CN103937224B - A kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material - Google Patents
A kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material Download PDFInfo
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- CN103937224B CN103937224B CN201410085447.3A CN201410085447A CN103937224B CN 103937224 B CN103937224 B CN 103937224B CN 201410085447 A CN201410085447 A CN 201410085447A CN 103937224 B CN103937224 B CN 103937224B
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Abstract
The present invention is to provide a kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material.(1) carbon nanotube and polyurethane elastomer particle are dissolved in respectively in organic solvent, carbon nano-tube solution are dropwise added in elastic polyurethane liquid solution, the content of carbon nanotube is 0.1 ~ 1wt%; (2) mixing solutions that step (1) obtains is placed in vacuum drying oven to be vented, temperature remains on 70 ~ 100 DEG C, and the time is 0.5h ~ 1.5h; (3) NiTi alloy spring is put into acetone ultrasonic cleaning; (4) NiTi alloy spring is slowly embedded in the mixed system obtained of step (2); (5) in air blast thermostat container, remove solvent, temperature remains on 70 ~ 100 DEG C, and molding time is 24 ~ 48h, after solvent is removed completely, namely obtain product.Preparation technology of the present invention is simple, good moldability, cost are low; The composite material exhibits of preparation goes out good damping characteristic and shape memory recovery characteristic.
Description
Technical field
That the present invention relates to is a kind of preparation method of composite functional material, the method preparing NiTi spring/carbon nano-tube/poly ammonia ester matrix material of specifically a kind of improvement.
Background technology
The harm of noise and vibration is huge, and it not only destroys mechanical means reliability of operation and stability, and pollutes the environment, the health of harm humans.Fact proved, employing damping material is the most effectual way of control texture resonance and noise.Study the damping behavior of material, develop the damping material had compared with high damping properties, the harm caused by vibration reduction and solution and problem have very important realistic meaning.Single damping material often can not meet the service requirements on engineer applied completely.Such as, although superpolymer has very high damping loss factor, due to rigidity with specific tenacity is low, creep resistance is poor, can not use as structural part.Therefore, consider in polymeric matrix, add mineral filler and steel fiber, play the mechanical property feature of adding material, realize the mutual supplement with each other's advantages of differing materials, prepare the vibration damping composite material of high strength.
Polyurethane material is the segmented copolymer that a class obtains with isocyanic ester and polyol reaction, main chain is lower than the soft segment of room temperature and the second-order transition temperature rigid chain segment block higher than room temperature by second-order transition temperature, the structure of its uniqueness imparts its excellent over-all properties, maximum feature is high resilience, wear resistance is remarkable, and good oil-proofness and ozone resistance, have certain shape-memory properties, and can produce larger damping, but to be exactly mechanical strength lower for obvious shortcoming.Carbon nanotube is as monodimension nanometer material, and its superpower mechanical property greatly can improve intensity and the toughness of polymer materials, is therefore the desirable strongthener of matrix material in theory.In addition, carbon nanotube filler has very large length-to-diameter ratio, surface-area, very large with resin matrix interfacial contact area.When carbon nanotube and resin matrix produce Relative sliding, can interface friction dissipation energy be passed through, thus the damping capacity of matrix material is improved.In addition, polymer materials often shows high damping capacity near second-order transition temperature, and this limits its damping range of application to a certain extent.After adding carbon nanotube, due to interface friction loss of energy, the dependency of the damping capacity of material to temperature is decreased.Therefore, carbon nano tube-doped polyurethane matrix is utilized to be the effective way improving composite materials property and damping capacity.
Along with the fast development in the field such as space flight and aviation, precision instrument, high damping material, while possessing high strength, excellent corrosion resistance, also should possess and adapt to external environment change and the intelligent attributes suitably adjusting self mechanical property and dynamic mechanical behavior.Therefore, the damping material developing intelligent attributes following gives priority to trend.Select NiTi shape memory alloy and polyurethane damping material compound, NiTi shape memory alloy is utilized to issue in temperature or stress drive good super-elasticity, shape memory effect and the damping characteristic that raw Thermoelastic Martensitic Transformation in A shows, environmental change response be can make to external world, self mechanical property and dynamic mechanical behavior adjusted.Therefore, utilize NiTi alloy and polyurethane-base volume recombination, while ensureing that material has high damping, the intelligent control of mechanical attribute and damping capacity can also be realized.
To sum up, carbon nanotube and NiTi shape memory alloy effectively can improve the mechanical property of polymer materials, damping capacity and functional performance.What relate generally in the open document reported at present is single interpolation carbon nanotube or NiTi B alloy wire etc. in viscoelastic resin material, all fails the advantage of carbon nanotube, NiTi alloy and viscoelastic material effectively to combine.Given this, applicant by carbon nanotube and NiTi alloy composite mixed in urethane resin matrix, utilized hot melt molding legal system standby to have the damp composite material (number of patent application: 201310099996.1) of temperature response characteristics.Hot melt molding method has the features such as shaping efficiency is high, cost is low.But find under study for action, when adopting hot melt process to prepare matrix material, because the overall flow of resin matrix is bad, so carbon nanotube effectively can only disperse in local, overall dispersion effect is bad.In addition, owing to needing to prepare different moulds in advance when preparing difform material, thus production cost is added.
Summary of the invention
The object of the present invention is to provide a kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material that technique is simple, good moldability, cost are low.
The object of the present invention is achieved like this:
(1) carbon nanotube and polyurethane elastomer particle are dissolved in respectively in organic solvent, carbon nano-tube solution are dropwise added in elastic polyurethane liquid solution, the content of carbon nanotube is 0.1 ~ 1wt%;
(2) mixing solutions that step (1) obtains is placed in vacuum drying oven to be vented, temperature remains on 70 ~ 100 DEG C, and the time is 0.5h ~ 1.5h;
(3) NiTi alloy spring is put into acetone ultrasonic cleaning;
(4) NiTi alloy spring is slowly embedded in the mixed system obtained of step (2);
(5) in air blast thermostat container, remove solvent, carry out composite material forming, temperature remains on 70 ~ 100 DEG C, and molding time is 24 ~ 48h, namely obtains NiTi spring and carbon nanotube and compound polyurethane material after solvent is removed completely.
Described carbon nanotube and polyurethane elastomer particle being dissolved in organic solvent respectively refers to: and by carbon nano-tube solution ultrasonic disperse 1h ~ 3h; Elastic polyurethane liquid solution is placed in magnetic stirring apparatus stir.
The problem such as although utilize the solution method of forming to exist preparation efficiency that solvent evaporates causes is low, but the entirety dispersiveness of carbon nanotube can effectively improve, and the method for casting can be adopted shaping due to solution, therefore greatly save the production cost of matrix material.The present invention carries out preparation method's improvement and the solution method of forming that utilizes proposed prepares NiTi spring/carbon nano-tube/poly ammonia ester matrix material on the basis of previous research.
Advantage of the present invention is mainly reflected in:
(1) preparation technology of the present invention is simple, good moldability, cost are low;
(2) the present invention utilizes the solution method of forming shaping, effectively avoids and eliminate the tissue defects that hot melt molding method is introduced due to temperature and stress problems;
(3) carbon nanotube in the present invention can stir in a solvent, disperse, and improves its overall dispersion effect in the base;
(4) composite material exhibits that prepared by the present invention goes out good damping characteristic and shape memory recovery characteristic.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of NiTi/CNT/TPU matrix material;
The Fracture scan photo that Fig. 2 (a)-Fig. 2 (c) is NiTi/CNT/TPU matrix material;
Fig. 3 is the stretching cyclic curve of NiTi/CNT/TPU matrix material;
Fig. 4 is the dynamic thermomechanometry test curve of NiTi/CNT/TPU matrix material;
Fig. 5 is the recovery of shape test pattern of NiTi/CNT/TPU matrix material;
Fig. 6 is the shape recovery rate test curve of NiTi/CNT/TPU matrix material.
Embodiment
The of the present invention basic step utilizing the solution method of forming to prepare NiTi alloy spring and the composite mixed compound polyurethane material of carbon nanotube is: carbon nanotube (CNT) and polyurethane elastomer (TPU) particle are dissolved in organic solvent by (1) respectively, and by CNT solution ultrasonic disperse 1h ~ 3h, subsequently TPU solution is placed in magnetic stirring apparatus to stir, CNT dropwise after dispersion is added in TPU solution simultaneously, make CNT be dispersed in TPU solution, the content of CNT is 0.1 ~ 1wt%; (2) CNT-TPU mixing solutions is placed in vacuum drying oven to be vented, temperature remains on 70 ~ 100 DEG C, and the time is 0.5h ~ 1.5h; (3) NiTi alloy spring is put into acetone ultrasonic cleaning; (4) NiTi alloy spring is slowly embedded in the CNT-TPU mixed system of step (2).(5) in air blast thermostat container, remove solvent, carry out composite material forming, temperature remains on 70 ~ 100 DEG C, and molding time is 24 ~ 48h, after solvent is removed completely, namely obtain NiTi/CNT/TPU matrix material.
Illustrate below and the present invention be described in more detail:
(1) CNT containing carboxyl and 8185 types (the Yantai Wan Hua urethane company trade mark) TPU is dissolved in DMF respectively.Then by CNT solution ultrasonic disperse 2h, subsequently TPU solution is placed in magnetic stirring apparatus and stirs, more finely dispersed CNT dropwise is added TPU solution, make CNT be dispersed in TPU solution, CNT content is 0.5wt% simultaneously;
(2) CNT-TPU mixing solutions is placed in vacuum drying oven exhaust-gas disposal, temperature remains on 80 DEG C;
(3) NiTi alloy spring acetone is carried out ultrasonic cleaning;
(4) NiTi alloy spring is slowly embedded in the CNT-TPU mixed system of step (2);
(5) in air blast thermostat container, remove solvent, carry out composite material forming, temperature remains on 80 DEG C, and molding time is 36h, after removal of solvents, namely obtain NiTi/CNT/TPU matrix material.
(6) microstructure of sem observation matrix material is utilized.By matrix material brittle failure under liquid nitrogen condition, the scanned photograph of fracture is as shown in Fig. 2 (a)-Fig. 2 (c), the rear section polyurethane matrix that ruptures as can be observed from Figure still sticks to NiTi spring surface, the interface cohesion of NiTi alloy and TPU matrix is described better (Fig. 2 (a), Fig. 2 (b)).In addition, can find from the enlarged photograph of structure, the interface cohesion of CNT and TPU matrix is good, and be uniformly dispersed (Fig. 2 (c));
(7) the stretching cyclic curve of universal electrical tensile testing machine test compound material is utilized.As shown in Figure 3, along with adding of CNT and NiTi, Young's modulus and the tensile strength of matrix material increase gradually, describe the enhancement of CNT and NiTi alloy to resin matrix.Narrow Hystersis in working cycle can the energy waste of exosyndrome material in working cycle indirectly, as can be seen from the figure, after adding CNT and NiTi spring, area of hysteresis loop increases to some extent, shows that being added in of CNT and NiTi spring adds somewhat to the energy waste of matrix material under large sstrain condition;
(8) utilize dynamic thermomechanical analysis apparatus test compound material damping loss characteristic at different temperatures, test frequency is 10Hz.As shown in Figure 4, CNT and NiTi spring add the dissipation factor that effectively can improve matrix material, after adding CNT and NiTi spring, the highest loss factor of matrix material is 0.43 simultaneously;
(9) the recovery of shape characteristic of self-control recovery of shape device to test matrix material is utilized.Figure 5 shows that the shape memory effect of the principle test compound material producing recovery of shape according to NiTi alloy spring generation martensite reverse transformation, first sample is put into-50 DEG C of liquid nitrogen alcohol mixed solutions ((a) step), make NiTi alloy spring generation martensitic transformation, then by matrix material flexural deformation ((b) step), permanent set ((c) step) is produced after removing external force, again sample is heated to room temperature, make NiTi spring generation martensite reverse transformation, composite shapes is replied, record angle ((d) step) now, calculate the shape recovery rate of matrix material, Fig. 6 is the recovery of shape rate curve of matrix material, and as can be seen from the figure, along with the increase of content of carbon nanotubes, shape recovery rate has certain reduction, but shape recovery rate all remains on more than 90%, shows good recovery of shape characteristic.
Claims (1)
1. prepare a method for NiTi spring and carbon nanotube and compound polyurethane material, it is characterized in that:
(1) carbon nanotube and polyurethane elastomer particle are dissolved in organic solvent respectively, carbon nano-tube solution ultrasonic disperse 2h, elastic polyurethane liquid solution is placed in magnetic stirring apparatus and stirs, carbon nano-tube solution is dropwise added in elastic polyurethane liquid solution to the content of carbon nanotube be 0.1 ~ 1wt%; Described organic solvent is DMF, carbon nanotube is carbon nanotube containing carboxyl;
(2) mixing solutions that step (1) obtains is placed in vacuum drying oven to be vented, temperature remains on 70 ~ 100 DEG C, and the time is 0.5h ~ 1.5h;
(3) NiTi alloy spring is put into acetone ultrasonic cleaning;
(4) NiTi alloy spring is slowly embedded in the mixed system obtained of step (2);
(5) in air blast thermostat container, remove solvent, carry out composite material forming, temperature remains on 70 ~ 100 DEG C, and molding time is 24 ~ 48h, namely obtains NiTi spring and carbon nanotube and compound polyurethane material after solvent is removed completely.
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