CN105602213B - A kind of preparation of shape memory Micron-nano composites and its application in 4D printings - Google Patents
A kind of preparation of shape memory Micron-nano composites and its application in 4D printings Download PDFInfo
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- CN105602213B CN105602213B CN201511018486.2A CN201511018486A CN105602213B CN 105602213 B CN105602213 B CN 105602213B CN 201511018486 A CN201511018486 A CN 201511018486A CN 105602213 B CN105602213 B CN 105602213B
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- 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
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- 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
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- 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
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- 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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Abstract
A kind of preparation of shape memory Micron-nano composites and its application in 4D printings, print field, and in particular to a kind of shape memory Micron-nano composites can be applied to the field of 4D printing techniques the present invention relates to the 4D of intellectual material.Present invention aim to address the technical problem that shape memory Micron-nano composites 4D printings are difficult to.The shape memory Micron-nano composites of the present invention are by the way that material and low boiling high volatile organic solvent containing active hydrogen in hydrogen-capture-type light initiator, feature micro-and nano-particles, strand according to certain mass mixing, are obtained by ultrasonically treated.It is to control three-dimensional mobile platform in x by software that the composite, which is used for 4D printing techniques, y, then the direction of motion, movement velocity and application pressure in z-axis apply pressure by air pump to the high pressure spot plastic pin cylinder equipped with micro needle head, and required three-dimensional structure can be built by being poured by the model of structure.The shape memory Micron-nano composites of the present invention are printed for 4D.
Description
Technical field
Field is printed the present invention relates to the 4D of intellectual material, and in particular to a kind of shape memory Micron-nano composites can be answered
Field for 4D printing techniques.
Background technology
3D printing industry is at the early-stage, 4D printing concept cocoon-break and go out.4D refers to increase on the basis of 3D printing
One time, so as to become 4D technologies.In fact, it is exactly a kind of 3D printing for employing energy auto Deformation material：Scientist
Completed by software after modeling and setting time, with 3D printing technique by a kind of preliminary printing shaping of deformable material, according to initial
Setting, deformable material can at the appointed time be automatically deformed to required shape.4D prints this technology will be to software, machine
Bring revolutionary change in people, the art even field such as space probation, and 4D prints had potential advantages and causes industry
Highest attention.Current 4D technologies also rest on the experimental stage, and its bottleneck is not find also suitably perceive outside stimulus
Intellectual material.So far, the material that 4D printing techniques are used can only sense the stimulation of water, and light, thermal and magnetic can be experienced by finding
Field even the novel intelligent material of time are very necessary to the development for promoting 4D printing techniques.
Shape memory Micron-nano composites are that, using shape-memory polymer as matrix, feature micro-and nano-particles are filling
One class intellectual material of phase.By the species of regulatory function particle, shape memory Micron-nano composites can perceive electricity,
The outside stimulus such as magnetic, light, solution, and its original shapes is spontaneously actively returned back to, without the effect of any external force.Shape memory
Micron-nano composites have the advantages that many traditional materials are incomparable, and such as deformation quantity is big, easy to use；Raw material is sufficient, product
Plant many, shape memory recovery temperature scope is wide；Light weight, transport easy to package；Stimulate and drive by physical environment, without outer masterpiece
With；It is cheap；It is corrosion-resistant, electrical insulating property and high insulating effect etc..In addition its unique active deformation characteristic, shape memory is micro-
Nano composite material is realization and develops one of key material of 4D printing techniques.
Although shape memory Micron-nano composites illustrate huge application potential and practical valency in 4D printings field
Value, but its application is still within the starting stage.One of important the reason for be because influenceed by traditional contour machining procedure,
Shape memory Micron-nano composites are usually processed into the simple two-dimensional shapes such as sheet material, sheet material, film, it is difficult to realize it is three-dimensional into
Type.This largely influences and limited the development of 4D printing techniques.Therefore, the shape memory that exploitation can be three-dimensionally shaped
Polymer micro-nano nano composite material and technology, the development for printing field to promotion shape-memory material field and 4D are most important.
The content of the invention
The invention aims to solve the technical problem that shape memory Micron-nano composites 4D printings are difficult to,
There is provided a kind of preparation available for the 4D shape memory Micron-nano composites printed.Meanwhile, technology of the invention is applicable
In various shapes memory Micron-nano composites 4D printings, so as to realize the system of complex three-dimensional forms memory structures and device
It is standby.
The preparation method of the shape memory Micron-nano composites of the present invention is carried out according to the following steps：
First, by the material containing active hydrogen in strand in temperature for dried in 40 DEG C~60 DEG C of vacuum drying chamber 12h~
24h is removed water, and influence of the moisture to experiment is excluded to greatest extent, the material containing active hydrogen in dry strand is obtained；
2nd, it is the material in hydrogen-capture-type light initiator, feature micro-and nano-particles, strand containing active hydrogen and low boiling is high
Volatile organic solvent is according to (4~10):(10~20)：(80~120)：The mass ratio of (1000~1500) inserts in container
Row mechanical agitation 18h~26h, obtains well mixed solution；Then resulting solution is poured into container, and container opening is put
Disperse in ultrasonic disperse equipment and evaporate solvent, until the concentration of the material containing active hydrogen is 20% in molecules in solution chain
~30%, shape memory Micron-nano composites solution is prepared, it is stand-by；In whole solution preparation process, body needs to use
Opaque tinfoil is covered, to prevent light irradiation.
Shape memory Micron-nano composites prepared by the present invention are used for 4D printing techniques, specifically realize according to the following steps：
First, shape-memory polymer solution is loaded in the high pressure spot plastic pin cylinder equipped with micro needle head, and passes through air pump pair
High pressure spot plastic pin cylinder applies pressure；Three-dimensional mobile platform is controlled in x by software, y, the direction of motion and movement velocity in z-axis
0.1mm/s-10mm/s, it is described that pressure is applied for 50MPa-500MPa to high pressure spot plastic pin cylinder by air pump；In whole process,
UV LED point light sources irradiate the solution of extrusion always, to trigger the cross-linking reaction of molecule segment, obtain with SME
Three-dimensional structure；(solution in syringe can be internally formed capillary shear flow in the presence of high pressure in micro needle head, then from
Flowed out in micro needle head and discharge internal stress.In this process, the solvent meeting in shape memory Micron-nano composites solution
Evaporation, causes the hardness of material to rise, the shape printed is changed into solid from liquid) internal diameter of the syringe needle is 30um-
250um；
2nd, the prepared three-dimensional structure with SME is heated to its glass transition temperature (Tg) with
On, change shape and be fixed as required temporary structure；External force is kept to be cooled to TgFix temporary structure below；In outfield thorn
Under swashing, corresponding temporary structure can return to initial three-dimensional structure, after the three-dimensional structure with SME is manufactured
Remain able to change form, show characteristic of the three-dimensional article with time dynamic, so far complete 4D printings；
The material containing active hydrogen is PLA, polycaprolactone, poly butylene succinate, poly- ammonia in described strand
One or more mixtures in ester, polylactide-co-glycolide, polymethyl methacrylate, makrolon, polyacrylate；
Described hydrogen-capture-type light initiator is benzophenone, 2,4 dihydroxyl benzophenone, the one or more of Michler's keton
Mixture；
Described low boiling high volatile organic solvent is dichloromethane, chloroform, tetrahydrofuran, toluene, ethanol, third
One or more mixtures in ketone, DMF；
Described feature micro-and nano-particles are micro-nano ferroso-ferric oxide, single armed CNT, both arms CNT, many
One or more in arm CNT, graphene, graphene oxide, zinc oxide, titanium dioxide, organic salt, cellulose, nickel are mixed
Compound.
Described outfield is stimulated as one in alternating magnetic field excitation, electric excitation, uv light induction, water excitation, solution excitation
Plant or a variety of.
Compared with prior art, the invention has the advantages that：
1. printing technique has designability, it is possible to achieve the 4D printings of various shapes memory Micron-nano composites, fit
It is wide and wide with scope.
2. can realize to the 4D of shape memory Micron-nano composites printing, can to print solution is designed rule
Draw, prepared three-dimensional structure is made corresponding stimuli responsive sexual behaviour according to residing external environment difference, and not only
It is limited to thermostimulation response.
3. by selecting various sizes of printing syringe needle, formed precision can be adjustable from 30um-250um, while compact dimensions
From micron order to grade.The preparation of large scale three-dimensional structure can be not only realized, while can also realize that microsize is three-dimensional
The preparation of structure.Machining accuracy is high, and compact dimensions scope is wide.
4. whole printing process can be carried out at room temperature, no particular surroundings requirement, cost is low, suitable for technological requirement.
Embodiment
Technical solution of the present invention is not limited to act embodiment set forth below, in addition between each embodiment
Any combination.
Embodiment one：The preparation method of the shape memory nano composite material of present embodiment is entered according to the following steps
OK：
First, by the material containing active hydrogen in strand in temperature for dried in 40 DEG C~60 DEG C of vacuum drying chamber 12h~
24h is removed water, and influence of the moisture to experiment is excluded to greatest extent, the material containing active hydrogen in dry strand is obtained；
2nd, it is the material in hydrogen-capture-type light initiator, feature micro-and nano-particles, strand containing active hydrogen and low boiling is high
Volatile organic solvent is according to (4~10):(10~20)：(80~120)：The mass ratio of (1000~1500) inserts in container
Row mechanical agitation 18h~26h, obtains well mixed solution；Then resulting solution is poured into container, and container opening is put
Disperse in ultrasonic disperse equipment and evaporate solvent, until the concentration of the material containing active hydrogen is 20% in molecules in solution chain
~30%, shape memory Micron-nano composites solution is prepared, it is stand-by；In whole solution preparation process, body needs to use
Opaque tinfoil is covered, to prevent light irradiation.
The material containing active hydrogen is PLA, polycaprolactone, poly butylene succinate, poly- ammonia in described strand
One or more mixtures in ester, polylactide-co-glycolide, polymethyl methacrylate, makrolon, polyacrylate；
Described hydrogen-capture-type light initiator is benzophenone, 2,4 dihydroxyl benzophenone, the one or more of Michler's keton
Mixture；
Described low boiling high volatile organic solvent is dichloromethane, chloroform, tetrahydrofuran, toluene, ethanol, third
One or more mixtures in ketone, DMF；
Described feature micro-and nano-particles are micro-nano ferroso-ferric oxide, single armed CNT, both arms CNT, many
One or more in arm CNT, graphene, graphene oxide, zinc oxide, titanium dioxide, organic salt, cellulose, nickel are mixed
Compound.
Embodiment two：Present embodiment is lived from containing unlike embodiment one, in described strand
The material for sprinkling hydrogen is PLA.Other steps are identical with embodiment one with parameter.
Embodiment three：Present embodiment from unlike embodiment one, step 2 draws hydrogen-abstraction light
Material and low boiling high volatile organic solvent containing active hydrogen are according to 5 in hair agent, functional particle, strand：11：100：
1200 mass ratio inserts progress mechanical agitation 24h in container, obtains well mixed solution.Other steps are with parameter and specifically
Embodiment one is identical.
Embodiment four：Present embodiment is lived from containing unlike embodiment one, in step 2 strand
The concentration for sprinkling the material of hydrogen is 28%.Other steps are identical with embodiment one with parameter.
Embodiment five：Present embodiment from unlike embodiment one, the hydrogen-abstraction described in step 2
Light trigger is benzophenone.Other steps are identical with embodiment one with parameter.
Embodiment six：Present embodiment from unlike embodiment one, the low boiling described in step 2
High volatile organic solvent is dichloromethane.Other steps are identical with embodiment one with parameter.
Embodiment seven：Present embodiment from unlike embodiment one, the feature described in step 2
Particle is nano ferriferrous oxide.Other steps are identical with embodiment one with parameter.
Embodiment eight：The shape memory nano composite material that present embodiment utilizes embodiment one to prepare is used for
4D printing techniques, are specifically realized according to the following steps：
First, shape-memory polymer solution is loaded in the high pressure spot plastic pin cylinder equipped with micro needle head, and passes through air pump pair
High pressure spot plastic pin cylinder applies pressure；Three-dimensional mobile platform is controlled in x by software, y, the direction of motion and movement velocity in z-axis
0.1mm/s-10mm/s, it is described that pressure is applied for 50MPa-500MPa to high pressure spot plastic pin cylinder by air pump；In whole process,
UV LED point light sources irradiate the solution of extrusion always, to trigger the cross-linking reaction of molecule segment, obtain with SME
Three-dimensional structure；The internal diameter of the syringe needle is 30um-250um；
2nd, the prepared three-dimensional structure with SME is heated to its glass transition temperature (Tg) with
On, change shape and be fixed as required temporary structure；External force is kept to be cooled to TgFix temporary structure below；In outfield thorn
Under swashing, corresponding temporary structure can return to initial three-dimensional structure, after the three-dimensional structure with SME is manufactured
Remain able to change form, show characteristic of the three-dimensional article with time dynamic, so far complete 4D printings.
Embodiment nine：Present embodiment from unlike embodiment eight, described outfield stimulates to hand over
One or more in varying magnetic field excitation, electric excitation, uv light induction, water excitation, solution excitation.Other steps and parameter and tool
Body embodiment eight is identical.
Embodiment 1
A kind of preparation method of shape memory Micron-nano composites is carried out according to the following steps：
First, PLA is removed water in temperature to dry 14h in 50 DEG C of vacuum drying chamber, moisture pair is excluded to greatest extent
The influence of experiment, obtains the material containing active hydrogen in dry strand；
2nd, by benzophenone, nano ferriferrous oxide, PLA and DMF according to (5：11：100：
1200 mass ratio inserts progress mechanical agitation 24h in container, obtains well mixed solution；Then resulting solution is poured into appearance
In device, and container opening is placed in ultrasonic disperse equipment scattered and solvent is evaporated, until containing active in molecules in solution chain
The concentration of the material of hydrogen is 28%, prepares shape memory Micron-nano composites solution, stand-by；Prepared in whole solution
Cheng Zhong, body need to be covered with opaque tinfoil, to prevent light irradiation.
The photo-crosslinking type shape memory nano ferriferrous oxide/PLA printed available for 4D has successfully been made in the present embodiment
Solution.
It is used for 4D printing techniques using the shape memory Micron-nano composites of preparation, specifically realizes according to the following steps：
First, shape memory Micron-nano composites solution is loaded in the high pressure spot plastic pin cylinder equipped with micro needle head, syringe needle
Internal diameter be 60um) and pressure is applied to it by air pump；Three-dimensional mobile platform is controlled in x by software, y, the motion in z-axis
Direction, movement velocity 5mm/s and application pressure 200MPa can build required three-dimensional structure；In whole process, UV LED
Spot light is used for the solution for irradiating extrusion, to trigger the cross-linking reaction of molecule segment, obtains the three-dimensional with SME
Structure；
2nd, the prepared three-dimensional structure with SME is heated to more than 65 DEG C, changes shape and be fixed as
Required temporary structure；Keeping external force to be cooled to less than 65 DEG C fixes temporary structure；In the alternating magnetic field that frequency is 30Hz
Under stimulation, corresponding temporary structure can return to initial three-dimensional structure, and the three-dimensional structure with SME is manufactured
After remain able to change form, show characteristic of the three-dimensional article with time dynamic, so far complete 4D printing.
The present embodiment is successfully realized the 4D printings of photo-crosslinking type nano ferriferrous oxide/PLA, while be prepared for can
The three-dimensional structure with SME of active deformation occurs under the stimulation of alternating magnetic field.
Claims (9)
1. a kind of preparation method of shape memory Micron-nano composites, it is characterised in that：The micro-nano composite wood of the shape memory
The preparation method of material is carried out according to the following steps：
First, the material containing active hydrogen in strand is removed in temperature to dry 12h~24h in 40 DEG C~60 DEG C of vacuum drying chamber
Water, obtains the material containing active hydrogen in dry strand；
2nd, the material in hydrogen-capture-type light initiator, feature micro-and nano-particles, strand containing active hydrogen and low boiling height are volatilized
Property organic solvent is according to (4~10):(10~20)：(80~120)：The mass ratio of (1000~1500), which is inserted, carries out machine in container
Tool stirs 18h~26h, obtains well mixed solution；Then resulting solution is poured into container, and container opening is placed in super
Disperse in sound dispersing apparatus and evaporate solvent, until in molecules in solution chain the concentration of the material containing active hydrogen for 20%~
30%, shape memory Micron-nano composites solution is prepared, it is stand-by；In whole solution preparation process, body need to be with not
Transparent tinfoil is covered, to prevent light irradiation；
In described strand the material containing active hydrogen be PLA, it is polycaprolactone, poly butylene succinate, polyurethane, poly-
One or more mixtures in lactide coglycolide, polymethyl methacrylate, makrolon, polyacrylate；
Described hydrogen-capture-type light initiator is one or more mixing of benzophenone, 2,4 dihydroxyl benzophenone, Michler's keton
Thing；
Described low boiling high volatile organic solvent be dichloromethane, chloroform, tetrahydrofuran, toluene, ethanol, acetone,
One or more mixtures in DMF；
Described feature micro-and nano-particles are micro-nano ferroso-ferric oxide, single-walled carbon nanotube, multi-walled carbon nanotube, graphite
One or more mixtures in alkene, graphene oxide, zinc oxide, titanium dioxide, organic salt, cellulose, nickel.
2. a kind of preparation method of shape memory Micron-nano composites according to claim 1, it is characterised in that：It is described
Strand in the material containing active hydrogen be PLA.
3. a kind of preparation method of shape memory Micron-nano composites according to claim 1, it is characterised in that：Step
Two have material and low boiling high volatile containing active hydrogen in hydrogen-capture-type light initiator, feature micro-and nano-particles, strand
Machine solvent is according to 5：11：100：1200 mass ratio inserts progress mechanical agitation 24h in container, obtains well mixed solution.
4. a kind of preparation method of shape memory Micron-nano composites according to claim 1, it is characterised in that：Step
The concentration of the material containing active hydrogen is 28% in two strands.
5. a kind of preparation method of shape memory Micron-nano composites according to claim 1, it is characterised in that：Step
Hydrogen-capture-type light initiator described in two is benzophenone.
6. a kind of preparation method of shape memory Micron-nano composites according to claim 1, it is characterised in that：Step
Low boiling high volatile organic solvent described in two is dichloromethane.
7. a kind of preparation method of shape memory Micron-nano composites according to claim 1, it is characterised in that：Step
Feature micro-and nano-particles described in two are micro-nano ferroso-ferric oxide.
8. the shape memory Micron-nano composites as prepared by claim 1 are used for 4D printing techniques, it is characterised in that：Specifically
Realize according to the following steps：
First, shape memory Micron-nano composites solution is loaded in the high pressure spot plastic pin cylinder equipped with micro needle head, and passes through gas
Pump applies pressure to high pressure spot plastic pin cylinder；Three-dimensional mobile platform is controlled in x by software, y, the direction of motion and motion in z-axis
Speed 0.1mm/s-10mm/s, described is 50MPa-500MPa to high pressure spot plastic pin cylinder application pressure by air pump；In whole mistake
Cheng Zhong, UV LED point light source irradiate the solution of extrusion always, to trigger the cross-linking reaction of molecule segment, obtain with shape memory
The three-dimensional structure of effect；The internal diameter of the syringe needle is 30um-250um；
2nd, the prepared three-dimensional structure with SME is heated to more than its glass transition temperature, changes shape
Shape is fixed as required temporary structure；Keeping external force to be cooled to below glass transition temperature fixes temporary structure；Outside
Under field is stimulated, corresponding temporary structure can return to initial three-dimensional structure, and the three-dimensional structure with SME is made
Remain able to change form after making, show characteristic of the three-dimensional article with time dynamic, so far complete 4D printings.
9. shape memory Micron-nano composites according to claim 8 are used for 4D printing techniques, it is characterised in that：It is described
Outfield stimulate for alternating magnetic field excitation, electric excitation, uv light induction, water excitation, solution encourage in one or more.
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