CN105602213A - Preparation of shape memory micro-nano composite material and application of shape memory micro-nano composite material in 4D (four-dimensional) printing - Google Patents
Preparation of shape memory micro-nano composite material and application of shape memory micro-nano composite material in 4D (four-dimensional) printing Download PDFInfo
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- CN105602213A CN105602213A CN201511018486.2A CN201511018486A CN105602213A CN 105602213 A CN105602213 A CN 105602213A CN 201511018486 A CN201511018486 A CN 201511018486A CN 105602213 A CN105602213 A CN 105602213A
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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
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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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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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
Abstract
The invention discloses preparation of a shape memory micro-nano composite material and application of the shape memory micro-nano composite material in 4D (four-dimensional) printing. The invention relates to the field of the 4D printing of intelligent materials, in particular to the field that the shape memory micro-nano composite material can be applied to a 4D printing technology. The invention aims to solve the technical problem of difficulty in realizing the 4D printing of the shape memory micro-nano composite material. The shape memory micro-nano composite material disclosed by the invention is formed by means of mixing a hydrogen-abstracting type photoinitiator, functional micro-nano particles, a substance containing active hydrogen in a molecular chain and an organic solvent with a low boiling point and high volatility according to a certain mass, and performing ultrasonic treatment. The composite material is applied to the 4D printing technology by means of controlling a motion direction, a motion speed and an applied pressure of a three-dimensional movement platform on an X-axis, a Y-axis and a Z-axis through software, applying pressure force on a high-pressure dispensing needle cylinder equipped with a micro-needle head through an air pump, and constructing a required three-dimensional structure by means of casting according to a constructed model. The shape memory micro-nano composite material disclosed by the invention is applied to the 4D printing.
Description
Technical field
The 4D that the present invention relates to intellectual material prints field, and being specifically related to a kind of shape memory Micron-nano composites can applyIn the field of 4D printing technique.
Background technology
It is at the early-stage that 3D prints industry, and 4D prints cocoon-break and going out of concept. 4D refers on the basis of printing at 3D and increasesAdd a time, thereby become 4D technology. In fact, it is exactly that a kind of 3D that has adopted energy auto Deformation material prints:Scientist completes after modeling and setting-up time by software, uses 3D printing technique by preliminary a kind of deformable material printing shaping,According to initial setting, deformable material at the appointed time auto Deformation becomes needed shape. 4D prints this technology willEven bring revolutionary variation in the field such as space probation to software, robot, art, 4D prints have potential excellentGesture is causing showing great attention to of industry. At present 4D technology also rests on the experimental stage, its bottleneck be also do not find suitableCan perception the intellectual material of outside stimulus. Up to now, the material that 4D printing technique uses can only be responded to the stimulation of water,Find can experience light, thermal and magnetic field even the novel intelligent material of time be very must to the development that promotes 4D printing techniqueWant.
Shape memory Micron-nano composites is taking shape-memory polymer as matrix, and functional micro-and nano-particles is to fill phaseOne class intellectual material. By the kind of regulatory function particle, shape memory Micron-nano composites can perception electricity, magnetic,The outside stimulus such as light, solution, and initiatively spontaneously return back to its original shapes, and without any External Force Acting. Shape memoryMicron-nano composites has advantages of that a lot of traditional materials are incomparable, as large in deformation quantity, easy to use; Raw material abundance,Wide in variety, shape memory recovery temperature wide ranges; Quality is light, easily packed and transported; Rely on physical environment to stimulate and drive, withoutExternal Force Acting; Low price; Corrosion-resistant, electrical insulating property and high insulating effect etc. In addition its unique active deformation characteristic,Shape memory Micron-nano composites is one of key material of realization and development 4D printing technique.
Although shape memory Micron-nano composites has shown huge application potential and practical value in 4D printing field,But it is applied still in the starting stage. One of important reason is because be subject to the impact of traditional contour machining procedure, shapeShape memory Micron-nano composites is processed to the simple two-dimensional shapes such as sheet material, sheet material, film conventionally, is difficult to realize three-dimensionally shaped.This affects and has limited the development of 4D printing technique largely. Therefore the shape memory that, exploitation can be three-dimensionally shapedPolymer micro-nano nano composite material and technology, to promoting the development in shape-memory material field and 4D printing field most important.
Summary of the invention
The object of the invention is to print in order to solve shape memory Micron-nano composites 4D the technical problem that is difficult to realization, carrySupply a kind of preparation of shape memory Micron-nano composites of the 4D of can be used for printing. Meanwhile, technology of the present invention is applicableIn various shape memory Micron-nano composites, 4D prints, thereby can realize complex three-dimensional forms memory structures and devicePreparation.
The preparation method of shape memory Micron-nano composites of the present invention carries out according to the following steps:
One, vacuum drying chamber inner drying 12h～24h that in strand, the material containing active hydrogen is 40 DEG C～60 DEG C in temperature is removedWater, gets rid of the impact of moisture on experiment to greatest extent, obtains the material containing active hydrogen in dry strand;
Two, by hydrogen-capture-type light initiator, functional micro-and nano-particles, strand containing the material of active hydrogen with low boiling is high wavesSend out property organic solvent according to (4～10): (10～20): (80～120): the mass ratio of (1000～1500) inserts in containerRow mechanical agitation 18h～26h, the solution that obtains mixing; Then gained solution is poured in container, and container is uncoveredBe placed in ultrasonic dispersing apparatus and disperse and make solvent evaporation, until contain the concentration of the material of active hydrogen in molecules in solution chain be20%～30%, prepare shape memory Micron-nano composites solution, stand-by; In whole solution preparation process, bottleBody need cover with opaque tinfoil, to prevent irradiation.
Shape memory Micron-nano composites prepared by the present invention, for 4D printing technique, is specifically realized according to the following steps:
One, shape-memory polymer solution is packed in the high pressure spot plastic pin cylinder of being furnished with miniature syringe needle, and by air pump to high pressurePoint plastic pin cylinder is exerted pressure; By the three-dimensional mobile platform of software control at x, y, the direction of motion on z axle and movement velocity 0.1Mm/s-10mm/s, describedly exerts pressure as 50MPa-500MPa to high pressure spot plastic pin cylinder by air pump; In whole processIn, UVLED spot light irradiates the solution of extruding always, with the cross-linking reaction of trigger molecule segment, obtains having shape noteRecall the three-dimensional structure of effect; (solution in syringe can be sheared stream at the inner capillary that forms of miniature syringe needle under the effect of high pressure,From miniature syringe needle, flow out and discharge subsequently internal stress. In this process, in shape memory Micron-nano composites solutionSolvent can evaporate, and causes the hardness of material to rise, and the shape printing becomes solid from liquid) internal diameter of described syringe needle is30um-250um；
Two, the prepared three-dimensional structure with SME is heated to its glass transition temperature (Tg) more than, changeDistortion shape is fixed as needed temporary structure; Keep external force to be cooled to TgBelow make temporary structure fix; Stimulate in outfieldUnder, corresponding temporary structure can return to initial three-dimensional structure, have the three-dimensional structure of SME manufactured after stillSo can change form, demonstrate the characteristic of three-dimensional article dynamic change in time, so far complete 4D and print;
In described strand containing the material of active hydrogen be PLA, polycaprolactone, poly butylene succinate, polyurethane,One or more mixtures in polylactide-co-glycolide, polymethyl methacrylate, Merlon, polyacrylate;
Described hydrogen-capture-type light initiator is one or more mixing of benzophenone, 2,4-DihydroxyBenzophenone, Michler's ketonThing;
Described low boiling high volatile volatile organic solvent is carrene, chloroform, oxolane, toluene, ethanol, thirdOne or more mixtures in ketone, DMF;
Described functional micro-and nano-particles is micro-nano tri-iron tetroxide, single armed CNT, both arms CNT, multi-armOne in CNT, Graphene, graphene oxide, zinc oxide, titanium dioxide, organic salt, cellulose, nickel or manyPlant mixture.
Described outfield stimulates as the one in alternating magnetic field excitation, electric excitation, uv light induction, water excitation, solution excitationOr multiple.
Compared with prior art, the beneficial effect that the present invention has is:
1. printing technique has designability, and the 4D that can realize various shape memory Micron-nano composites prints, and is suitable forWide ranges and wide.
2. can realize the 4D of shape memory Micron-nano composites is printed, can to print to such an extent that solution designs ruleDraw, make prepared three-dimensional structure make corresponding stimuli responsive sexual behaviour according to residing external environment is different, and not onlyBe limited to thermostimulation response.
3. by selecting the printing syringe needle of different size, formed precision can be adjustable from 30um-250um, simultaneously compact dimensionsFrom micron order to grade not etc. Not only can realize the preparation of large scale three-dimensional structure, also can realize microsize three-dimensional simultaneouslyThe preparation of structure. Machining accuracy is high, and compact dimensions scope is wide.
4. whole print procedure at room temperature can carry out, and without particular surroundings requirement, cost is low, is suitable for technological requirement.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprise between each detailed description of the invention arbitrarilyCombination.
Detailed description of the invention one: the preparation method of the shape memory nano composite material of present embodiment carries out according to the following steps:
One, vacuum drying chamber inner drying 12h～24h that in strand, the material containing active hydrogen is 40 DEG C～60 DEG C in temperature is removedWater, gets rid of the impact of moisture on experiment to greatest extent, obtains the material containing active hydrogen in dry strand;
Two, by hydrogen-capture-type light initiator, functional micro-and nano-particles, strand containing the material of active hydrogen with low boiling is high wavesSend out property organic solvent according to (4～10): (10～20): (80～120): the mass ratio of (1000～1500) inserts in containerRow mechanical agitation 18h～26h, the solution that obtains mixing; Then gained solution is poured in container, and container is uncoveredBe placed in ultrasonic dispersing apparatus and disperse and make solvent evaporation, until contain the concentration of the material of active hydrogen in molecules in solution chain be20%～30%, prepare shape memory Micron-nano composites solution, stand-by; In whole solution preparation process, bottleBody need cover with opaque tinfoil, to prevent irradiation.
In described strand containing the material of active hydrogen be PLA, polycaprolactone, poly butylene succinate, polyurethane,One or more mixtures in polylactide-co-glycolide, polymethyl methacrylate, Merlon, polyacrylate;
Described hydrogen-capture-type light initiator is one or more mixing of benzophenone, 2,4-DihydroxyBenzophenone, Michler's ketonThing;
Described low boiling high volatile volatile organic solvent is carrene, chloroform, oxolane, toluene, ethanol, thirdOne or more mixtures in ketone, DMF;
Described functional micro-and nano-particles is micro-nano tri-iron tetroxide, single armed CNT, both arms CNT, multi-armOne in CNT, Graphene, graphene oxide, zinc oxide, titanium dioxide, organic salt, cellulose, nickel or manyPlant mixture.
Detailed description of the invention two: present embodiment is different from detailed description of the invention one, contains active hydrogen in described strandMaterial be PLA. Other steps are identical with detailed description of the invention one with parameter.
Detailed description of the invention three: present embodiment is different from detailed description of the invention one, step 2 by hydrogen-capture-type light initiator,In functional particle, strand containing the material of active hydrogen and low boiling high volatile volatile organic solvent according to 5:11:100:1200Mass ratio insert and in container, carry out mechanical agitation 24h, the solution that obtains mixing. Other steps and parameter and concrete realExecute mode one identical.
Detailed description of the invention four: present embodiment is different from detailed description of the invention one, contains active hydrogen in step 2 strandThe concentration of material be 28%. Other steps are identical with detailed description of the invention one with parameter.
Detailed description of the invention five: present embodiment is different from detailed description of the invention one, the hydrogen-abstraction light described in step 2 drawsSending out agent is benzophenone. Other steps are identical with detailed description of the invention one with parameter.
Detailed description of the invention six: present embodiment is different from detailed description of the invention one, high the waving of low boiling described in step 2The property sent out organic solvent is carrene. Other steps are identical with detailed description of the invention one with parameter.
Detailed description of the invention seven: present embodiment is different from detailed description of the invention one, the functional particle described in step 2For nano ferriferrous oxide. Other steps are identical with detailed description of the invention one with parameter.
Detailed description of the invention eight: present embodiment utilizes shape memory nano composite material prepared by embodiment one for 4DPrinting technique, specifically realize according to the following steps:
One, shape-memory polymer solution is packed in the high pressure spot plastic pin cylinder of being furnished with miniature syringe needle, and by air pump to high pressurePoint plastic pin cylinder is exerted pressure; By the three-dimensional mobile platform of software control at x, y, the direction of motion on z axle and movement velocity 0.1Mm/s-10mm/s, describedly exerts pressure as 50MPa-500MPa to high pressure spot plastic pin cylinder by air pump; In whole processIn, UVLED spot light irradiates the solution of extruding always, with the cross-linking reaction of trigger molecule segment, obtains having shape noteRecall the three-dimensional structure of effect; The internal diameter of described syringe needle is 30um-250um;
Two, the prepared three-dimensional structure with SME is heated to its glass transition temperature (Tg) more than, changeDistortion shape is fixed as needed temporary structure; Keep external force to be cooled to TgBelow make temporary structure fix; Stimulate in outfieldUnder, corresponding temporary structure can return to initial three-dimensional structure, have the three-dimensional structure of SME manufactured after stillSo can change form, demonstrate the characteristic of three-dimensional article dynamic change in time, so far complete 4D and print.
Detailed description of the invention nine: present embodiment is different from detailed description of the invention eight, described outfield stimulates as alternation magneticOne or more in field excitation, electric excitation, uv light induction, water excitation, solution excitation. Other steps and parameter and toolBody embodiment eight is identical.
Embodiment 1
A kind of preparation method of shape memory Micron-nano composites carries out according to the following steps:
One, the vacuum drying chamber inner drying 14h that is 50 DEG C by PLA in temperature dewaters, and gets rid of to greatest extent moisture pairThe impact of experiment, obtains the material containing active hydrogen in dry strand;
Two, by benzophenone, nano ferriferrous oxide, PLA and DMF according to (5:11:100:1200 mass ratio is inserted and in container, is carried out mechanical agitation 24h, the solution that obtains mixing; Then gained solution is poured intoIn container, and be placed in ultrasonic dispersing apparatus and disperse and make solvent evaporation uncovered container, until in molecules in solution chain containing livingThe concentration of sprinkling the material of hydrogen is 28%, prepares shape memory Micron-nano composites solution, stand-by; At whole solutionIn preparation process, body need cover with opaque tinfoil, to prevent irradiation.
The present embodiment successfully made can be used for 4D print photo-crosslinking type shape memory nano ferriferrous oxide/PLA moltenLiquid.
Utilize the shape memory Micron-nano composites of preparation for 4D printing technique, specifically realize according to the following steps:
One, shape memory Micron-nano composites solution is packed in the high pressure spot plastic pin cylinder of being furnished with miniature syringe needle, in syringe needleFootpath is 60um) and by air pump, it is exerted pressure; By the three-dimensional mobile platform of software control at x, y, the motion on z axleDirection, movement velocity 5mm/s and the 200MPa that exerts pressure can build required three-dimensional structure; In whole process,UVLED spot light, for irradiating the solution of extruding, with the cross-linking reaction of trigger molecule segment, obtains having shape memory effectThe three-dimensional structure of answering;
Two, the prepared three-dimensional structure with SME is heated to more than 65 DEG C, changes shape and be fixed as instituteThe temporary structure needing; Keeping external force to be cooled to 65 DEG C makes temporary structure fix below; The alternating magnetic field that is 30Hz in frequencyUnder stimulation, corresponding temporary structure can return to initial three-dimensional structure, and the three-dimensional structure with SME is manufacturedAfter still can change form, demonstrate the characteristic of three-dimensional article dynamic change in time, so far complete 4D print.
The 4D that the present embodiment has successfully been realized photo-crosslinking type nano ferriferrous oxide/PLA prints, and has prepared simultaneously and can hand overUnder the stimulation of varying magnetic field, there is the three-dimensional structure with SME of active deformation.
Claims (9)
1. a preparation method for shape memory Micron-nano composites, is characterized in that: the preparation method of this polymer by withLower step is carried out:
One, vacuum drying chamber inner drying 12h～24h that in strand, the material containing active hydrogen is 40 DEG C～60 DEG C in temperature is removedWater, obtains the material containing active hydrogen in dry strand;
Two, by hydrogen-capture-type light initiator, functional micro-and nano-particles, strand containing the material of active hydrogen with low boiling is high wavesSend out property organic solvent according to (4～10): (10～20): (80～120): the mass ratio of (1000～1500) inserts in containerRow mechanical agitation 18h～26h, the solution that obtains mixing; Then gained solution is poured in container, and container is uncoveredBe placed in ultrasonic dispersing apparatus and disperse and make solvent evaporation, until contain the concentration of the material of active hydrogen in molecules in solution chain be20%～30%, prepare shape memory Micron-nano composites solution, stand-by; In whole solution preparation process, bodyNeed cover with opaque tinfoil, to prevent irradiation;
In described strand containing the material of active hydrogen be PLA, polycaprolactone, poly butylene succinate, polyurethane,One or more mixtures in polylactide-co-glycolide, polymethyl methacrylate, Merlon, polyacrylate;
Described hydrogen-capture-type light initiator is one or more mixtures of benzophenone, 2,4-DihydroxyBenzophenone, Michler's keton;
Described low boiling high volatile volatile organic solvent is carrene, chloroform, oxolane, toluene, ethanol, thirdOne or more mixtures in ketone, DMF;
Described functional micro-and nano-particles is micro-nano tri-iron tetroxide, single armed CNT, both arms CNT, multi-armOne in CNT, Graphene, graphene oxide, zinc oxide, titanium dioxide, organic salt, cellulose, nickel or manyPlant mixture.
2. the preparation method of a kind of shape memory Micron-nano composites according to claim 1, is characterized in that: instituteMaterial containing active hydrogen in the strand of stating is PLA.
3. the preparation method of a kind of shape memory Micron-nano composites according to claim 1, is characterized in that: stepRapid two by organic molten material and the low boiling high volatile volatile containing active hydrogen in hydrogen-capture-type light initiator, functional particle, strandAgent is inserted and in container, is carried out mechanical agitation 24h, the solution that obtains mixing according to the mass ratio of 5:11:100:1200.
4. the preparation method of a kind of shape memory Micron-nano composites according to claim 1, is characterized in that: stepThe concentration that contains the material of active hydrogen in rapid two strands is 28%.
5. the preparation method of a kind of shape memory Micron-nano composites according to claim 1, is characterized in that: stepHydrogen-capture-type light initiator described in rapid two is benzophenone.
6. the preparation method of a kind of shape memory Micron-nano composites according to claim 1, is characterized in that: stepLow boiling high volatile volatile organic solvent described in rapid two is carrene.
7. the preparation method of a kind of shape memory Micron-nano composites according to claim 1, is characterized in that: stepFunctional micro-and nano-particles described in rapid two is micro-nano tri-iron tetroxide.
8. shape memory Micron-nano composites as prepared in claim 1, for 4D printing technique, is characterized in that:Specifically realize according to the following steps:
One, shape-memory polymer solution is packed in the high pressure spot plastic pin cylinder of being furnished with miniature syringe needle, and by air pump to high pressurePoint plastic pin cylinder is exerted pressure; By the three-dimensional mobile platform of software control at x, y, the direction of motion on z axle and movement velocity 0.1Mm/s-10mm/s, describedly exerts pressure as 50MPa-500MPa to high pressure spot plastic pin cylinder by air pump; In whole process,UVLED spot light irradiates the solution of extruding always, with the cross-linking reaction of trigger molecule segment, obtains having shape memory effectThe three-dimensional structure of answering; The internal diameter of described syringe needle is 30um-250um;
Two, the prepared three-dimensional structure with SME is heated to its glass transition temperature (Tg) more than, changeShape is fixed as needed temporary structure; Keep external force to be cooled to TgBelow make temporary structure fix; Under outfield stimulates,Corresponding temporary structure can return to initial three-dimensional structure, has the three-dimensional structure of SME and still can after manufacturedEnough change form, demonstrate the characteristic of three-dimensional article dynamic change in time, so far complete 4D and print.
9. shape memory Micron-nano composites according to claim 8, for 4D printing technique, is characterized in that:Described outfield stimulates as the one in alternating magnetic field excitation, electric excitation, uv light induction, water excitation, solution excitation or manyKind.
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