CN105001586B - A kind of 3D printing wire conduction ABS/PLA composites and its preparation method and application - Google Patents
A kind of 3D printing wire conduction ABS/PLA composites and its preparation method and application Download PDFInfo
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- CN105001586B CN105001586B CN201510411122.4A CN201510411122A CN105001586B CN 105001586 B CN105001586 B CN 105001586B CN 201510411122 A CN201510411122 A CN 201510411122A CN 105001586 B CN105001586 B CN 105001586B
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- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000000463 material Substances 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
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- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
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- 239000002131 composite material Substances 0.000 claims abstract description 13
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- 239000003575 carbonaceous material Substances 0.000 claims description 21
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
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- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 abstract 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 abstract 1
- 229920000638 styrene acrylonitrile Polymers 0.000 abstract 1
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- 238000005516 engineering process Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
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- 238000007639 printing Methods 0.000 description 3
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- XQMVBICWFFHDNN-UHFFFAOYSA-N 5-amino-4-chloro-2-phenylpyridazin-3-one;(2-ethoxy-3,3-dimethyl-2h-1-benzofuran-5-yl) methanesulfonate Chemical compound O=C1C(Cl)=C(N)C=NN1C1=CC=CC=C1.C1=C(OS(C)(=O)=O)C=C2C(C)(C)C(OCC)OC2=C1 XQMVBICWFFHDNN-UHFFFAOYSA-N 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Abstract
It is made the invention provides a kind of 3D printing wire conduction ABS/PLA composites, including the raw material of following percentage：Substance law ABS 15 ~ 30%；Emulsion method ABS 15 ~ 30%；Styrene-acrylonitrile glycidyl methacrylate copolymer 1 ~ 10%；Butyltriphenylphosphonium bromide phosphine 0.01 ~ 0.05%；Metal nickel powder 5 ~ 15%；PLA 30 ~ 50%；Multi-walled carbon nanotube 1 ~ 5%；Graphene microchip 1 ~ 5%, the present invention is arranged in pairs or groups using the optimization of nickel powder, graphene microchip and CNT, obtain the electric conductivity requirement that relatively low specific insulation is realized under relatively low conductive additive content, the ABS material of different-grain diameter mixing make it that bimodal distribution is presented in particle diameter in composite, and toughness strengthens, ABS and the PLA cocontinuity that mixes are good, the highly conductive material strip material needed for the double end that is particularly suitable for use in 3D printing.
Description
Technical field
The invention belongs to 3D printing wire conductive material technical field, used more particularly, to a kind of 3D printing wire
Conductive ABS/PLA composites and its preparation method and application.
Background technology
There are the STRATASYS P400ABS of import, domestic montmorillonite in the 3D printing ABS material bar of China's sale at present
Modified ABS (CN104672755A), fiber glass reinforced ABS (CN104559034A), polycarbonate modified ABS
(CN104559023A), the ABS (CN104072935A, CN103980429A) of rubber particles bimodal distribution, carbon black conductive are modified
ABS (CN103788565A), wherein conductive 3D printing ABS material bar has carbon black conductive disclosed in CN103788565A to be modified
ABS, but carbon black conductive content reaches more than 35 mass parts, because the printing effect that filer content height has a strong impact on ABS material bar (occurs
Precision is low, be layered).And the specific insulation of the conductive ABS preferably can only achieve 102* centimetres of level of ohm, discomfort is used as
Guidewire use in ABS matter 3D printing parts.
The wire that current useful 3D printing is printed with ABS material bar in consuming parts, but consuming parts, which is still used, to be painted
Envelope curve, PVC copper-clads wire, PE copper-clad wires, it is impossible to integrated molding, the bonding with ABS substrate are poor, there is electric leakage risk.
With PLA material strips and conductive 3D printing PLA material strips, (Proto-pasta is conductive for existing non-conductive 3D printing
PLA, specific insulation is 15 ohm * centimetres and Black Magic 3D conduction PLA, and specific insulation is 1 ohm * centimetres) warp
Double end is printed as compact consuming parts, but on the one hand because appliance field use habit, consuming parts are all with ABS materials
Based on matter, PLA materials are not received, another aspect PLA base material electrical appliances there is a possibility that water suction degraded and mouldy, durability
Difference.
The method that the possibility occurred at present solves above technological deficiency is to utilize double end 3D printing technique, with non-conductive
ABS material bar and conductive 3D printing print consuming parts with PLA material strips together, but ABS in the part that goes out of current file printing
It is poor to be bonded with PLA, and there is also the risk leaked electricity during high humidity.
Therefore, for above technical barrier, the present invention seeks to provide a kind of highly conductive material of suitable double end 3D printing technique
Bar, can simultaneously be solved in highly conductive 3D printing material strip with non-conductive ABS material Application of composite in printing consuming parts
Conductive filler content is high, the defect that precision is low, be layered occurs, and meet the highly conductive need of 1 ohm less than * centimetres of specific insulation
Ask.
The content of the invention
It is an object of the invention to led according to existing 3D printing with the deficiency of ABS material bar technology there is provided a kind of 3D printing
Line conduction ABS/PLA composites.
It is another object of the present invention to provide the preparation side of 3D printing wire conduction ABS/PLA composites
Method and application.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
The invention provides a kind of 3D printing wire conduction ABS/PLA composites, the composite includes as follows
The raw material of number meter by weight percentage is made：
Substance law ABS 15~30%
Emulsion method ABS 15~30%
Styrene-acrylonitrile-glycidyl methacrylate copolymer 1~10%
Methyltriphenylphosphonium bromide 0.01~0.05%
Metal nickel powder 5~15%
PLA 30~50%
Multi-walled carbon nanotube 1~5%
Graphene microchip 1~5%.
Preferably, raw material of the composite including the following meter of number by weight percentage is made：
Substance law ABS 15~25%
Emulsion method ABS 15~25%
Styrene-acrylonitrile-glycidyl methacrylate copolymer 3~7%
Methyltriphenylphosphonium bromide 0.01~0.05%
Metal nickel powder 8~12%
PLA 32~45%
Multi-walled carbon nanotube 1~4%
Graphene microchip 1~4%.
The present invention is closely piled up using metal nickel powder, graphene microchip and multi-walled carbon nanotube optimization collocation, can be relatively low
Conductive additive content under realize 1 ohm * centimetres with lower wire conduction require, be blended in the preferable PLA of mobility
In PLA material, and it is compound with ABS material realization, processing fluidity requirement of the 3D printer to material strip can be met.
The preparation method of 3D printing wire conduction ABS/PLA composites of the present invention, comprises the following steps：
S1. multi-walled carbon nanotube and graphene microchip are added in solvent, ultrasound adds PLA, continues ultrasound, will
The heating of gained mixture, obtains PLA/ carbon material master batches after ultrasound；
S2. gained PLA/ carbon materials master batch, PLA and metal nickel powder in S1 steps are added into melt blending in banbury,
Obtain PLA/Ni/ carbon material conductive agglomerates；
S3. by gained PLA/Ni/ carbon materials conductive agglomerate in S2 steps and substance law ABS, emulsion method ABS, styrene-the third
Alkene nitrile-glycidyl methacrylate copolymer and methyltriphenylphosphonium bromide mixing, are melted through double screw extruder
Blending, then the 3D printing for preparing conductive modified through material strip forming machine ABS material bar.
Preferably, in the S1 quality of multi-walled carbon nanotube and graphene microchip account for PLA/ carbon material master batches 15~
25%.
Preferably, the quality of metal nickel powder accounts for the 15~25% of PLA/Ni/ carbon material conductive agglomerates in the S2.
Preferably, the quality of metal nickel powder accounts for the 8~12% of conductive ABS/PLA composites in the S3.
Preferably, the quality of multi-walled carbon nanotube and graphene microchip accounts for the 3 of conductive ABS/PLA composites in the S3
~8%.
The present invention first passes through solution blended process and PLA, multi-walled carbon nanotube (MWCNTs) and graphene microchip (GNP) is blended
The master batch of 15~25wt% carbon material concentration is prepared as, then the master batch and PLA, metal nickel powder are prepared through banbury melt blending
Carbon material concentration (MWCNTs and GNP) is about 6~10%, conductive agglomerate of metal nickel powder concentration 15~25%, then by the master batch
ABS, ABS, the styrene-acrylonitrile-glycidyl methacrylate copolymer (SAN- of emulsion synthesis synthesized with substance law
GMA), methyltriphenylphosphonium bromide (TPB) carries out melt blending in double screw extruder, obtains nickel powder concentration 8~12%, carbon
The conductive ABS/PLA composites of material concentration 3~8% or so, then used through material strip shaping mechanism for the 3D printing of conductive modified
Material strip.
Preferably, solvent is chloroform in the S1, and ultrasonic time is 6~9h, and it is 3~5, the heating to continue ultrasonic time
Temperature is 100~140 DEG C.
It is highly preferred that the heating-up temperature is 120 DEG C.
Preferably, melt blending temperature is 180~200 DEG C in the S2.
Preferably, double screw extruder heating-up temperature is 180~200 DEG C in the S3.
ABS and PLA formation co-cable transmission in the present invention, on material strip top layer, existing ABS phases have PLA phases again, when melting material strip
It is compatible good when being contacted with non-conductive ABS, when melting billot is contacted with other conductive ABS/PLA layers, because of depositing for top layer PLA
And bond also very close, reach enhancing interlayer bond effect more more preferable than prior art.
The ABS mixing of ABS and the emulsion method synthesis synthesized using substance law is used as the main of 3D printing ABS/PC alloys
Matrix, is and the less rubber of ABS particle diameters of emulsion method synthesis because the ABS that synthesizes of substance law is containing the larger rubber phase of particle diameter
Phase, both, which mix, can obtain the ABS matrixes that bimodal distribution is presented in rubber phase particle diameter, and the toughness of final material can be made more preferable,
The method of this melt blending obtains bimodal ABS, and it is more simple, adjustable with the method polymerizeing to obtain bimodal ABS than prior art
Section property is higher.
Compared with prior art, the present invention has the advantages that：
The present invention is arranged in pairs or groups by the optimization of metal nickel powder, graphene microchip and CNT, obtains relatively low conductive addition
The electric conductivity requirement of relatively low specific insulation is realized under agent content, the ABS material of different-grain diameter mixing causes in composite
Bimodal distribution is presented in ABS particle diameters, and toughness strengthens, and ABS and the PLA cocontinuity that mixes are good, the double end that is particularly suitable for use in 3D printing skill
Highly conductive material strip material needed for art.
Brief description of the drawings
Fig. 1 is the composite synthesis step figure that the embodiment of the present invention 1 is provided.
Fig. 2 is the SEM figures for the composite that the embodiment of the present invention 1 is provided.
Embodiment
This technology is further illustrated below in conjunction with specific embodiment, but embodiment does not do any type of to this technology
Limit.Unless stated otherwise, the reagent of the invention used, method and apparatus is the art conventional reagent, methods and apparatus.
The PLA trades mark：NatureWorks 4043D PLA
SAN-GMA：SAG-002, the rise molecule new material Science and Technology Ltd. of Nantong day
Methyltriphenylphosphonium bromide (TPB)：Shanghai Yu Mei Chemical Co., Ltd.s
Substance law ABS：Tao Shi MAGNUM 213
Emulsion method ABS：The strange U.S. 747 in Taiwan, the strange U.S. 757 in Taiwan, the strange U.S. 756 in Taiwan
GNP：KNG-180 Xiamen Knano Graphene Technology Corporation Limited
CNT：CNT-3 Shanghai Ka Jite Chemical Industry Science Co., Ltd
Tensile strength：Using universal testing machine, according to ASTM-D638 standard testings
Notch impact strength：Using shock machine, according to GB/T1043 standard testings
Specific insulation：Using the digital ultra-high resistance of EST121 types, micro current instrument, surveyed according to GB/T1410-2006
Examination, sample diameter 82mm, thick 2mm, each sample surveys five groups, takes its average value.
Embodiment 1：
1st, according to the raw material proportioning of embodiment 1 in table 1, weigh CNT and GNP and be placed in beaker, add chloroform, side high-speed stirring
Mix, side ultrasound (power 120W) adds PLA after 8 hours, continue ultrasound and stir 4 hours, after mixture is air-dried, be placed in
4 hours in 120 degrees Celsius of baking ovens, PLA/ carbon material master batches are obtained.
2nd, pure PLA, PLA/ carbon material master batch and metal nickel powder are added in banbury in 185 degrees Celsius of lower melt blendings,
Prepare PLA/Ni/ carbon material conductive agglomerates.
CNT and GNP quality accounts for the 15~25% of PLA/ carbon material master batches in step 1.
The quality of metal nickel powder accounts for the 15~25% of PLA/Ni/ carbon material conductive agglomerates in step 2.
3rd, PLA/Ni/ carbon materials conductive agglomerate and substance law ABS (Tao Shi MAGNUM 213), (Taiwan is very beautiful by emulsion method ABS
747), styrene-acrylonitrile-glycidyl methacrylate copolymer (SAN-GMA), methyltriphenylphosphonium bromide (TPB)
Mixing, through double screw extruder in carrying out melt blending under 185 degrees Celsius, prepares carbon material and nickel powder is composite modified connects altogether
Continuous ABS/PLA alloys, then the 3D printing ABS material bar through material strip forming machine manufacture conductive modified.
Fig. 1 is the composite synthesis step figure that embodiment 1 is provided, and Fig. 2 is the SEM for the composite that embodiment 1 is provided
Figure.
Embodiment 2
Preparation method be the same as Example 1, emulsion method ABS raw materials are the strange U.S. 757 in Taiwan, and raw material proportion of composing is shown in Table 1.
Embodiment 3：
Preparation method be the same as Example 1, emulsion method ABS raw materials are the strange U.S. 756 in Taiwan, and raw material proportion of composing is shown in Table 1.
Embodiment 4：
Preparation method be the same as Example 1, raw material proportion of composing is shown in Table 1.
Embodiment 5：
Preparation method be the same as Example 1, raw material proportion of composing is shown in Table 1.
Embodiment 6：
Preparation method be the same as Example 1, raw material proportion of composing is shown in Table 1.
Embodiment 7:
Preparation method be the same as Example 1, raw material proportion of composing is shown in Table 1.
Comparative example 1：：
Preparation method be the same as Example 1, unlike the substance law ABS purchasing of raw materials from Sinopec Shanghai branch company 8391.
Comparative example 2：
Preparation method be the same as Example 1, the difference is that the certainly German BASF GP-22 of the emulsion method ABS purchasing of raw materials.
Comparative example 3：
Preparation method be the same as Example, the difference is that the substance law ABS purchasing of raw materials is from Sinopec Shanghai branch company 8391, it is newborn
The certainly German BASF GP-22 of the liquid method ABS purchasing of raw materials.
Table 1 is the raw material of embodiment 1~7 and consumption, is mass percent concentration (wt%).
Table 1
Table 2 is the machinery and electric conductivity data that embodiment 1~7 and comparative example 1~3 are measured：
Table 2
Wherein, in commercially available material, Proto-pasta conductions PLA specific insulation is 15 Ω * cm, Black Magic
3D conductions PLA specific insulation is 1 Ω * cm.
As can be seen from the above data, arranged in pairs or groups, be prepared into using the optimization of metal nickel powder, graphene microchip and CNT
The materials conductive additive level arrived is low, and realizes the electric conductivity requirement of relatively low specific insulation, reaches below 1 Ω * cm, than
Existing two kinds of commercially available highly conductive Proto-pasta conduction PLA and Black Magic 3D conductions PLA specific insulation will also
It is low.
In addition, the two kinds of specific ABS provided using the present invention are as base material, the ABS composite material being mixed with, its toughness
And electric conductivity is compared with other ABS substrate effects more preferably, shows its good blended characteristic.
Claims (10)
1. a kind of 3D printing wire conduction ABS/PLA composites, it is characterised in that the composite includes following by weight
The raw material of amount percentage number meter is made：
Substance law ABS 15 ~ 30%
Emulsion method ABS 15 ~ 30%
Styrene-acrylonitrile-glycidyl methacrylate copolymer 1 ~ 10%
Methyltriphenylphosphonium bromide 0.01 ~ 0.05%
Metal nickel powder 5 ~ 15%
PLA 30 ~ 50%
Multi-walled carbon nanotube 1 ~ 5%
Graphene microchip 1 ~ 5%.
2. 3D printing wire conduction ABS/PLA composites according to claim 1, it is characterised in that described compound
The raw material that material includes the following meter of number by weight percentage is made：
Substance law ABS 15 ~ 25%
Emulsion method ABS 15 ~ 25%
Styrene-acrylonitrile-glycidyl methacrylate copolymer 3 ~ 7%
Methyltriphenylphosphonium bromide 0.01 ~ 0.05%
Metal nickel powder 8 ~ 12%
PLA 32 ~ 45%
Multi-walled carbon nanotube 1 ~ 4%
Graphene microchip 1 ~ 4%.
3. a kind of preparation method of the 3D printing wire conduction ABS/PLA composites described in claim 1 or 2, its feature
It is, comprises the following steps：
S1. multi-walled carbon nanotube and graphene microchip are added in solvent, ultrasound adds PLA, continues ultrasound, will be super
The heating of gained mixture, obtains PLA/ carbon material master batches after sound；
S2. gained PLA/ carbon materials master batch, PLA and metal nickel powder in S1 steps are added into melt blending in banbury, obtained
To PLA/Ni/ carbon material conductive agglomerates；
S3. by gained PLA/Ni/ carbon materials conductive agglomerate in S2 steps and substance law ABS, emulsion method ABS, styrene-propene
Nitrile-glycidyl methacrylate copolymer and methyltriphenylphosphonium bromide mixing, carry out melting altogether through double screw extruder
It is mixed, obtain conductive ABS/PLA composites, then the 3D printing for preparing conductive modified through material strip forming machine ABS material bar.
4. preparation method according to claim 3, it is characterised in that multi-walled carbon nanotube and graphene microchip in the S1
Quality account for the 15 ~ 25% of PLA/ carbon material master batches.
5. preparation method according to claim 3, it is characterised in that the quality of metal nickel powder accounts for PLA/Ni/ in the S2
The 15 ~ 25% of carbon material conductive agglomerate.
6. preparation method according to claim 3, it is characterised in that the quality of metal nickel powder accounts for conductive ABS/ in the S3
The 8 ~ 12% of PLA composites.
7. preparation method according to claim 3, it is characterised in that multi-walled carbon nanotube and graphene microchip in the S3
Quality account for the 3 ~ 8% of conductive ABS/PLA composites.
8. preparation method according to claim 3, it is characterised in that solvent is chloroform in the S1, ultrasonic time is 6 ~
9h, continuation ultrasonic time is 3 ~ 5h, and the heating-up temperature is 100 ~ 140 DEG C.
9. preparation method according to claim 3, it is characterised in that melt blending temperature is 180 ~ 200 DEG C in the S2.
10. preparation method according to claim 3, it is characterised in that double screw extruder heating-up temperature is in the S3
180~200℃。
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