CN105238007A - Flexible polymer conductor, and preparation method and applications thereof - Google Patents
Flexible polymer conductor, and preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses a flexible polymer conductor, and a preparation method and applications thereof. According to the preparation method, 0.01 to 20 parts of a nano conductive filler is uniformly dispersed in an aqueous solution or an ethanol solution containing 0 to 1 part of a surfactant via ultrasonic dispersion; 100 parts of a flexible polymer powder is added, full stirring is carried out so as to coat the surfaces of the flexible polymer particles with the nano conductive filler uniformly; the flexible polymer powder coated with the nano conductive filler is obtained via filtering, drying, and screening, and is dispersed onto a selective laser sintering device workbench for 3D printing so as to obtain the flexible polymer conductor. The flexible polymer conductor possesses excellent mechanical properties and electrical conductivity; electrical conductivity can be as high as 5.06S/m; cyclic tension can be carried out for one thousand times under deformation of 50%, and electrical conductivity is maintained to be essentially constant; the flexible polymer conductor can be applied to the fields such as electronic skin, flexible electrode, flexible implantable device, wearable devices, flexible display screen, artificial blood vessel, or dielectric elastomer drivers.
Description
Technical field
The present invention relates to a kind of flexible polymer conductor and its production and use, belong to field of high polymer material processing.
Background technology
There is flexible electro-conductive material, because of it can keep its excellence conductivity stretching, under the reactive force such as bending, distortion, be widely used in fields such as Intelligent worn device, human body implanted device, flexible circuitry, flexible display screen, dielectric elastomer drivers.The kind of current fexible conductor can be divided into three kinds: the polymer elastomer 1, with conductive capability, and its conductivity principle utilizes material internal conjugatedπbond to transmit electric charge; 2, there is the conductor of certain geometric deformation ability, generally conductor is made latticed, biaxially oriented has certain extension ability; 3, electro-conductive material is added mix in flexible polymeric materials, form conductive network, or be coated in its surface, form conductive layer.Wherein the fexible conductor of the third form is widely used.
3D printing technique is the novel material molding technology of one risen in recent years, and it is cut into numerous section based on computer three-dimensional designs a model, and successively prints in vertical direction and is piled into 3D solid.By the difference of process principle and starting material form, current 3D printing technique is mainly divided into fusion sediment technology, Selective Laser Sintering, layer separated growth technology and Stereolithography technology.
Compared to conventional machining techniques, 3D printing technique makes product structure digitizing, eliminates the Design and manufacture link of mould, substantially reduces the R&D cycle of product innovation; It is shaping that 3D solid STRUCTURE DECOMPOSITION becomes two-dirnentional structure to pile up by it, and printable any complex construction, realizes personalized customization; All 3D prints goods all can once shaped, does not need follow-up assembled process, improves product manufacturing efficiency.Therefore, 3D printing technique receives to be paid attention to widely, and from birth till now, especially in recent years, development rapidly, had been widely used the fields such as education, communication, shipbuilding, automobile, aerospace, defence and military, biomedicine.
Selective Laser Sintering uses one of 3D printing technique the most widely.First it proposed at patent US4863538 by U.S. C.R.Dechard etc., and successfully developed selective laser sintering processing unit in 1989.Laser sintered for powdered material be raw material, by computer-controlled program laser, selectivity is carried out to powder body material and successively sinters, sintered rear removing excessive powder can obtain 3D print goods.The material source of selective laser sintering is extensive, and metal, pottery and polymer materials may be used to this course of processing, and wherein polymer materials receives much concern because of the performance of its excellence.Due to the restriction of current material preparation technology, be applied to the polymer materials mainly PA-12 of Selective Laser Sintering at present, other polymer materialss, as polycarbonate, polystyrene and polyether-ether-ketone etc. use less.The simultaneously performance of goods that obtained by selective laser sintering technique of these materials and polymkeric substance conventional machining process, such as injection moulding, is extruded to compare with the performance of casting the goods obtained and also has larger gap.So based on the 3D printing technique of selective laser sintering technique also not for the suitability for industrialized production of product.
Technology of preparing all relative complex of the preparation method of many fexible conductors of current report, are difficult to realize big area and produce.And 3D printing technique is simply too much relative to technique, but can shaping more complicated structure, the realization that 3D prints fexible conductor makes directly to manufacture wearable device, flexible electrode, human body implanted device, dielectric elastomer driver become possibility.
Summary of the invention
The object of the invention is a kind of flexible polymer conductor developed for the deficiencies in the prior art and its production and use, be characterized at flexible polymer powdered material Surface coating one deck conductive nano filler, owing to there is no shear force in 3D print procedure, pile up by polymer material powder the conductive network formed would not be destroyed, obtained goods have good flexibility and excellent conductivity.The range of application that 3D prints has been widened in the utilization of the method in 3D printing, and for 3D printing fexible conductor, 3D prints flexible electrode, 3D prints wearable device, 3D printing electronic skin is used and laid a good foundation.
Object of the present invention is realized by following technical measures, and wherein said raw material number, except specified otherwise, is parts by weight.
The starting raw material of flexible polymer conductor is made up of following component,
Flexible polymer powdered material 100 parts
0 ~ 1 part, tensio-active agent
Conductive nano filler 0.01 ~ 20 part
Described flexible polymer is any one of polyurethane termoplastic elastomer, thermoplasticity silicon rubber, thermoplastic polyamide elastomer, polypropylene thermoplastic elastomer, thermoplastic elastomer of polyvinyl-chloride, butadiene styrene block copolymerization thing or styrene isoprene block multipolymer.
Described tensio-active agent is any one in stearic acid, Brij 35 sodium sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, Seconary Alkane Sulphonate Sodium, fatty alcohol sodium isethionate, 1-isobutyl-3,5-dimethylhexylphosphoric acid, 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, two fourth sodium dioctyl sulfo or dioctyl succinate disulfonate acid.
Described conductive nano filler is any one in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, Graphene, carbon black, gold and silver, copper, iron or aluminium.
The preparation method of described flexible polymer conductor:
1) preparation of the coated flexible polymer powdered material of conductive nano filler
After 0 ~ 1 part of surfactant dissolves is in excessive water or ethanol, then add 0.01 ~ 20 part of conductive nano filler, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of flexible polymer powdered materials and be above-mentionedly dispersed with in the dispersion liquid of nanometer conductive material, rapid stirring, makes conductive nano filler can be coated on polymer beads sub-surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the flexible polymer powdered material obtaining being coated with conductive nano filler;
2) preparation of flexible polymer conductor
The above-mentioned polymer material powder being coated with conductive nano filler is laid on the worktable of Selective Laser Sintering, after design temperature 70 ~ 250 DEG C, thickness in monolayer 0.05 ~ 0.3mm, laser power 10 ~ 60w and sweep span 0.08 ~ 0.3mm, carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface, be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Described flexible polymer conductor is used for electronic skin, flexible electrode, flexible implantable devices, wearable device, flexible display screen, artificial blood vessel or dielectric elastomer driver field.
Performance test
1, adopt scanning electron microscope to observe at the coated pattern of polymer surfaces multi-walled carbon nano-tubes, refer to described in Fig. 1, result shows that multi-walled carbon nano-tubes can well be attached to polymer particle surface.
2, adopt transmission electron microscope to observe the carrying out that multi-walled carbon nano-tubes prints dispersion state in goods at 3D, refer to described in Fig. 2, result shows that multi-walled carbon nano-tubes reticulates distribution in polymeric matrix, defines three-dimensional conductive network.
3, coat conductive silver paste at the flexible polymer conductor two ends that 3D is printed, after dry, test resistance change when it stretches, refer to described in Fig. 3, result shows the rising of the electrical resistance stretch ratio of flexible polymer conductor and increases, and electroconductibility reduces.At removal drawing force, after deformation recovery, resistance can return to former level substantially.
The mechanical property (tensile strength, tensile modulus, elongation at break) of the flexible polymer conductor 4, adopting universal testing machine test 3D to be printed as, refer to described in table 1, result shows, along with the increase of conductive nano filler, tensile strength and the elongation at break of flexible polymer conductor all decline, modulus increases thereupon, but flexibility still meets the demands.
5, conductive silver paste is coated at the flexible polymer conductor two ends that 3D is printed, after dry, adopt resistance meter to test its electrical property, refer to described in table 2, result shows, along with the increase of conductive nano filler content, the electroconductibility of flexible polymer conductor strengthens, and it has very low percolation threshold, and about 0.2%.
6, conductive silver paste is coated at the flexible polymer conductor two ends that 3D is printed, resistance change after its cyclic tension is tested after dry, refer to described in table 3, the conductivity of flexible polymer conductor is not obvious with the change of the increase of stretching cycle index, illustrates that this flexible polymer conductor has good weather resistance.
The present invention has the following advantages:
1, there is excellent conductivity and flexibility;
2, preparation technology is simple.Preparation process is without chemical reaction, simple to operate;
3, environmentally friendly.Solvent used in preparation process completely can recycling;
4, adaptability for materials is wide.Can carry out in multiple flexible polymeric materials;
5, conductivity is excellent.3D print procedure does not have extraneous shear action, makes the Nano filling being coated on flexible polymer particles surface can keep good network structure;
6, achieve 3D and print flexible polymer conductor, widen the range of application that 3D prints.
Accompanying drawing explanation
Fig. 1 is that multi-walled carbon nano-tubes is at the surface coated scanning electron microscope (SEM) photograph of flexible polymer particles
Fig. 2 is that multi-walled carbon nano-tubes prints the projection Electronic Speculum figure disperseed in goods at 3D
The variation diagram of resistance when Fig. 3 is embodiment 2 made flexible polymer conductor-stretch
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only for further illustrating of carrying out the present invention; can not be interpreted as limiting the scope of the invention, person skilled in art can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
Be dissolved in excessive water by 0.1 part of stearic acid, then add the Single Walled Carbon Nanotube of 0.01 part, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of polyurethane termoplastic elastomer powder and be above-mentionedly dispersed with in the dispersion liquid of Single Walled Carbon Nanotube, rapid stirring, makes Single Walled Carbon Nanotube can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with Single Walled Carbon Nanotube;
The above-mentioned polyurethane termoplastic elastomer powder being coated with Single Walled Carbon Nanotube is laid on the worktable of Selective Laser Sintering, design temperature is 70 DEG C, and thickness in monolayer is 0.05mm, and laser power is 60w, sweep span is 0.08mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 2
Be dissolved in excessive water by 0.2 part of Brij 35 sodium sulfate, then add the Single Walled Carbon Nanotube of 2 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of polyurethane termoplastic elastomer powder and be above-mentionedly dispersed with in the dispersion liquid of Single Walled Carbon Nanotube, rapid stirring, makes Single Walled Carbon Nanotube can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with Single Walled Carbon Nanotube;
The above-mentioned polyurethane termoplastic elastomer powder being coated with Single Walled Carbon Nanotube is laid on the worktable of Selective Laser Sintering, design temperature is 70 DEG C, and thickness in monolayer is 0.05mm, and laser power is 60w, sweep span is 0.08mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 3
Be dissolved in excessive water by 0.3 part of ammonium lauryl sulfate, then add the Single Walled Carbon Nanotube of 4 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of polyurethane termoplastic elastomer powder and be above-mentionedly dispersed with in the dispersion liquid of Single Walled Carbon Nanotube, rapid stirring, makes Single Walled Carbon Nanotube can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with Single Walled Carbon Nanotube;
The above-mentioned polyurethane termoplastic elastomer powder being coated with Single Walled Carbon Nanotube is laid on the worktable of Selective Laser Sintering, design temperature is 70 DEG C, and thickness in monolayer is 0.05mm, and laser power is 60w, sweep span is 0.08mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 4
Be dissolved in excessive water by 0.4 part of triethanolamine lauryl sulfate, then add the Single Walled Carbon Nanotube of 6 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of polyurethane termoplastic elastomer powder and be above-mentionedly dispersed with in the dispersion liquid of Single Walled Carbon Nanotube, rapid stirring, makes Single Walled Carbon Nanotube can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with Single Walled Carbon Nanotube;
The above-mentioned polyurethane termoplastic elastomer powder being coated with Single Walled Carbon Nanotube is laid on the worktable of Selective Laser Sintering, design temperature is 70 DEG C, and thickness in monolayer is 0.05mm, and laser power is 60w, sweep span is 0.08mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 5
Be dissolved in excessive water by 0.5 part of Seconary Alkane Sulphonate Sodium, then add the gold nano conductive filler material of 8 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of thermoplasticity silicone rubber powders and be above-mentionedly dispersed with in the dispersion liquid of gold nano conductive filler material, rapid stirring, makes gold nano conductive filler material can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with gold nano conductive filler material;
The above-mentioned polyurethane termoplastic elastomer powder being coated with gold nano conductive filler material is laid on the worktable of Selective Laser Sintering, design temperature is 120 DEG C, and thickness in monolayer is 0.1mm, and laser power is 50w, sweep span is 0.15mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck that reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 6
Be dissolved in excessive water by 0.6 part of fatty alcohol sodium isethionate, then add the silver nanoparticle conductive filler material of 10 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of thermoplastic polyamide elastomer powder and be above-mentionedly dispersed with in the dispersion liquid of silver nanoparticle conductive filler material, rapid stirring, makes silver nanoparticle conductive filler material can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with silver nanoparticle conductive filler material;
The above-mentioned polyurethane termoplastic elastomer powder being coated with silver nanoparticle conductive filler material is laid on the worktable of Selective Laser Sintering, design temperature is 250 DEG C, and thickness in monolayer is 0.15mm, and laser power is 40w, sweep span is 0.2mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 7
Be dissolved in excessive water by 0.7 part of 1-isobutyl-3,5-dimethylhexylphosphoric acid, then add the copper conductive nano filler of 12 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of polypropylene thermoplastic elastomer powder and be above-mentionedly dispersed with in the dispersion liquid of copper conductive nano filler, rapid stirring, makes copper conductive nano filler can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with copper conductive nano filler;
The above-mentioned polyurethane termoplastic elastomer powder being coated with copper conductive nano filler is laid on the worktable of Selective Laser Sintering, design temperature is 140 DEG C, and thickness in monolayer is 0.2mm, and laser power is 30w, sweep span is 0.25mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 8
Be dissolved in excess ethyl alcohol by 0.8 part of 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium, then add the iron conductive nano filler of 14 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of thermoplastic elastomer of polyvinyl-chloride powder and be above-mentionedly dispersed with in the dispersion liquid of iron conductive nano filler, rapid stirring, makes iron conductive nano filler can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with iron conductive nano filler;
The above-mentioned polyurethane termoplastic elastomer powder being coated with iron conductive nano filler is laid on the worktable of Selective Laser Sintering, design temperature is 130 DEG C, and thickness in monolayer is 0.25mm, and laser power is 25w, sweep span is 0.25mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 9
Be dissolved in excess ethyl alcohol by 0.9 part of sodium laurylsulfonate, then add the aluminium conductive nano filler of 16 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of butadiene styrene block copolymerization thing powder and be above-mentionedly dispersed with in the dispersion liquid of aluminium conductive nano filler, rapid stirring, makes aluminium conductive nano filler can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with aluminium conductive nano filler;
The above-mentioned polyurethane termoplastic elastomer powder being coated with aluminium conductive nano filler is laid on the worktable of Selective Laser Sintering, design temperature is 175 DEG C, and thickness in monolayer is 0.3mm, and laser power is 20w, sweep span is 0.3mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 10
Be dissolved in excess ethyl alcohol by 1 part of Sodium dodecylbenzene sulfonate, then add the multi-walled carbon nano-tubes of 18 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of styrene isoprene block copolymer powders and be above-mentionedly dispersed with in the dispersion liquid of multi-walled carbon nano-tubes, rapid stirring, makes multi-walled carbon nano-tubes can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with multi-walled carbon nano-tubes;
The above-mentioned polyurethane termoplastic elastomer powder being coated with multi-walled carbon nano-tubes is laid on the worktable of Selective Laser Sintering, design temperature is 180 DEG C, and thickness in monolayer is 0.05mm, and laser power is 15w, sweep span is 0.2mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 11
Be dissolved in excess ethyl alcohol by 0.1 part of two fourth sodium dioctyl sulfo, then add the graphene nano conductive filler material of 20 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of thermoplasticity silicone rubber powders and be above-mentionedly dispersed with in the dispersion liquid of graphene nano conductive filler material, rapid stirring, makes graphene nano conductive filler material can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with graphene nano conductive filler material;
The above-mentioned polyurethane termoplastic elastomer powder being coated with graphene nano conductive filler material is laid on the worktable of Selective Laser Sintering, design temperature is 120 DEG C, and thickness in monolayer is 0.15mm, and laser power is 40w, sweep span is 0.2mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 12
Be dissolved in excess ethyl alcohol by 0.2 part of dioctyl succinate disulfonate acid, then add the carbon black of 1 part, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of thermoplastic polyamide elastomer powder and be above-mentionedly dispersed with in the dispersion liquid of carbon black, rapid stirring, makes carbon black can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with carbon black;
Be laid on the worktable of Selective Laser Sintering by the above-mentioned polyurethane termoplastic elastomer powder being coated with carbon black, design temperature is 250 DEG C, and thickness in monolayer is 0.15mm, and laser power is 40w, and sweep span is 0.2mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Embodiment 13
Join in excess ethyl alcohol by carbon black 4 parts, ultrasonic disperse under the condition stirred, obtains the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of polypropylene thermoplastic elastomer powder and be above-mentionedly dispersed with in the dispersion liquid of carbon black, rapid stirring, makes carbon black can be coated on polyurethane termoplastic elastomer particle surface fully, equably; Finally mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the polyurethane termoplastic elastomer powder obtaining being coated with carbon black;
Be laid on the worktable of Selective Laser Sintering by the above-mentioned polyurethane termoplastic elastomer powder being coated with carbon black, design temperature is 140 DEG C, and thickness in monolayer is 0.15mm, and laser power is 40w, and sweep span is 0.2mm, then carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface.Be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
Application example 1
According to human consumer's health practical situation, the flexible polymer conductor obtained by embodiment 2, use Computerized three-dimensional modeling program, the cad model of design wearable electronic associated components, prepare the wearable electronic that 3D prints, this wearable electronic can be good with human body laminating, there is better human comfort.
Application example 2
The flexible polymer conductor obtained by embodiment 3, uses Computerized three-dimensional modeling program, the cad model of design three-dimension flexible electrode, and prepare the flexible electrode that 3D prints, it has low resistance, high charge injection ability, and can resist chemical for a long time.
The mechanical property of flexible polymer conductor prepared by table 1. embodiment 1 ~ 4
The electric conductivity of flexible polymer conductor prepared by table 2. embodiment 1 ~ 4
Table 3. embodiment 2 flexible polymer conductor conductivity is with the change (50%) of stretching cycle index
Claims (6)
1. a flexible polymer conductor, is characterized in that the starting raw material of this flexible polymer conductor is made up of following component, counts by weight:
Flexible polymer powdered material 100 parts
0 ~ 1 part, tensio-active agent
Conductive nano filler 0.01 ~ 20 part.
2. flexible polymer conductor according to claim 1, is characterized in that flexible polymer powdered material is any one of polyurethane termoplastic elastomer, thermoplasticity silicon rubber, thermoplastic polyamide elastomer, polypropylene thermoplastic elastomer, thermoplastic elastomer of polyvinyl-chloride, butadiene styrene block copolymerization thing or styrene isoprene block multipolymer.
3. flexible polymer conductor according to claim 1, is characterized in that tensio-active agent is any one in stearic acid, Brij 35 sodium sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, Seconary Alkane Sulphonate Sodium, fatty alcohol sodium isethionate, 1-isobutyl-3,5-dimethylhexylphosphoric acid, 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, two fourth sodium dioctyl sulfo or dioctyl succinate disulfonate acid.
4. flexible polymer conductor according to claim 1, is characterized in that conductive nano filler is any one in Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, Graphene, carbon black, gold and silver, copper, iron or aluminium.
5., according to the preparation method of the described flexible polymer conductor of one of Claims 1 to 4, it is characterized in that the method comprises the following steps:
1) preparation of the coated flexible polymer powdered material of conductive nano filler
By 0 ~ 1 part of surfactant dissolves in excessive water or ethanol, add 0.01 ~ 20 part of conductive nano filler, under agitation ultrasonic disperse, obtain the dispersion liquid being dispersed with nanometer conductive material;
Joined by 100 parts of flexible polymer powdered materials and be above-mentionedly dispersed with in the dispersion liquid of nanometer conductive material, rapid stirring, makes conductive nano filler can be coated on polymer beads sub-surface fully, equably; Then mixing solutions is carried out suction filtration, the powder obtained is dried and is screened the flexible polymer powdered material obtaining being coated with conductive nano filler;
2) preparation of flexible polymer conductor
The above-mentioned flexible polymer powdered material being coated with conductive nano filler is laid on the worktable of Selective Laser Sintering, after design temperature 70 ~ 250 DEG C, thickness in monolayer 0.05 ~ 0.3mm, laser power 10 ~ 60w and sweep span 0.08 ~ 0.3mm, carries out 3D printing;
According to computer CAD 3D model, laser carries out selective scanning, sintering in specific region, powdered material surface, be excited light-struck region melted by heat, bond between particle, after one deck sintering, the height of working cylinder decline setting, carry out paving powder and the sintering of lower one deck again, and bond with front one deck, reprocessabilty like this is shaping until product is completely printed out, then take out product, namely obtain flexible polymer conductor.
6. the purposes of flexible polymer conductor according to claim 1, is characterized in that this flexible polymer conductor is for electronic skin, flexible electrode, flexible implantable devices, wearable device, flexible display screen, artificial blood vessel field or dielectric elastomer driver.
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