CN101003652A - Fiber enhanced composite material of shape memory, and application - Google Patents
Fiber enhanced composite material of shape memory, and application Download PDFInfo
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- CN101003652A CN101003652A CN 200710071621 CN200710071621A CN101003652A CN 101003652 A CN101003652 A CN 101003652A CN 200710071621 CN200710071621 CN 200710071621 CN 200710071621 A CN200710071621 A CN 200710071621A CN 101003652 A CN101003652 A CN 101003652A
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- shape memory
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Abstract
This invention relates to fiber-reinforced shape memory composite and its application. This invention solves the problems of low hardness and strength, poor reconversion performance, and poor motion stability band reliability faced by present shape memory polymer materials. The fiber-reinforced shape memory composite is composed of: shape memory polymer material 20-95 vol. %, and reinforcing fiber material 5-80 vol. %. The fiber-reinforced shape memory composite has such advantages as high reconversion strain, strong force output during reconversion, high motion stability and reliability, low density, high hardness, and high strength. The method has such advantages as simple process and easy operation. The fiber-reinforced shape memory composite can be used in such industries as toys, medicine, architecture, traffic, aviation, aerospace, etc.
Description
Technical field
The present invention relates to a kind of composite material of shape memory and application thereof.
Background technology
Smart material and structure is the interdisciplinary science of an emerging multidisciplinary intersection, has contained multiple subjects such as material, mechanics, machinery, electronics, control, electromagnetism, is the forward position of current engineering discipline development.In the past few decades, intelligent material finds broad application in military and civilian fields such as Aeronautics and Astronautics, naval vessel, building.Just with unprecedented speed fast development, shape-memory polymer wherein obtains more and more widely application with its excellent comprehensive performance to intelligent material especially at aspects such as bionical, transmitter, actuator.
Shape memory polymer material generally has two phase structure: one is the stationary phase of shape-memory material shape mutually, but another is anti-phase mutually.Stationary phase has physical crosslinking or chemically crosslinked structure: stationary phase be the physical crosslinking structure be called the thermoplasticity shape-memory polymer; What stationary phase had a chemically crosslinked structure is called the thermoset shape memory polymkeric substance.Reversible varying with temperature mutually can be solidified and soften by reversible, has the physical crosslinking structure.
In the smart material and structure field, the research of shape-memory polymer is ripe relatively, thermoset and thermoplasticity shape memory polymer materials such as shape memory polyurethane, shape memory polyester, shape memory epoxy resin, shape memory cyanate, shape memory vinylbenzene, shape memory styrene-butadiene copolymer, shape memory using trans-polyisoprene, shape memory polynorbornene have occurred.
The elementary heat of shape-memory polymer-mechanical deformation process is: at second-order transition temperature (T
g) more than, can apply external force and make its distortion; Keeping making it be cooled to T under the constant prerequisite of external constraint
gFollowing certain temperature removes external constraint, the energy of deformation of composing by being kept for a long time; When being heated to second-order transition temperature once more when above, shape-memory polymer can automatically revert to primary shape.
It is bigger that but the principal feature of shape-memory polymer is a recovery strain, generally can reach 200%.But main drawback is that mechanical properties such as the rigidity, intensity of material are relatively poor, the external force of exporting during deformation-recovery is less, stability of motion and reliability are relatively poor, shape hold facility relatively poor (having more serious creep and stress relaxation phenomenon), these shortcomings have had a strong impact on the application of shape-memory polymer, particularly in the spaceborne application that need work under exceedingly odious condition.
Existing conventional polymer matrix composites have excellent mechanical property such as high specific tenacity, specific rigidity, magnitude such as its intensity, rigidity and metal and density has only the part of steel.Conventional polymer matrix composites are mainly considered static or quasi-static mechanics load-carrying properties such as the intensity, rigidity of material, do not consider the drive characteristic of material, and its recoverable strain amount generally has only 1%～2%.Therefore, conventional polymer matrix composites are mainly used in the structural bearing material, and can not be used to be similar to this class of artificial-muscle drives distortion by material itself active gross distortion material.
Summary of the invention
The external force of exporting when the objective of the invention is, deformation-recovery relatively poor for mechanical properties such as the rigidity that solves present shape memory polymer material and intensity is less, stability of motion and reliability is relatively poor, the shape hold facility is relatively poor problem, and a kind of fiber enhanced composite material of shape memory and application thereof are provided.The invention provides the fiber-reinforced shape memory polymer composite material that a kind of thermal excitation initiatively is out of shape, this material has shape memory function, and it is repeatable that its memory effect has repeatedly circulation.The present invention mainly is the active controllable system gross distortion that realizes material.Fiber enhanced composite material of shape memory of the present invention is made up of shape memory polymer material and fiber reinforcement phase material; The volume percent content of each constituent materials of fiber enhanced composite material of shape memory is: shape memory polymer material 20～95%, fiber reinforcement phase material 5～80%; More suitably content is shape memory polymer material 40～90%, fiber reinforcement phase material 10～60%; Optimal content is shape memory polymer material 50～80%, fiber reinforcement phase material 20～50%.
Shape memory polymer material of the present invention is shape memory vinylbenzene, shape memory epoxy resin, shape memory styrene-butadiene copolymer, shape memory using trans-polyisoprene, shape memory polynorbornene or shape memory cyanate.
Fiber reinforcement phase material of the present invention is one or more the mixture in the chopped strand of carbon fiber, glass fibre, Kevlar fiber, boron fibre, silicon carbide fiber, the fabric of above fiber, above fiber.
Fiber enhanced composite material of shape memory of the present invention (is lower than the second-order transition temperature of shape-memory polymer, T when room temperature
g) Young's modulus is bigger, when the second-order transition temperature that is heated to shape-memory polymer was above, the shape-memory material Young's modulus reduced, and plasticity-strengthens, and under extraneous stress, composite material of shape memory can the passive ideal form that is deformed into; (＜T when under the situation that keeps external force constraint, cooling the temperature to room temperature
g), the composite material of shape memory Young's modulus raises, and after the external force unloading, composite material of shape memory can keep the shape after the distortion, and the energy standing storage; When being heated to shape-memory polymer T once more
gWhen above, fiber enhanced composite material of shape memory can initiatively return back to the shape of the most original (after the demoulding).Fiber enhanced composite material of shape memory can show hot mechanical cycles performances such as the elongation-retraction, bending-stretching, extension, compression-elongation of not damaged or less damage.
Preparation methods of the present invention is the conventional preparation method of polymer matrix composites, comprising: method moulding, lamination and pipe crimping moulding, pultrusion, continuous pipe twining, continuous plate are moulded in hand pasting forming, compression molding, Wrapping formed, spray up n., resin transfer molding, pressure bag method moulding, vacuum bag-hot pressing pot process moulding, the moulding of hot pressing pot process, the moulding of hydroclave method, thermal expansion.Because polymer matrix composites preparation method's the diversity and the lack of standard of technology, three kinds of manufacture method that this patent described in detail are concrete example among the numerous preparation methods of polymer matrix composites, are not the restriction to its preparation method.
Method one:
The preparation process of present method is as follows: a, preparation shape-memory polymer, post reaction mixture is preserved under cold condition; B, fiber reinforced material clean with organic solution, and 150～200 ℃ of following drying treatment 40～60min volatilize fully until organic solution in baking oven; C, releasing agent is placed on the mould; D, will through a certain amount of fiber reinforced material after step b handles pack into mould, inject shape-memory polymer, mold closing after a handles, make each component volume percent be: shape memory polymer material 20～95%, fiber reinforcement phase material 5～80%; E, with mould in thermocompressor, the solidification value and the time of pressing shape-memory polymer regulation solidify; F, take out mould, the demoulding when treating that die temperature is reduced to room temperature from thermocompressor; Fiber enhanced composite material of shape memory product after obtaining solidifying.
Method two:
The preparation process of present method is as follows: a, preparation shape-memory polymer, post reaction mixture is preserved under cold condition; B, the core that will scribble releasing agent are installed on the mandrel of matrix material wrapping machine; Temperature to the certain temperature of c, adjusting mandrel makes it close with the temperature of shape-memory polymer resin; D, step a bonded shape-memory polymer resin is injected the glue groove; E, draw fibrous termination, and make it, be fixed on the core at last successively by roller, tenslator, the silk mouth of glue groove from creel; F, adjustment of tonicity control device make fiber tension satisfy the requirement of winding process; G, be wound to the required number of plies, make each component final volume per-cent of composite panel be: shape memory polymer material 20～95%, fiber reinforcement phase material 5～80%, and under rotation dress attitude, toast, make the shape-memory polymer resin evenly soak into fiber; H, the flat board that twines is placed between two increased pressure boards together with core, places certain thickness cushion block in position, four angles; I, it is directly put into press, pressurization makes the upper and lower increased pressure board of mould contact with cushion block, uses sharp cutter at core two ends staple fiber then; I, with mould in thermocompressor, the solidification value of regulation and the time of pressing shape-memory polymer solidify; J, naturally cool to room temperature, take mould apart, get one and go out flat board; K, the flat board that takes out is repaired, cut a section of certain-length on perpendicular to fiber edge, obtain fiber enhanced composite material of shape memory through the preparation of winding method.
Method three:
The preparation process of present method is as follows: a, preparation shape-memory polymer, post reaction mixture is preserved under cold condition; B, from cryostat, take out the prepreg sealing bag made from shape-memory polymer and fiber, place under the certain temperature environment, storage period 1～72h, direction is broken seal; C, cut the prepreg of certain number of plies of certain length and width, make each component final volume per-cent of composite panel be: shape memory polymer material 20～95%, fiber reinforcement phase material 5～80% by cutting template; D, be laid in together the prepreg that cuts is successively unidirectional, after completing, take by weighing prepreg blank weight; E, metal bottom template and top board are coated with releasing agent; F, cut out the suction glue material of desired number and size by the requirement of each component final volume per-cent of composite panel; G, prepreg blank and relevant subsidiary material are made up in the following order: 1). on the metal bed die, put isolated film; 2). the porose release cloth of one deck is respectively spread on the upper and lower surface of prepreg blank; 3). place on the end template isolated film and inhale glue material, quantity is half of its total number of plies.To be placed on the suction glue material with the material that soaks of porose release cloth again, and then place the suction glue material of second half number of plies; Simultaneously, lay periphery shelves bar at the laminated periphery of prepreg; 4). place porose sealing coat successively and the mesoporous metal top board is arranged; 5). between top board periphery and end template, paste peripheral seal strip; H, the aforesaid combination part is put on the metal substrate of autoclave, lay gas permeable material, vacuum bag material and joint strip constitute the vacuum bag system; I, with mould in autoclave, the solidification value and the time of pressing shape-memory polymer regulation solidify; J, solidify after, under pressure with the jar cool to room temperature.Subassembly is shifted out autoclave, take out the fibre reinforced plastics flat board.Every limit cuts a section of certain-length; Obtain fiber enhanced composite material of shape memory through vacuum bag-autoclave method preparation.
Mechanical properties such as the rigidity of simple shape polymer materials, intensity are relatively poor, and rigidity is lower in the shape memory Recovery Process, deformation-recovery power is less, stability of motion and reliability is relatively poor, have the lax and creep than serious stress.And composite material of shape memory can overcome above-mentioned defective preferably, and its rigidity, intensity in the shape memory Recovery Process are higher, and deformation-recovery power is bigger, and stability of motion and reliability are higher, and the shape hold facility is better.
Conventional polymer matrix composites are mainly considered static or quasi-static mechanics load-carrying properties such as the intensity, rigidity of material, are mainly used in structured material.And fiber enhanced composite material of shape memory is mainly considered driving, the gross distortion dynamic mechanics driveabilities such as (finite deformations) of material, but has the recovery strain more much higher than conventional polymer matrix composites.With respect to the polymer matrix composites of routine, fiber enhanced composite material of shape memory is revolutionary innovation.
Chopped strand with carbon fiber or carbon fiber of the present invention is made the composite material of shape memory of wild phase, and through suitably regulating the wild phase mass percent, it has good electrical conductivity, but promptly has the electricity heating property and need not extraneous thermal source heating.Need the particularly occasion of little distortion of accurate control material distortion at some, it is more convenient that electric control adds thermal control than the external world, so the conductive shapes memory composite material has wide application space.
Fiber enhanced composite material of shape memory is applied in bending-the stretch deployable hinge driving mechanism of formula, the deployable girder construction of formula curls-extends, by crooked-stretch the extending girder construction that the deployable driving mechanism of formula constitutes, rely on material self unfolded expandable truss structure, the eyeglasses frame of energy arbitrary deformation, the wing of the aircraft of energy arbitrary deformation, the antenna that can curl-stretch, the artificial-muscle of energy contraction-stretching, extension, the artificial blood vessel spreader, can change the artificial facial skin of expression, the artificial spine support, the driving mechanism of robot, the collision bumper of automobile, the directional drive of automobile rearview mirror, the hotness triggering device of automatic fire fighting unit, energy is the wheel of sex change arbitrarily, the toy of energy arbitrary deformation, the hair of the rag baby of energy arbitrary deformation, plastic flower that can arbitrary deformation or can roll automatically-the unfolded curtain, tail and the fin of the bionical fish of energy arbitrary deformation, on the wing of the bionical bird of energy arbitrary deformation.
Advantages such as the external force that material of the present invention has, and but recovery strain is big, export during deformation-recovery is big, stability of motion is good, the high and low density of reliability, high rigidity, high strength and low cost.Preparation method of the present invention has simple, the easy to operate advantage of technology.Material of the present invention is widely used in numerous areas such as toy, medical science, building, traffic, aerospace.
Description of drawings
Recovery of shape rate under Fig. 1 condition of different temperatures-flexural deformation cycle index figure, Fig. 2 recovery of shape rate-flexural deformation number of times figure, the recovery of shape residual set angle-distortion cycle index figure of Fig. 3 under different initial bending corner conditions.Among Fig. 1-▲-95 ℃ of conditions of expression under the recovery of shape rate-flexural deformation frequency curve of test sample, among Fig. 1-■-85 ℃ of conditions of expression under the recovery of shape rate-flexural deformation frequency curve of test sample, among Fig. 1-+-75 ℃ of conditions of expression under the recovery of shape rate-flexural deformation frequency curve of test sample, among Fig. 1-● the recovery of shape rate-flexural deformation frequency curve of test sample under 65 ℃ of conditions of-expression, among Fig. 1-*-55 ℃ of conditions of expression under the recovery of shape rate-flexural deformation frequency curve of test sample; Among Fig. 3-■-expression angle of bend is recovery of shape residual set angle-flexural deformation cycle index curve of 180 °, among Fig. 3-▲-the expression angle of bend is recovery of shape residual set angle-flexural deformation cycle index curve of 135 °, among Fig. 3-●-expression angle of bend is recovery of shape residual set angle-flexural deformation cycle index curve of 90 °, among Fig. 3-and *-expression angle of bend is recovery of shape residual set angle-flexural deformation cycle index curve of 45 °.
Embodiment
Embodiment one: the fiber enhanced composite material of shape memory of present embodiment is made up of shape memory polymer material and fiber reinforcement phase material; The volume percent content of each constituent materials of fiber enhanced composite material of shape memory is: shape memory polymer material 20～95%, fiber reinforcement phase material 5～80%.
Embodiment two: the volume percent content of each constituent materials of fiber enhanced composite material of shape memory of present embodiment is: shape memory polymer material 40～90%, fiber reinforcement phase material 10～60%.
Embodiment three: the volume percent content of each constituent materials of fiber enhanced composite material of shape memory of present embodiment is: shape memory polymer material 50～80%, fiber reinforcement phase material 20～50%.
Embodiment four: the shape memory polymer material of present embodiment is shape memory vinylbenzene, shape memory epoxy resin, shape memory styrene-butadiene copolymer, shape memory using trans-polyisoprene, shape memory polynorbornene or shape memory cyanate.Other is identical with embodiment one.
Embodiment five: the shape memory vinylbenzene of present embodiment is formed by styrene monomer, vinyl mixture, linking agent, initiator and/or the polymer-modified chemical combination of viscosity modifier.Other is identical with embodiment four.
Embodiment six: the vinyl mixture of present embodiment is vinyl neodecanoic acid, vinyl M-nitro benzoic acid, vinylacrylic acid, vinyl stearate and vinyl toluene, vinyl pyrimidine.Other is identical with embodiment five.
Embodiment seven: the linking agent of present embodiment is fumaric acid diallyl, allyl methacrylate(AMA), diallyl phthalate, suberic acid diallyl, divinyl ethyl glycol, divinyl base benzene, two-[4-(vinyl oxygen) butyl] terephthalate, two-[4-(vinyl oxygen) methylcyclohexane] methyltetraphthalic acid ester.Other is identical with embodiment five.
Embodiment eight: the initiator of present embodiment is radical initiator or cationic initiator.Other is identical with embodiment five.
Embodiment nine: the radical initiator of present embodiment is an organo-peroxide.
Any business-like organo-peroxide all can utilize in the present embodiment, and t-butyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, dodecyl hydrogen peroxide are first-selected.Other is identical with embodiment eight.
Embodiment ten: the cationic initiator of present embodiment is boron trifluoride, aluminum chloride and tin tetrachloride.Other is identical with embodiment eight.
Embodiment 11: the viscosity modifier of present embodiment is multipolymer, polyethylene or the polypropylene of polystyrene, styrene butadiene.Other is identical with embodiment five.
Embodiment 12: present embodiment shape memory vinylbenzene is made by weight percentage by following ingredients: styrene monomer: vinyl mixture 35%～95%: linking agent 5%～60%: initiator 0.5%～5%: 0.1%～0.5%.Other is identical with embodiment five.
Embodiment 13: present embodiment shape memory vinylbenzene is made by weight percentage by following ingredients: styrene monomer 40%～85%, vinyl monomer 5%～20%, linking agent is 0.6%～3%, and initiator is 0.5%～3%, and is polymer-modified 5%～50%.Other is identical with embodiment five.
Embodiment 14: styrene monomer 50%～80%, vinyl monomer 5%～14%, initiator are 1%～2.5%, and be polymer-modified 10%～40%.Other is identical with embodiment five.
Embodiment 15: shape memory epoxy resin is the diglycidyl ether of hydrogenation phthalic acid in the present embodiment, derive from the block oligomers of aliphatic epoxy resin and sour monoether, Resins, epoxy (molecular weight: 390-430), different-the methyltetrahydro Tetra hydro Phthalic anhydride, three-(dimethylaminomethyl) phenol, mass ratio: 77,5: 20: 2,7 or 77,5: 68: 0,7.Other is identical with embodiment four.
Embodiment 16: the common prescription of present embodiment shape memory using trans-polyisoprene has: using trans-polyisoprene, light calcium carbonate, zinc white, stearic acid, sulphur, dicumyl peroxide, and each composition quality ratio of filling a prescription is 100: 30: 5: 1: 0.5: 3; Preparation process is: batching, mixing, sulfidization molding.Using trans-polyisoprene after cooperation and sulfuration has shape memory effect.Other is identical with embodiment four.
Embodiment 17: present embodiment shape memory styrene-butadiene block copolymer is prepared from anionoid polymerization, method is as follows: vinylbenzene, divinyl and isoprene monomer react in hydrocarbon solution hexane or toluene, and through deoxygenation, dewater and the removal of impurity.Wherein the used initiator of anionoid polymerization is an organolithium compound.Other is identical with embodiment four.
Organolithium compound is a butyllithium in the present embodiment.
Embodiment 18: the shape memory polynorbornene is synthetic through the Diels-Alder reaction by cyclopentadiene and ethene.Other is identical with embodiment four.
Embodiment 19: the fiber reinforcement phase material of present embodiment is one or more mixing of the chopped strand of carbon fiber, glass fibre, Kevlar fiber, boron fibre, silicon carbide fiber, the fabric of above fiber, above fiber.Other is identical with embodiment one.
Embodiment 20: fiber enhanced composite material of shape memory preparation method's step is as follows in the present embodiment: a, preparation shape-memory polymer, post reaction mixture is preserved under cold condition; B, fiber reinforced material clean with organic solution, and 150～200 ℃ of following drying treatment 40～60min volatilize fully until organic solution in baking oven; C, releasing agent is placed on the mould; D, will through a certain amount of fiber reinforced material after step b handles pack into mould, inject shape-memory polymer, mold closing after a handles, make each component volume percent be: shape memory polymer material 20～95%, fiber reinforcement phase material 5～80%; E, with mould in thermocompressor, under 40～200 ℃, 0.1～20MPa condition, heated 2～72 hours; F, take out mould, the demoulding when treating that die temperature is reduced to room temperature, the fiber enhanced composite material of shape memory product after obtaining solidifying from thermocompressor.
Embodiment 21: the organic solvent of present embodiment is an acetone or alcohol.Other is identical with embodiment 21.
Embodiment 22: the releasing agent of present embodiment is polyvinyl alcohol solution, polyacrylamide, silicone oil, polyester film or glassine paper.Other is identical with embodiment 21.
Embodiment 23: the fiber enhanced composite material of shape memory of present embodiment is applied in bending-the stretch deployable hinge driving mechanism of formula, the deployable girder construction of formula curls-extends, by crooked-stretch the extending girder construction that the deployable driving mechanism of formula constitutes, rely on material self unfolded expandable truss structure, the eyeglasses frame of energy arbitrary deformation, the wing of the aircraft of energy arbitrary deformation, the antenna that can curl-stretch, the artificial-muscle of energy contraction-stretching, extension, the artificial blood vessel spreader, can change the artificial facial skin of expression, the artificial spine support, the driving mechanism of robot, the collision bumper of automobile, the directional drive of automobile rearview mirror, the hotness triggering device of automatic fire fighting unit, energy is the wheel of sex change arbitrarily, the toy of energy arbitrary deformation, the hair of the rag baby of energy arbitrary deformation, plastic flower that can arbitrary deformation or can roll automatically-the unfolded curtain, tail and the fin of the bionical fish of energy arbitrary deformation, on the wing of the bionical bird of energy arbitrary deformation.
Embodiment 24: fiber enhanced composite material of shape memory preparation method's step is as follows in this implementation method: a, shape memory vinylbenzene by following ingredients by weight percentage chemical combination form: vinyl neodecanoic acid: divinyl base benzene 7%: vinylbenzene 1%: benzoyl peroxide 90%: 2%, with the post reaction mixture cooling preservation in refrigerator; B, carbon cloth alcohol wash, 180 ℃ of following drying treatment 30min in baking oven; C, silicone oil is placed on the mould; D, the continuous fibre after b handles is cut into the long chopped strand of 3mm and makes it loose; E, will be through resin that a handles and the chopped strand thorough mixing after d handles, each component volume percent is: shape-memory polymer 80%, carbon fiber 20%; F, will inject rectangular parallelepiped die cavity, the mold closing of 40 * 20 * 0.4cm through the Preblend that the chopped strand after step e handles strengthens composite material of shape memory; G, with mould in thermocompressor, heating is 24 hours under 75 ℃, 2MPa condition; H, take out the mould and the demoulding when treating die temperature＜60 ℃, the chopped strand after promptly obtaining solidifying strengthens composite material of shape memory sample, T
g=62 ℃.
Embodiment 25: fiber enhanced composite material of shape memory preparation method's step is as follows in this implementation method: a, shape memory vinylbenzene by following ingredients by weight percentage chemical combination form: vinyl neodecanoic acid: divinyl base benzene 7%: vinylbenzene 1%: benzoyl peroxide 90%: 2%, with the post reaction mixture cooling preservation in refrigerator; B, with plain weave carbon-fiber cloth alcohol wash, 180 ℃ of following drying treatment 30min in baking oven; C, silicone oil is placed on the mould; D, carbon-fiber cloth is cut into the sheet material of 40 * 20cm, it is packed in the rectangular parallelepiped die cavity of 40 * 20 * 0.4cm by [0/90] direction; E, will inject mould, mold closing, make each component volume percent be: shape-memory polymer 95%, carbon fiber 5% through the shape-memory polymer after step a handles; F, with mould in thermocompressor, heating is 24 hours under 75 ℃, 2MPa condition; G, take out the mould and the demoulding when treating die temperature＜60 ℃, the cloth after promptly obtaining solidifying strengthens composite material of shape memory sample, T
g=62 ℃.
Embodiment 26: fiber enhanced composite material of shape memory preparation method's step is as follows in this implementation method: a, shape memory vinylbenzene by following ingredients by weight percentage chemical combination form: vinyl neodecanoic acid: divinyl base benzene 7%: vinylbenzene 1%: benzoyl peroxide 90%: 2%, with the post reaction mixture cooling preservation in refrigerator; B, the core that will scribble silicone oil are installed on the mandrel of matrix material wrapping machine; C, the temperature to 25 of regulating mandrel ℃ make it close with the temperature of shape memory styrene resin; D, step a bonded shape memory styrene resin is injected the glue groove; E, draw fibrous termination from creel, and make its successively roller, tenslator, the silk mouth by the glue groove, be fixed on the core at last; F, adjustment of tonicity control device make fiber tension satisfy the requirement of winding process; G, be wound to the required number of plies, make each component final volume per-cent of composite panel be: shape-memory polymer 40%, carbon fiber 60%, and under rotation dress attitude in 55 ℃ of bakings, make the shape memory styrene resin evenly soak into carbon fiber; H, (20 * 20cm) are placed between two increased pressure boards together with core, and placing thickness in position, four angles is the cushion block of 4mm the flat board that twines; I, it is directly put into press, be forced into 2MPa, the upper and lower increased pressure board of mould is contacted with cushion block, cut off carbon fiber at the core two ends with sharp cutter then; I, with mould in thermocompressor, under 75 ℃, 2MPa condition, solidified 24 hours; J, naturally cool to room temperature, take mould apart, take out dull and stereotyped; K, the flat board that takes out is repaired, on perpendicular to fiber edge, cut 15mm, obtain strengthening composite material of shape memory, T through the carbon fiber of winding method preparation
g=62 ℃.
Embodiment 27: fiber enhanced composite material of shape memory preparation method's step is as follows in this implementation method: a, shape memory vinylbenzene by following ingredients by weight percentage chemical combination form: vinyl neodecanoic acid: divinyl base benzene 7%: vinylbenzene 1%: benzoyl peroxide 90%: 2%, with the post reaction mixture cooling preservation in cryostat; B, the prepreg sealing bag that taking-up is made with shape memory vinylbenzene and carbon fiber from cryostat place 23 ± 2 ℃ of temperature, and under the environment of temperature 55 ± 5%, storage period, direction was broken seal greater than 2h; C, cut the prepreg of certain number of plies of 20 * 20cm, make each component final volume per-cent of composite panel be: shape-memory polymer 60%, carbon fiber 40% by cutting template; D, be laid in together the prepreg that cuts is successively unidirectional, after completing, take by weighing prepreg blank weight; E, metal bottom template and top board are coated with silicone oil; F, be that the suction glue material of desired number is cut out in the requirement of shape-memory polymer 60%, carbon fiber 40% by each component final volume per-cent of composite panel.Inhale glue material and be of a size of 20 * 20cm; G, prepreg blank and relevant subsidiary material are made up in the following order: 1). on the metal bed die, put isolated film (the not polytetrafluoroethylglass glass cloth of seep through); 2). the porose release cloth of one deck (polytetrafluoroethylglass glass cloth) is respectively spread on the upper and lower surface of prepreg blank; 3). place on the end template isolated film and inhale glue material (0.1mm woven fiber glass), quantity is half of its total number of plies.To be placed on the suction glue material with the material that soaks of porose release cloth again, and then place the suction glue material of second half number of plies; Simultaneously, lay periphery shelves bar (vulcanized India-rubber strip) at the laminated periphery of prepreg; 4). place porose sealing coat successively and the mesoporous metal top board is arranged; 5). between top board periphery and end template, paste peripheral seal strip; H, the aforesaid combination part is put on the metal substrate of autoclave, lay gas permeable material, vacuum bag material and joint strip constitute the vacuum bag system; I, with mould in autoclave, in solidifying 36 hours under 75 ℃, 0.5MPa condition: j, solidify after, under pressure with the jar cool to room temperature.Subassembly is shifted out autoclave, take out the fibre reinforced plastics flat board.Every limit cuts 15mm; Obtain strengthening composite material of shape memory through the carbon fiber of vacuum bag-autoclave method preparation.
The present invention verifies that with following test carbon fiber strengthens the expansion recoverability of composite material of shape memory.The content and the result of test are as follows:
The carbon fiber that embodiment 25 is obtained strengthens some of the strip test samples that the composite material of shape memory plate is made 85mm * 15mm * 4mm, to be used for following test.
One end of straight plate strip test sample is fixed in the trier jig, the other end freedom, and interlude can be the cylindrical rod bending of 2mm along a diameter that is fixed on the trier panel.Testing sequence: 1) the strip test sample was left standstill 3 minutes in 85 ℃ of water-baths, 2) under external force the remollescent test sample is folded into certain angle (α) around cylindrical rod, test sample after the bending distortion is placed cold water (external constraint is constant) frozen strss and bending shape, 3) water-bath that again bending shape fixed test sample is placed a certain temperature, 4) the recovery of shape performance of experiment with measuring sample: mark with the residual set angle (β) after measuring deformation-recovery as measurement point at strip test sample free end.Recovery of shape rate=[(alpha-beta)/α] * 100%.
Recovery of shape rate under 1 condition of different temperatures-flexural deformation cycle index test
The strip test sample is around 180 ° of thin cylindrical rod bendings, and to measure the recovery of shape rate of 5 test samples under condition of different temperatures, each temperature spot is surveyed 5 times.By figure one at the rate of the recovery of shape under the condition of different temperatures-flexural deformation cycle index curve as can be known: when temperature when 55 ℃ rise to 95 ℃, the recovery of shape rate of test sample is between 89%～96%, and along with the rising of temperature, the recovery of shape rate of test sample presents faint ascendant trend.This tests explanation, and carbon fiber strengthens composite material of shape memory at T
gNear or be higher than T
gTemperature, its curved shape response rate is higher, and along with the rising of temperature, the recovery of shape rate that carbon fiber strengthens composite material of shape memory presents faint ascendant trend.
2 recoveries of shape rate-flexural deformation cycle index test
The strip test sample is around 180 ° of thin cylindrical rod bendings, and to record the trial curve of test sample recovery of shape rate-flexural deformation number of times under 85 ℃ of conditions, the flexural deformation cycle index is 50 times.Known by Fig. 2: the recovery of shape rate of test sample is between 91%～96%, and along with the rising of being out of shape cycle index, the recovery of shape rate of test sample is on a declining curve.This tests explanation, and carbon fiber strengthens composite material of shape memory and is being higher than T
gTemperature condition under the curved shape response rate higher, and along with the rising of distortion cycle index, it is on a declining curve that carbon fiber strengthens the recovery of shape rate of composite material of shape memory.
3 recovery of shape residual set angle-flexural deformation cycle index tests under different initial bending corner conditions
Under 85 ℃ of conditions, to record the residual set angle of strip test sample under the initial bending angle of difference, the initial bending angle is respectively: 45 °, 90 °, 135 °, 180 °, 5 distortion round-robin tests are done at each initial bending angle.By shown in Figure 3, the residual set angle is between 4 °～14 °, and along with the increase at test sample initial bending angle, the residual set angle after its deformation-recovery also increases thereupon.This tests explanation, and carbon fiber strengthens composite material of shape memory and is being higher than T
gTemperature condition under, the bending angle that strengthens composite material of shape memory along with carbon fiber increases, the residual set angle after its deformation-recovery also increases thereupon.
Claims (6)
1, a kind of fiber enhanced composite material of shape memory is characterized in that it is made up of shape memory polymer material and fiber reinforcement phase material; The volume percent content of each constituent materials of fiber enhanced composite material of shape memory is: shape memory polymer material 20～95%, fiber reinforcement phase material 5～80%.
2, a kind of fiber enhanced composite material of shape memory according to claim 1 is characterized in that its each constituent materials volume percent content is: shape memory polymer material 40～90%, fiber reinforcement phase material 10～60%.
3, a kind of fiber enhanced composite material of shape memory according to claim 1 is characterized in that its each constituent materials volume percent content is: shape memory polymer material 50～80%, fiber reinforcement phase material 20～50%.
4,, it is characterized in that shape memory polymer material is shape memory vinylbenzene, shape memory epoxy resin, shape memory styrene-butadiene copolymer, shape memory using trans-polyisoprene, shape memory polynorbornene or shape memory cyanate according to claim 1,2 or 3 described a kind of fiber enhanced composite material of shape memory.
5,, it is characterized in that the fiber reinforcement phase material is one or more the mixing in the chopped strand of carbon fiber, glass fibre, Kevlar fiber, boron fibre, silicon carbide fiber, the fabric of above fiber, above fiber according to claim 1,2 or 3 described a kind of fiber enhanced composite material of shape memory.
6, according to claim 1, the application of 2 or 3 described a kind of fiber enhanced composite material of shape memory is characterized in that fiber enhanced composite material of shape memory is applied in bending-the stretch deployable hinge driving mechanism of formula, the deployable girder construction of formula curls-extends, by crooked-stretch the extending girder construction that the deployable driving mechanism of formula constitutes, rely on material self unfolded expandable truss structure, the eyeglasses frame of energy arbitrary deformation, the wing of the aircraft of energy arbitrary deformation, the antenna that can curl-stretch, the artificial-muscle of energy contraction-stretching, extension, the artificial blood vessel spreader, can change the artificial facial skin of expression, the artificial spine support, the driving mechanism of robot, the collision bumper of automobile, the directional drive of automobile rearview mirror, the hotness triggering device of automatic fire fighting unit, energy is the wheel of sex change arbitrarily, the toy of energy arbitrary deformation, the hair of the rag baby of energy arbitrary deformation, plastic flower that can arbitrary deformation or can roll automatically-the unfolded curtain, tail and the fin of the bionical fish of energy arbitrary deformation, on the wing of the bionical bird of energy arbitrary deformation.
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