Summary of the invention
Problems solved by the invention is that composite material shape tube complex forming technology, demoulds inconvenience in the prior art
Problem.
To solve the above problems, the present invention provides a kind of core model, it is used for forming composite shape tube, the core model to be shape
Shape memory material is made, and the cross section of the core model is circular ring shape, and the core model includes straight sections and bent portion, the straight sections
Axis be linear type, the axis of the bent portion is " L " type, " C " type or " S " type structure.
Core model of the invention is suitable for possessing the composite material shape tube product molding method of labyrinth, and shape memory
Material transitory state possesses some strength, can restore shape by thermostimulation;Shape memory core model restores in deformation process, core
Mode diameter becomes smaller, and core model and composite material abnormal shape pipe internal surface are removed, and core model journey high resiliency is, it can be achieved that smoothly demoulding.
Optionally, the middle part of the straight sections is gradually reduced to the diameter at both ends.
Another object of the present invention is to provide a kind of core model preparation methods, are used to prepare any of the above-described core model,
Include the following steps:
S1, shape memory polymer material pre-treatment: the ratio of each component in adjustable shape memory polymer stoste is stirred
It mixes, obtains shape-memory polymer modulating liquid A;
S2, the modulating liquid A curing molding: the modulating liquid A is solidified using casting craft, obtains tubulose solidification core model
B solidifies the original state that core model B is shape-memory polymer;
S3, solidification core model B are changed into deformed state by original state: the solidification core model B being heated, temperature is more than shape
The glass transition point of memory polymer, shape-memory material are changed into rubbery state, and it is rigid that the core model of rubbery state is placed in auxiliary
Property mold in, inflating pressure, and cooling down in the state of keeping pressure, temperature removes pressure after dropping to room temperature, and shape memory is poly-
It closes object core model and is changed into deformed state, obtain final core model product.
Preparation method is simple, can obtain tubular core mold, using shape-memory material due to possessing certain ductility, heats
Afterwards, the working condition for the shape that can be thickened by reset condition in the case where bearing external force, and original shape can be replied after certain excitation
Shape can be used as one kind of complicated shape composite material shape tube core model.
Optionally, in the step S1, in adjustable shape memory polymer stoste when the ratio of each component, it is added one
Quantitative reinforcing material, the reinforcing material include carbon nano-particle, carbon nanotube, carbon black, staple fiber, polyurethanes fiber,
One or more combinations of highly elastic fiber or fabric.
Optionally, in the step S3, the core model of rubbery state is placed in supplemental rigid mold, inflating pressure after molding,
The blowing pressure is within the scope of 0.2~0.5MPa.
Another object of the present invention is to provide a kind of composite material shape tube forming methods, which is characterized in that in use
It states any core model to be formed, include the following steps:
M1, composite molding: polymer matrix composites prepreg is pasted on the core model, is made composite material presoaked
Expect lamination, place into supplemental rigid mold, pressurize, be heating and curing, obtains cured article C after cooling;
M2, core mould removal: it is corresponding greater than the glass transition point of the core model that the cured article C is warming up to temperature
Temperature, the core model is changed into rubbery state, and removes with solid union material, extracts the core model out, obtains composite material abnormal shape
Pipe prefabrication;
M3, micro-shaping: carrying out polishing and polishing treatment to the surface of the composite material shape tube prefabrication of step M2 preparation,
Obtain composite material shape tube.
The technique is formed relative to common metal mold for composite product, and demoulding is simple, and product surface precision is high,
The polymorphic structure demoulded is difficult to suitable for metal core die, and shape memory core model can be used for multiple times, production cost is low, is applicable in
In all kinds of complicated shape composite products.
And the technique is pasted using material prepreg, is molded with rigid die.The technique relative to
Carbon fiber winding technique has the advantage that not needing machine is wound, manual operations, low in cost;It saves and twines
Impregnation steps are carried out after fiber filament, are directly solidified, and process pollution is few;It is used just after having pasted material prepreg
Property mold is molded, and surface smoothness is higher.
Optionally, which is characterized in that in the step M1, the polymer matrix composites prepreg is immersed in by fiber filament
Impregnating resin is formed, and the fiber filament includes one or more combinations of carbon fiber, glass fibre or aramid fiber;The dipping
Resin includes one or more combinations that epoxy resin, unsaturated polyester resin, novolac epoxy resin or span carry out amide resin.
Optionally, in the step M1, the polymer matrix composites prepreg is pasted onto institute using segmentation barbola work
It states on core model, the segmentation barbola work includes:
N1, material prepreg is cut along machine direction, is cut into multiple elongate strips, the length of the elongate strip
Degree is more than or equal to the length of the core model;
N2, by the elongate strip segmentation be pasted on the core model, paste direction be the elongate strip machine direction with
The length direction of the core model is identical, and the two neighboring elongate strip partly overlaps;
N3, the elongate strip is successively pasted on the core model according to the method for step N2, until shape tube needed for meeting
The thickness of test specimen.
Optionally, in the step M1, after the supplemental rigid mold clamping, clamping pressure is in 500~5000N range
It is interior.
Optionally, in the step M1, the cured article C is warming up to the glass transition that temperature is greater than the core model
When the corresponding temperature of point, the inside of the core model is inflated, keep the air pressure of the inside of the core model 0.02~
Within the scope of 0.1Mpa.
Specific embodiment
To make the above purposes, features and advantages of the invention more obvious and understandable, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.
The shape tube more complicated for structure, especially composite material shape tube, since its structure is complicated, manufacture craft
Cumbersome, so that core model is more difficult in subtractive process, core model easily damages shape tube in subtractive process or moulding is special-shaped
The deformation of pipe.
The present invention is intended to provide readily removed core model, the core model is shape memory in a kind of shape tube manufacture craft
Material is made.The core model is made of shape-memory polymer, and shape-memory polymer (SMP) is a kind of new intelligent material
Material can actively reply the original shape of oneself under extraneous stimulation, use scene with wide.
Typical thermotropic shape-memory polymer Recovery Process is, shape-memory polymer in case of heating by
Outer load deformation, becomes rubber-like, cools down in the case where keeping load, removes load, and deformation is not replied, and shape memory is poly- at this time
Conjunction object is deformed state, has certain rigidity;It heats again, the shape-memory polymer of deformed state deforms and returns back to shape
The original state of shape memory polymer is replied and is externally done work in deformation process.
Specifically, the cross section of the core model is circular ring shape, that is, core model is according to shape tube shape to be prepared
Tubular structure, specifically, core model is according to the structure needs of shape tube, including straight sections and bent portion, the axis of the straight sections
Axis for linear type, the bent portion is " L " type, " C " type or " S " type structure, and at the different location of bent portion, described
The diameter of core model is identical, it is ensured that caliber of the shape tube prepared in bending part is identical, even thickness;The structure of straight sections is
Lantern-shaped, that is, the trend for being distributed as diameter first increases and then decreases in the axial direction, the i.e. middle part of straight sections are to both ends
Diameter is gradually reduced, and meets the requirement of this kind of shape shape tube, and the effective conventional tubeless mold of abnormal shape of the type is as core
Mould can not carry out demoulding or not easy mold release, and shape memory mold is as the available effective solution of core model.
Specifically, as shown in connection with fig. 1, the preparation method of the core model includes the following steps:
Step S1, shape memory polymer material pre-treatment: the ratio of each component in adjustable shape memory polymer stoste
Example, stirring, obtains shape-memory polymer modulating liquid A;In the step, adjustable shape memory polymer is former according to different needs
The ratio of each component of liquid obtains the shape-memory polymer modulating liquid of different performance;Preferably, in shape-memory polymer tune
Reinforcing material is added in liquid processed, wherein the content that reinforcing material is added accounts for the 3%-10% of gross mass, obtains mechanical property enhancing
Shape memory polymer composite material modulating liquid.
Step S2, the described modulating liquid A curing molding: the modulating liquid A is solidified using casting craft, obtains tubulose solidification
Core model B solidifies the original state that core model B is shape-memory polymer, and different formulations modulating liquid A corresponding with proportion is according to specific
Solidification process solidified, different modulating liquid be heating and curing course difference, be specifically, for phenylethylene: at 80 DEG C
At a temperature of heat 8 hours, or 70 DEG C heat 24 hours;For epoxies: first being heated 3 hours at 80 DEG C, then be warming up to 100 DEG C
Heating 3 hours, then be warming up to 150 DEG C and heat 5 hours;For cyanate: first being heated 2 hours at 120 DEG C, then be warming up to 150
DEG C heating 2 hours, then be warming up to 180 DEG C heat 2 hours, be finally warming up to 210 DEG C heat 3 hours.
Step S3, solidification core model B is changed into deformed state by original state: the solidification core model B being heated, temperature is more than
The glass transition point of shape-memory polymer, shape-memory material are changed into rubbery state, the core model of rubbery state are placed in auxiliary
It helps in rigid die, inflating pressure, and cools down in the state of keeping pressure, temperature removes pressure, shape note after dropping to room temperature
Material is recalled in glassy state, and shape-memory polymer core model is changed into deformed state, obtains final core model product, and core model is to face at this time
When working condition, i.e., needed for prepare the core model end-state of composite material shape tube and be specifically placed in the core model of rubbery state
It in supplemental rigid mold, pressurizes after molding, the blowing pressure obtains tubular core mold product within the scope of 0.2~0.5MPa.
Specifically, shape-memory polymer stoste described in step S1 includes polyurethane shape memory polymer, epoxy
The shape-memory polymer of class, the shape-memory polymer of phenylethylene, the shape-memory polymer of cyanate, span carry out acyl
The shape-memory polymers of imines, polyimides shape-memory polymer, polyimides shape-memory polymer one kind or
Person's multiple combinations;When a certain amount of reinforcing material is added in shape-memory polymer modulating liquid, the reinforcing material includes
Carbon nano-particle, carbon nanotube, carbon black, staple fiber, polyurethanes fiber, one or more groups of highly elastic fiber or fabric
It closes.
Prepare in step s 2 solidify core model B have the property that when temperature be lower than material glass transition point when,
Shape-memory material is in glassy state, and material can keep temporary shapes;When temperature is higher than the glass transition point of material, shape
Memory material is in rubbery state, and material can reply original-shape;The corresponding temperature of the glass transition point of different materials is at 50 DEG C
~150 DEG C of ranges are adjustable;The deformability of material is not less than 50% after solidification, and tubular core mold wall thickness is between 2mm~5mm.
Specifically, the deformed state of shape memory core model requires shape memory core model and composite material contact portion, i.e., in
Between section, radial-deformation be not less than 10%;As shown in connection with fig. 3, it is shunk to prevent core model 1 from restoring deformation in the curing process,
It need to carry out inflation processing;1 both ends of core model need to fill plug 2 in blowing process, are inserted into gas tube 3 in plug 2, guarantee that its is airtight
Property, deformation occurs for blowing process.
The core model of shape-memory material preparation is one kind based on shape-memory polymer intelligence core model, has shape memory,
The characteristics of variation rigidity, can change the shape of oneself under environmental stimuli to achieve the purpose that aspect demoulding, can be used for manufacturing
The production of composite material shape tube process core mould.
On the basis of the core model, a kind of forming method that composite material shape tube is prepared using the core model is provided,
As shown in connection with fig. 2, specifically include:
Step M1, composite molding: polymer matrix composites prepreg is pasted on the core model, composite material is made
Prepreg lamination places into supplemental rigid mold, and pressurization is heating and curing, and obtains cured article C after cooling, specifically,
Material prepreg lamination is made on core model, the core model for being stained with material prepreg lamination is put into rigid auxiliary mould
In, rigid die is molded, for mold clamping force between 500~5000N, the effect of molding is to squeeze out material prepreg
Bubble and the higher surface smoothness of composite material test piece for assigning processing;
Step M2, the cured article C core mould removal: is warming up to the glass transition point pair that temperature is greater than the core model
The temperature answered, the core model is changed into rubbery state, and removes with solid union material, extracts the core model out, obtains composite material
Shape tube prefabrication;It raises the temperature on temperature corresponding to the glass transition point of shape-memory material, shape memory
Material is in rubbery state, and it is original shape that core model is replied from deformed state, and Stiffness is between original 1%~3%,
Convenient for the removing of core model;It extracts core model out, obtains composite product;It should be noted that being prepared by supplemental rigid mold
When core model, core model is made to be deformed into deformation state by original shape, it is desirable that the diameter of core model and material prepreg contact portion
Deflection is all not less than 10%, so that stimulation shape memory core model, when core model replys original shape, and core model shrinkage, core model and multiple
Condensation material abnormal shape pipe internal surface is removed naturally, is extracted out convenient for core model.
Step M3, micro-shaping: for the surface roughness situation of composite material shape tube, to the composite wood of step M2 preparation
The surface of material shape tube prefabrication carries out polishing and polishing treatment, requires for production, cuts extra size, obtain composite wood
Expect shape tube.
Specifically, in step M1, the polymer matrix composites prepreg is immersed in impregnating resin by fiber filament and is formed, institute
State one or more combinations that fiber filament includes carbon fiber, glass fibre or aramid fiber;The impregnating resin includes asphalt mixtures modified by epoxy resin
Rouge, unsaturated polyester resin, novolac epoxy resin or span carry out one or more combinations of amide resin.
Specifically, in step M1, the polymer matrix composites prepreg is pasted onto the core using segmentation barbola work
On mould, the segmentation barbola work includes:
N1, material prepreg is cut along machine direction, is cut into multiple elongate strips, the length of the elongate strip
Degree is more than or equal to the length of the core model;
N2, by the elongate strip segmentation be pasted on the core model, paste direction be the elongate strip machine direction with
The length direction of the core model is identical, and the two neighboring elongate strip partly overlaps;
N3, the elongate strip is successively pasted on the core model according to the method for step N2, until shape tube needed for meeting
The thickness of test specimen.
The outer secondary used when it should be noted that solidifying composite material when preparing core model in step s3 and in step M1
It is same set of for helping rigid die;If material prepreg lamination is too thick, lead to the core model for being covered with material prepreg lamination
It can not be molded with same set of rigid die, then need to reuse a set of larger-sized rigid die, until can mold.
It in step M1, is heating and curing to the core model for being covered with material prepreg lamination, if solidification temperature is higher than
Or the glass transition point close to shape memory core model, it shrinks, needs to prevent core model from restoring deformation in the curing process
Pressure is inflated to core model, is equally inflated using plug 2 with gas tube 3, air pressure size is 0.02~0.1MPa.
Specifically, in step M1, shape memory core model is stimulated by the way of heating, heating method includes high temperature
Any one of drying box, autoclave or heat gun.
Shape-memory polymer core model provided in this embodiment is using steps are as follows: 1. according to composite material abnormal shape inside pipe wall
Shape design shape remembers the original shape of core model, designs according to minimum diameter in the original size for being less than composite material shape tube
For straight tube-like, then according to design machining shape memory polymer straight tube;2. making rigid stamps according to cast;With the side of blow molding
Method makes tubular form memory polymer core model be deformed into required shape;3. using deformed shape-memory polymer core model
Make composite material shape tube core model;4. a pair core model motivates, so that it becomes initial straight tube-like, takes out core from port
Mould can return to step 2 reuse.
Shape memory intelligence core model can be used as the core model of the composite material shape tube manufacturing process of labyrinth, demoulding letter
Single, the core model of relative complex shape, traditional metal die can not be demoulded as core model, be compared using composable mold demoulding
Complexity, manufacture craft is cumbersome, and the composite material shape tube of opposite elbow-shaped, can not also be demoulded using composable mold.
Using shape-memory material due to possessing certain ductility, after heating, can be become by reset condition in the case where bearing external force
For the working condition of complicated shape, and original form can be replied after certain excitation, it is special-shaped to can be used as complicated shape composite material
One kind of tube core mould.
On the basis of described above, one kind specifically core model and composite material shape tube forming method are now provided, in conjunction with
Shown in Fig. 3-Fig. 6, include the following steps:
One, it is each the pre-treatment of phenylethylene shape memory polymer composite material: to adjust styrene resin base modulating liquid
Component ratio.With the styrene of the catechol stabilizer of tert-butyl containing 10-15ppm4- and the stabilizer containing 10-60ppmmEHQ
Butyl acrylate mixes according to the volume ratio of 3:1, makes its 80 DEG C of corresponding glass transition point, and the total matter of content Zhan is added
3% carbon nanotube of amount stirs 3h with ultrasonoscope, obtains the phenylethylene composite material of shape memory of mechanical property reinforcement
Modulating liquid.
Two, the core model 1 of " L " type carbon fiber bend pipe is prepared with styrene shape-memory material: benzene second prepared by step 1
Alkene modulating liquid is solidified into round tube, wall thickness 3mm using casting craft, wherein it is 80 DEG C that solidification process, which is temperature, curing time is 8 small
When.After solidification, round tube is formed, is cut to suitable length, both ends fill plug 2, are warming up to 120 degrees Celsius, material is in
Core model 1 is bent approximately in " L " type by rubbery state, until can be put into rigid auxiliary mould, is molded, in rigid auxiliary mould
Under effect, apply 0.2MPa air pressure from gas tube 3, inflationtime 2min carries out the inflation of intermediate stage.1 both ends of core model
It is blocked with plug 2, shape memory core model 1 is bonded in blowing process with 4 inner wall of rigid die, is formed ' L ' that interlude is heaved
Shape bend pipe is the deformed state of core model 1.Deformed state requires shape memory core model 1 and composite material contact portion, i.e., intermediate
Section, radial-deformation are not less than 10%, carry out inflation;1 both ends of core model need to fill plug 2 in blowing process, to guarantee its gas
Close property, so 1 both ends of blowing process core model are without inflation.The deformed state of last core model 1 is " L " broad in the middle, small in ends
Type bend pipe shape.Air pressure is removed after inflation, core model 1 is put into refrigerator cooling, and core model 1 is not replied, and deformation shape is kept
State.
Three, polymer matrix composites prepreg is pasted on styrene shape memory core model 1, it is composite material presoaked to being covered with
The core model 1 of material lamination is solidified: first in the interlude sticking carbon fiber prepreg elongate strip 5 of shape memory core model 1: will answer
Condensation material prepreg is cut along machine direction, is cut into multiple elongate strips 5 according to required composite material test piece size,
Segmentation is pasted on shape memory core model 1, wherein adjacent material prepreg elongate strip 5 overlaps each other.In this manner
Material prepreg single layer is formed on shape memory core model 1, each single layer layer needs about 16 material prepregs
Elongate strip 5, each thickness in monolayer are 0.2mm or so.It repeats this step to carry out repeating stickup, lamination is formed, until laminated thickness
Greater than 2mm.The core model 1 for being stained with carbon fibre laminates is placed in rigid auxiliary mould, is molded with rigid die 4, rigid
Property 4 upper die and lower die of mold on effect size be 1000N clamping pressure;Under mold clamping force effect, composite product is squeezed out
Bubble, while composite product inner surface is contacted with 1 outer surface of core model, composite product outer surface and rigid mould
Have the contact of 4 inner walls, guarantees the surface smoothness of composite product.Heater box is put into be solidified, condition of cure be 130 DEG C/
8h.It is solid in order to prevent since carbon fiber prepreg solidification temperature is higher than the glass transition point of phenylethylene shape memory mold
Recovery of shape occurs for change process core model 1, in heat curing process, applies 0.05MPa air pressure in gas tube 3, carries out at pressure maintaining
Reason.
Four, shape memory core model 1 is stimulated, core model 1 is made to restore original shape, core model 1 is extracted out, finally obtains composite material structure
Part: after solidification, removing the air pressure of gas tube 3, and the core model 1 for being stained with carbon fibre laminates is continued to keep 130 DEG C of heating 0.5h,
In heating process, 1 interlude of core model is shunk, and 1 outer surface of core model is detached from gradually with composite material pipe internal surface, does not stick together,
And core model 1 is in rubbery state, and Stiffness is original 1%, is in high resiliency, from composite product slowly by core model 1
Demoulding is completed in extraction.
Five, surface and size micro-shaping are carried out to composite product, obtains composite material tubing products: " L " that will be obtained
Type carbon fiber pipe is trimmed, is polished, obtaining required carbon fiber product.
The technique is formed relative to common metal mold for composite product, and demoulding is simple, and product surface precision is high,
The polymorphic structure demoulded is difficult to suitable for metal core die, abnormal shape is tied and shape memory core model can be used for multiple times, production cost
It is low, it is suitable for all kinds of complicated shape composite products.
And the technique is pasted using material prepreg, is molded with rigid die.The technique relative to
Carbon fiber winding technique has the advantage that not needing machine is wound, manual operations, low in cost;It saves and twines
Impregnation steps are carried out after fiber filament, are directly solidified, and process pollution is few;It is used just after having pasted material prepreg
Property mold is molded, and surface smoothness is higher.
Although the disclosure discloses as above, the protection scope of the disclosure is not limited only to this.Those skilled in the art are not
Under the premise of being detached from spirit and scope of the present disclosure, it can make various changes and modify, these changes will fall into this with modification
The protection scope of invention.