resistance, excellent mechanical property etc. can be given, cause people and pay much attention to.
Melt-blending process is that surface-treated clay and polymkeric substance are passed through the effects such as heat, power more than softening temperature, polymer macromolecule is entered between layered silicate clay lamella, and makes the increase of clay sheet interlayer spacing or clay limellar stripping become a kind of Nano-composite materials method of nanoscale lamella.In the last few years, melt intercalated method had become against its exclusive advantage the conventional means preparing laminated nano composition.
For the problem existing for existing FDM type 3D printer polynite/ABS material, research and development one prepares novel polynite/ABS nano composite material, and this preparation method is simple, suitability is wide, with low cost, thus FDM type 3D printer ABS consumptive material key issue urgently to be resolved hurrily can be solved, there is very important using value and academic significance.
Summary of the invention
In order to overcome the deficiency that prior art exists, the object of the present invention is to provide a kind of ABS nano composite material with strong mechanical performance and preparation method thereof.This preparation method is simple, suitability is wide, with low cost, thus ABS mechanical strength and problem such as dimensional precision is poor in FDM technology 3D prints can be solved.
To achieve the above object of the invention, the technical solution used in the present invention is: provide a kind of fusion sediment type 3D printer polynite ABS nano composite material, it is characterized in that: by weight, it comprises ABS and 0.1 ~ 100 part of organic modified nano polynite of 100 parts.
Described ABS is the one in commercialization ABS virgin material or ABS reworked material, or their combination; Described organic modification montmonrillonite is commercialization organic modification montmonrillonite or self-control organic modification montmonrillonite, or their combination.
A kind of preparation method of fusion sediment type 3D printer polynite/ABS nano composite material, is characterized in that step comprises: 1) polynite is organically-modified; 2) preparation of polynite/ABS nano composite material.
Described polynite organically-modified ties up to the appropriate organic modifiers of the interlayer intercalation of inorganic polynite.
Described organic modifiers is the one in 18 (16) alkyl trimethyl ammonium chloride, 18 (16) alkyl double hydroxyethyl ammonio methacrylate, 18 (16) alkyl dimethyl benzyl ammonium chloride, two 18 (16) alkyl dimethyl ammonium chloride, amidcaproic acid, octadecylamine, aminopropan triethoxyl silane etc., or their combination;
The median size of described organic modification montmonrillonite powder is 0.01um ~ 10um.
The preparation of described polynite/ABS nano composite material refers to by weight, by 100 parts of ABS and 0.1 ~ 100 part organic modification montmonrillonites after high-speed mixing and double-screw extruding pelletizing, obtain a kind of fusion sediment type 3D printer polynite/ABS nano composite material.
Described montmorillonite layer presents uniform intercalation configuration or lift-off structure in ABS matrix.
Useful achievement acquired by the technology of the present invention principle: 1) by introducing suitable organic modifiers, and then give consistency good between montmorillonite layer and ABS; And when organo montmorillonite and ABS pellet mixing time, ABS can enter between cheating engaging layer by fusion intercalation, and forms intercalation configuration, and then can increase the mechanical property of ABS, improves the strength and modulus of goods; 2) special 3D melt extrudes forming technique will make the arrangement in local order in ABS matrix of the montmorillonite layer of intercalation or stripping, and then significantly promotes the mechanical property of resulting product.
Accompanying drawing explanation
Fig. 1 is the TEM figure of polynite of the present invention/ABS thermoplastic resin.
Fig. 2 is for printing the comparison diagram of the tensile strength performance of rear polynite/ABS nano composite material goods.
Fig. 3 is for printing the comparison diagram of the flexural strength performance of rear polynite/ABS nano composite material goods.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
1. the preparation of organic modification montmonrillonite
1) inorganic for 100g polynite is dissolved in 4L distilled water, is stirred at 60 DEG C and forms uniform suspension;
2) toward step 1) in slowly add suitable octadecyl trimethyl ammonium chloride in the suspension that obtains, stir 5 hours;
3) by step 2) in the mixture that obtains carry out suction filtration, and repeatedly use distilled water wash, until halogen ion-free exists, obtain filter cake, after put into oven dried overnight;
4) by step 3) in the dry cake that obtains put into disintegrating apparatus and be ground into the powder that median size is 5 μm, namely obtain organic modification montmonrillonite.
2. the preparation of polynite/ABS nano composite material
Be after the organic modification montmonrillonite of 5 μm and the ABS of 1000g carry out high speed by 1g median size, extrude through twin screw extruder, after pelletizing, obtain nano montmorillonite modified ABS pellet.
Embodiment 2
1. the preparation of organic modification montmonrillonite
1) inorganic for 100g polynite is dissolved in 4L distilled water, is stirred at 60 DEG C and forms uniform suspension;
2) toward step 1) in slowly add suitable cetalkonium chloride in the suspension that obtains, stir 5 hours;
3) by step 2) in the mixture that obtains carry out suction filtration, and repeatedly use distilled water wash, until halogen ion-free exists, obtain filter cake, after put into oven dried overnight.
4) by step 3) in the dry cake that obtains put into disintegrating apparatus and be ground into the powder that median size is 0.01 μm, namely obtain organic modification montmonrillonite.
2. the preparation of polynite/ABS nano composite material
Be after the organic modification montmonrillonite of 0.01um and 1000g ABS carry out high-speed mixing by 30g median size, extrude through twin screw extruder, after pelletizing, obtain nano montmorillonite modified ABS pellet.
Embodiment 3
1. the preparation of organic modification montmonrillonite
1) inorganic for 100g polynite is dissolved in 4L distilled water, is stirred at 60 DEG C and forms uniform suspension.
2) toward step 1) in slowly add appropriate hexadecyl double hydroxyethyl ammonio methacrylate in the suspension that obtains, stir 5 hours;
3) by step 2) in the mixture that obtains carry out suction filtration, and repeatedly use distilled water wash, until halogen ion-free exists, obtain filter cake, after put into oven dried overnight.
4) by step 3) in the dry cake that obtains put into disintegrating apparatus and be ground into the powder that median size is 10 μm, namely obtain organic modification montmonrillonite.
2. the preparation of polynite/ABS nano composite material
Be after the organic modification montmonrillonite of 10 μm and 1000g ABS carry out high-speed mixing by 1000g median size, extrude through twin screw extruder, after pelletizing, obtain nano montmorillonite modified ABS pellet.
Embodiment 4
1. the preparation of organic modification montmonrillonite
Adopt the DK3 nano organic montmorillonite of Zhejiang Fenghong New Material Co., Ltd..
2. the preparation of polynite/ABS nano composite material
Be after the DK2 organo montmorillonite of 0.5 μm and 1000g ABS carry out high-speed mixing by 30g median size, extrude through twin screw extruder, after pelletizing, obtain nano montmorillonite modified ABS pellet.
See Fig. 1, it is the TEM figure of the embodiment of the present invention 1 gained polynite/ABS thermoplastic resin, and as seen from Figure 1, in ABS matrix, the interlamellar spacing of polynite greatly increases; See Fig. 2, it is the comparison diagram that the present invention prints the tensile strength performance of rear polynite/ABS nano composite material goods, and as seen from Figure 2, the organo montmorillonite added greatly can improve the tensile strength of ABS; See Fig. 2, it is the comparison diagram that the present invention prints the flexural strength performance of rear polynite/ABS nano composite material goods, and as seen from Figure 3, the organo montmorillonite added can improve the flexural strength of ABS.
Claims (7)
1. a fusion sediment type 3D printer nano composite material, is characterized in that: this material is a kind of polynite/acrylonitrile-butadiene-styrene (ABS) nano composite material, and wherein acrylonitrile-butadiene-styrene (ABS) is referred to as ABS; By weight, it comprises ABS and 0.1 ~ 100 part of organic modified nano polynite of 100 parts.
2. nano composite material according to claim 2, is characterized in that: described polynite presents uniform intercalation configuration or lift-off structure in ABS matrix.
3. nano composite material according to claim 1 and 2, is characterized in that: described ABS is the one in commercialization ABS virgin material or ABS reworked material, or their combination; Described organic modification montmonrillonite is commercialization organic modification montmonrillonite or self-control organic modification montmonrillonite, or their combination.
4. a preparation method for nano composite material described in claim 1, is characterized in that: comprise the steps: the organically-modified of (1) polynite; (2) preparation of polynite/ABS nano composite material.
5. preparation method according to claim 4, is characterized in that: the polynite in described step (1) organically-modified ties up to the appropriate organic modifiers of the interlayer intercalation of inorganic polynite.
6. preparation method according to claim 5, it is characterized in that: described organic modifiers is the one in palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, hexadecyl double hydroxyethyl ammonio methacrylate, octadecyl double hydroxyethyl ammonio methacrylate, cetalkonium chloride, stearyl dimethyl benzyl ammonium chloride, Varisoft 432PPG, distearyl dimethyl ammonium chloride amidcaproic acid, octadecylamine, aminopropan triethoxyl silane etc., or their combination; The median size of described polynite is 0.01 μm ~ 10 μm.
7. preparation method according to claim 4, it is characterized in that: the preparation of the nano composite material in described step (2) refers to by weight, by 100 parts of ABS and 0.1 ~ 100 part organic modification montmonrillonites after high-speed mixing and double-screw extruding pelletizing, obtain a kind of fusion sediment type 3D printer nano composite material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440200A (en) * | 2015-12-15 | 2016-03-30 | 中山职业技术学院 | Organic-inorganic hybrid 3D printing material and preparation method thereof |
| CN105482353A (en) * | 2015-12-22 | 2016-04-13 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Wear resistant resin material composition for printer and preparation method as well as application of wear resistant resin |
| CN105542431A (en) * | 2015-12-28 | 2016-05-04 | 成都新柯力化工科技有限公司 | Thermal insulation material for 3D (Three Dimensional) printing and preparation method thereof |
| CN105885330A (en) * | 2016-04-25 | 2016-08-24 | 中国科学院宁波材料技术与工程研究所 | Organically modified attapulgite/ABS composite, preparation method thereof and application of organic modified attapulgite/ABS composite in 3D printing |
| CN106186810A (en) * | 2016-07-22 | 2016-12-07 | 河北虹天电气科技有限公司 | A kind of 3D prints construction material |
| CN117362755A (en) * | 2023-10-12 | 2024-01-09 | 广州工程技术职业学院 | Modified filler, polypropylene composite material for 3D printing and preparation method of polypropylene composite material |
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| CN101205361A (en) * | 2007-11-29 | 2008-06-25 | 东华大学 | Montmorillonite layered nylon6/montmorillonite nano composite material and preparation thereof |
| CN102702667A (en) * | 2012-05-25 | 2012-10-03 | 浙江吉利汽车研究院有限公司杭州分公司 | Montmorillonite-modified resin and preparation method thereof |
| CN103980592A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | high-filling-content micro-nano powder/polymer composite material for 3D printing and preparation method and product thereof |
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| CN101205361A (en) * | 2007-11-29 | 2008-06-25 | 东华大学 | Montmorillonite layered nylon6/montmorillonite nano composite material and preparation thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440200A (en) * | 2015-12-15 | 2016-03-30 | 中山职业技术学院 | Organic-inorganic hybrid 3D printing material and preparation method thereof |
| CN105482353A (en) * | 2015-12-22 | 2016-04-13 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Wear resistant resin material composition for printer and preparation method as well as application of wear resistant resin |
| CN105542431A (en) * | 2015-12-28 | 2016-05-04 | 成都新柯力化工科技有限公司 | Thermal insulation material for 3D (Three Dimensional) printing and preparation method thereof |
| CN105542431B (en) * | 2015-12-28 | 2018-03-27 | 青岛美立华塑业有限公司 | A kind of heat preserving and insulating material for 3D printing and preparation method thereof |
| CN105885330A (en) * | 2016-04-25 | 2016-08-24 | 中国科学院宁波材料技术与工程研究所 | Organically modified attapulgite/ABS composite, preparation method thereof and application of organic modified attapulgite/ABS composite in 3D printing |
| CN106186810A (en) * | 2016-07-22 | 2016-12-07 | 河北虹天电气科技有限公司 | A kind of 3D prints construction material |
| CN106186810B (en) * | 2016-07-22 | 2018-06-29 | 河北虹天电气科技有限公司 | A kind of 3D printing construction material |
| CN117362755A (en) * | 2023-10-12 | 2024-01-09 | 广州工程技术职业学院 | Modified filler, polypropylene composite material for 3D printing and preparation method of polypropylene composite material |
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