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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
carbon nanotube
niti
spring
polyurethane
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410085447.3A
Other languages
Chinese (zh)
Other versions
CN103937224A (en
Inventor
李莉
田兵
郑玉峰
王杨辉
陈枫
佟运祥
刘二宝
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heilongjiang Henghe Sand Technology Development Co. Ltd.
Original Assignee
Harbin Engineering University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Engineering University filed Critical Harbin Engineering University
Priority to CN201410085447.3A priority Critical patent/CN103937224B/en
Publication of CN103937224A publication Critical patent/CN103937224A/en
Application granted granted Critical
Publication of CN103937224B publication Critical patent/CN103937224B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

A kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material
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.
CN201410085447.3A 2014-03-11 2014-03-11 A kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material Active CN103937224B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410085447.3A CN103937224B (en) 2014-03-11 2014-03-11 A kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410085447.3A CN103937224B (en) 2014-03-11 2014-03-11 A kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material

Publications (2)

Publication Number Publication Date
CN103937224A CN103937224A (en) 2014-07-23
CN103937224B true CN103937224B (en) 2015-12-02

Family

ID=51185115

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410085447.3A Active CN103937224B (en) 2014-03-11 2014-03-11 A kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material

Country Status (1)

Country Link
CN (1) CN103937224B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10427336B2 (en) 2014-11-20 2019-10-01 Baker Hughes, A Ge Company, Llc Periodic structured composite and articles therefrom
US9999920B2 (en) * 2015-04-02 2018-06-19 Baker Hughes, A Ge Company, Llc Ultrahigh temperature elastic metal composites
US10759092B2 (en) 2015-11-19 2020-09-01 Baker Hughes, A Ge Company, Llc Methods of making high temperature elastic composites
US10450828B2 (en) 2016-10-28 2019-10-22 Baker Hughes, A Ge Company, Llc High temperature high extrusion resistant packer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101372553A (en) * 2008-10-24 2009-02-25 南开大学 Functionalized single layer graphite and polyurethane photo-induced shape memory composite material and preparation thereof

Also Published As

Publication number Publication date
CN103937224A (en) 2014-07-23

Similar Documents

Publication Publication Date Title
CN103937224B (en) A kind of method preparing NiTi spring and carbon nanotube and compound polyurethane material
Kumar et al. Studies on mechanical, thermal and dynamic mechanical properties of untreated (raw) and treated coconut sheath fiber reinforced epoxy composites
Kumar et al. Layering pattern effects on vibrational behavior of coconut sheath/banana fiber hybrid composites
Rwawiire et al. Development of a biocomposite based on green epoxy polymer and natural cellulose fabric (bark cloth) for automotive instrument panel applications
CN104325652B (en) Ultimum Ti and the composite mixed compound polyurethane material of CNT and preparation method
Xiao et al. Enhancing the thermal and mechanical properties of epoxy resins by addition of a hyperbranched aromatic polyamide grown on microcrystalline cellulose fibers
Fonseca et al. Shape memory polyurethanes reinforced with carbon nanotubes
MY146826A (en) Thermoplastic resin composition, production method thereof, and molded article
Stalin et al. The performance of bio waste fibres reinforced polymer hybrid composite
Gu et al. Polyurethane/polyhedral oligomeric silsesquioxane shape memory nanocomposites with low trigger temperature and quick response
Debeli et al. Study on the pre-treatment, physical and chemical properties of ramie fibers reinforced poly (lactic acid)(PLA) biocomposite
Dayo et al. Impacts of hemp fiber diameter on mechanical and water uptake properties of polybenzoxazine composites
Reddy et al. Dynamic mechanical analysis of hemp fiber reinforced polymer matrix composites
Thakur et al. Free radical induced graft copolymerization of ethyl acrylate onto SOY for multifunctional materials
Ramakrishnan et al. Experimental investigation of mechanical properties of untreated new Agave Angustifolia Marginata fiber reinforced epoxy polymer matrix composite material
Obada et al. Effect of variation in frequencies on the viscoelastic properties of coir and coconut husk powder reinforced polymer composites
Aditya et al. Characterization of natural fiber reinforced composites
Kale et al. Fabrication of green composites based on rice bran oil and anhydride cross-linkers
Rwawiire et al. Short-term creep of barkcloth reinforced laminar epoxy composites
Behera et al. Effect of nanoclay on physical, mechanical, and microbial degradation of jute‐reinforced, soy milk‐based nano‐biocomposites
Alishiri et al. In situ preparation and characterization of biocompatible acrylate‐terminated polyurethane containing chemically modified multiwalled carbon nanotube
Das et al. The mechanics of biocomposites
Sharavanan et al. Experimental investigation of tensile and impact behaviour of hemp flax hybrid composite
Liu et al. Hybrid HNTs-kenaf fiber modified soybean meal-based adhesive with PTGE for synergistic reinforcement of wet bonding strength and toughness
Zhu et al. Editable and bidirectional shape memory chitin hydrogels based on physical/chemical crosslinking

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20161008

Address after: 150001, Heilongjiang province Harbin Harbin hi tech Industrial Development Zone, science and technology innovation city, innovation and entrepreneurship Plaza 14, 236 Lou Mingyue street, torch e-commerce building, room 513

Patentee after: Heilongjiang Henghe Sand Technology Development Co. Ltd.

Address before: 150001 Heilongjiang, Nangang District, Nantong street,, Harbin Engineering University, Department of Intellectual Property Office

Patentee before: Harbin Engineering Univ.