CN109596464A - A kind of interface performance test method of surface modification of carbon nanotube fiber - Google Patents
A kind of interface performance test method of surface modification of carbon nanotube fiber Download PDFInfo
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- CN109596464A CN109596464A CN201811609687.3A CN201811609687A CN109596464A CN 109596464 A CN109596464 A CN 109596464A CN 201811609687 A CN201811609687 A CN 201811609687A CN 109596464 A CN109596464 A CN 109596464A
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Abstract
The present invention provides a kind of interface performance test methods of surface modification of carbon nanotube fiber, surface modification of carbon nanotube fiber Zhan Sihou is successively carried out gas desorption processing to the present invention and monofilament is handled, it will obtain fibre single thread to be straightened and paste both ends horizontal on mold, the mold for being adhesive with fibre single thread will vertically be put into card slot fixed；Then resin solution is added dropwise on fibre single thread, carries out contact angle test after hanging；The test of microballon unsticking is carried out after resin liquid drop is solidified, and fiber/resin interface shear strength is obtained according to the diameter calculation of test result and the fibre single thread.The present invention is directed to the unique micron-nanometer composite construction feature of surface modification of carbon nanotube fiber, devise dedicated fiber pre-treatment and test sample preparation method, and test method provided by the invention can simultaneously test the important indicator of two fiber/resin interface performances of interface shear strength and contact angle evaluation, it is high-efficient, method is simple, and characterization result is accurate.
Description
Technical field
The present invention relates to material properties test technical field, in particular to a kind of interface of surface modification of carbon nanotube fiber
Performance test methods.
Background technique
The advantages of continuous fiber reinforced composites are with its high specific strength, high ratio modulus, lightweight and designability,
Nowadays the every field such as Aeronautics and Astronautics, wind-powered electricity generation, automobile, sport are had been widely used for.Fiber in polymer matrix composites/
Resin boundary surface plays the role of transmitting load, and the height of interface performance directly affects the mechanical property of composite material, therefore compound
The research of material interface properties is the focus and emphasis in the field always.
As a kind of emerging monodimension nanometer material, carbon nanotube has high mechanical property, the drawing of single carbon pipe
Intensity is stretched up to 100GPa, and stretch modulus is up to 1TPa.The researcher of Massachusetts Institute Technology is heavy by low temperature chemical vapor
Long-pending method deposited carbon nanotube in carbon fiber surface, come so as to improve the specific surface area and reinforcement mechanical engagement effect of fiber
Improve the interface stick performance of fiber/resin.(see document: Hierarchical carbon nanotube carbon fiber
unidirectional composites with preserved tensile and interfacial properties
[J] .Composites Science and Technology, 2015,117:139-145.) with research gradually deeply, lead to
Various methods are crossed to have become a kind of the common of reinforcing fiber/resin boundary surface performance in fiber surface deposition of carbon nanotubes and have
The method of effect.However the characterization of the interface performance for the fiber of this novel micron-nanometer composite construction across scale, it grinds
The persons of studying carefully establish unified and effective method not yet.
Microballon unsticking method and contact angle method are two kinds of most common methods for characterizing fiber/resin interface performance.Microballon is de-
Bonding is in 1997 by Japanese Dong Rong Co., Ltd. in a kind of composite material circle for publishing proposition on Japanese composite material proceedings
Face evaluation method, this method characterize the interface adhesion of fiber/resin by directly pulling the resin bead on single fiber
Energy.Simple due to operating, effect is intuitive, and this interface rating method has been widely used for commenting for composite material interface performance
Valence.Contact angle method refers to the infiltration by optical microphotograph sem observation resin to fiber, and the data processing tree for passing through image
Method of the rouge to a kind of evaluation fibre resin wellability of the infiltration angle of fiber.
At this stage, researchers are by almost the characterization of necessary parameter is surveyed in both fiber/resin interface ratings
Examination separately carries out, and Efficiency is low.It deposited the fiber of carbon nanotube for this novel surface simultaneously, it is unique micro-
Rice-nano composite structure causes the characteristics of micro-molecular gas such as vapor easily adsorbs, macromolecular resin difficulty infiltrates.This uniqueness
Structure a variety of uncertain factors are come to the junction belt of the infiltration of resin and resin and fiber, this is to by microballon unsticking method and connecing
Feeler method characterizes its interface performance and brings many difficulties and inconvenience, has seriously affected the development of the research field.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of interface performance test sides of surface modification of carbon nanotube fiber
Method.Test sample resin infiltration made from test method provided by the invention is good, internal tight, and can be contacted simultaneously
Angle test and the test of microballon unsticking, improve testing efficiency, method is simple, and characterization result is accurate.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of interface performance test method of surface modification of carbon nanotube fiber, comprising the following steps:
(1) surface modification of carbon nanotube fiber Zhan Sihou is successively subjected to gas desorption processing and monofilament is handled, obtain fibre
Tie up monofilament；The surface modification of carbon nanotube fiber includes fiber and the carbon nanotube for being deposited on fiber surface；
(2) fibre single thread is straightened and pastes both ends horizontal on mold, the mold of fibre single thread will be adhesive with
It is vertically put into fixed in card slot；The mold is concave character type sheet metal；The interlude of the fibre single thread is suspended on mold
Concave indentation, there；
(3) resin solution is added dropwise on fibre single thread, the contact angle of fiber and resin liquid drop is measured after hanging；
(4) fibre single thread for hanging with resin liquid drop is heat-treated, resin liquid drop is made to be solidified into resin microbeads, then into
The test of row microballon unsticking, obtains fiber/resin interface shear strength according to the diameter calculation of test result and the fibre single thread.
Preferably, the carbon nanotube includes chemical deposition or physical deposition in the deposition method of fiber surface.
Preferably, it when the carbon nanotube is when the deposition method of fiber surface is chemical deposition, also wraps before the exhibition silk
It includes:
The surface modification of carbon nanotube fiber is placed in liquid and is ultrasonically treated.
Preferably, the liquid includes one or more of water, ethyl alcohol and acetone；The frequency of the ultrasonic treatment is
20kHz~60kHz, power are 100W~500W, and the time is 5min~30min.
Preferably, gas desorption processing carries out under vacuum conditions in the step (1), the temperature of the gas desorption processing
Degree is 60~120 DEG C, and the time is 0.5h~3h.
Preferably, resin solution includes resin, curing agent and diluent in the step (3)；The diluent is acetone
And/or methylene chloride；The viscosity of the resin solution is 1Pas~10Pas.
Preferably, the time hung in the step (3) is 0.5~3h, and the environment temperature hung is 10~30 DEG C,
The ambient humidity hung is 40~60RH.
Preferably, the temperature being heat-treated in the step (4) is 80~200 DEG C.
Preferably, the diameter of the resin microbeads is 30~100 μm.
Preferably, the diameter of fibre single thread obtains by the following method in the step (4):
The fibre single thread for taking 10~20 surface modification of carbon nanotube fibers to be measured, using SEM to the fibre single thread into
Row shooting, diameter of the arithmetic average diameter as the fibre single thread；
Or, according to the monofilament root of the line density of surface modification of carbon nanotube fiber to be measured, fiber volume density and every bundle fiber
Number is calculated, and the diameter of the fibre single thread is obtained；
Or, retain the fibre single thread sample after the test of microballon unsticking, resin bead is shot by SEM and is fallen off the diameter at place, is made
For the diameter of the fibre single thread；
Or, directly using the diameter of the fibre single thread without surface modification of carbon nanotube.
The present invention provides a kind of interface performance test method of surface modification of carbon nanotube fiber, the present invention is by carbon nanometer
Pipe surface modified fibre Zhan Sihou successively carries out gas desorption processing and monofilament processing, will obtain fibre single thread and is straightened and by both ends
Level is pasted on mold, the mold for being adhesive with fibre single thread is vertically put into card slot fixed；Then resin solution is added dropwise
On fibre single thread, contact angle test is carried out after hanging；The test of microballon unsticking is carried out after resin liquid drop solidification, according to test result
Fiber/resin interface shear strength is obtained with the diameter calculation of the fibre single thread.Method provided by the invention has with following
Beneficial effect:
(1) present invention carries out exhibition silk to surface modification of carbon nanotube fiber and gas desorption is handled, and may make and is adsorbed on fibre
The abundant desorption of the gas in dimension table face prevents the generation of sealed porosity between fiber/resin after resin solidification, avoids vapor to boundary
The influence of surface intensity and mechanical strength of resin；
(2) present invention will be affixed directly on mold after fibre single thread sub-wire, both can be before resin solidification without other
Where reason carries out contact angle test, and can be directly used in the test of microballon unsticking after hardening, substantially increases test characterization efficiency,
In turn avoid the damage in fibre single thread transfer process；
(3) further, the present invention is directed to the surface modification of carbon nanotube fiber obtained using chemical deposition, in exhibition silk
Before be ultrasonically treated, the carbon nanotube that can cover to fiber surface and thereon carries out physically activated, is conducive to resin to fiber
Infiltration；
(4) further, the present invention uses acetone or methylene chloride to prepare resin solution as diluent, is conducive to resin
Abundant wetting fibre, and by control resin viscosity make the resin microbeads after solidifying on fiber it is of uniform size be distributed in 30~
It 100 μm, reduces the stress on single fiber sample and concentrates to reduce fibrous fracture, be conducive to the progress of microballon unsticking test.
(5) further, it the present invention provides the diameter acquisition methods of a variety of monfil, can be selected according to experimental conditions
Suitable fibre diameter acquisition methods, are conducive to more accurately calculate interface shear strength.
Embodiment the result shows that, the test sample resin infiltration that test method provided by the invention obtains is good and internal without sky
Gap can test fiber/resin contact angle and interface shear strength simultaneously, and test result is accurate, be conducive to correlative study into
One step is carried out.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of mould therefor of the embodiment of the present invention and card slot；
Fig. 2 is microballon unsticking test schematic diagram；
In Fig. 1~2: 1- mold, 2- adhesive, 3- fibre single thread, two side opening of 4- card slot, 5- card slot, 6- resin microbeads,
The swaging clamp of 7- test equipment, the test fixture of 8- connection load transducer；
Fig. 3 is the SEM figure of the fiber before and after deposition of carbon nanotubes；
Fig. 4 is the contact angle image of fibre single thread and resin to be measured in embodiment 1；
Fig. 5 is that fibre single thread surface topography and resin microbeads to be measured fall off the pattern of position in embodiment 1；
Fig. 6 is the T700S carbon fiber for the surface modification of carbon nanotube that different-diameter acquisition modes are calculated in embodiment 1
Interface shear strength；
Fig. 7 is that fibre single thread surface topography and resin microbeads to be measured fall off the pattern of position in embodiment 2；
Fig. 8 is the T300 carbon fiber for the surface modification of carbon nanotube that different-diameter acquisition modes are calculated in embodiment 2
Interface shear strength.
Specific embodiment
The present invention provides a kind of interface performance test methods of surface modification of carbon nanotube fiber, comprising the following steps:
(1) surface modification of carbon nanotube fiber Zhan Sihou is successively subjected to gas desorption processing and monofilament is handled, obtain fibre
Tie up monofilament；
(2) fibre single thread is straightened and pastes both ends horizontal on mold, the mold of fibre single thread will be adhesive with
It is vertically put into fixed in card slot；The mold is concave character type sheet metal；The interlude of fibre single thread is suspended on the concave of mold
Indentation, there；
(3) resin solution is added dropwise on fibre single thread, the contact angle of fiber and resin liquid drop is measured after hanging；
(4) fibre single thread for hanging with resin liquid drop is heat-treated, so that resin liquid drop is solidified into resin microbeads, so
The test of microballon unsticking is carried out afterwards, and fiber/resin interface shearing is obtained according to the diameter calculation of test result and the fibre single thread
Intensity.
Surface modification of carbon nanotube fiber Zhan Sihou is successively carried out gas desorption processing to the present invention and monofilament is handled, and obtains
Fibre single thread.In the present invention, the surface modification of carbon nanotube fiber includes fiber and the carbon nanometer for being deposited on fiber surface
Pipe；The carbon nanotube preferably includes chemical deposition or physical deposition in the deposition method of fiber surface；The present invention is to describedization
The specific method for learning deposition and physical deposition does not have particular/special requirement, specific chemical deposition such as chemical vapor deposition, chemistry
Grafting etc., physical deposition method such as electrophoretic deposition, spray deposited and solution immersion deposition etc..Type of the present invention to the fiber
There is no a particular/special requirement, the fiber of common type, it is specific as carbon fiber, glass fibre, basalt fibre, aramid fiber,
Pbo fiber and ceramic fibre etc..
In the present invention, when the carbon nanotube fiber surface deposition method be chemical deposition when, the Zhan Siqian
Further include: the surface modification of carbon nanotube fiber is placed in liquid and is ultrasonically treated.In the present invention, the liquid is excellent
Choosing includes one or more of water, ethyl alcohol and acetone；The supersonic frequency of the ultrasonic treatment is preferably 20~60kHz, more excellent
It is selected as 30~50kHz, most preferably 40kHz；Ultrasonic power is preferably 100~500W, more preferably 200~400W, most preferably
For 300W；Sonication treatment time is preferably 5~30min, more preferably 10~20min, most preferably 15min.
The present invention, which preferably immerses the surface modification of carbon nanotube fiber in liquid, carries out ultrasound using supersonic cleaning machine
Processing, should be noted that half of the amount of liquid in container no more than vessel volume, is also answered when using ethyl alcohol or acetone when ultrasonic
Paying attention to sealing using preservative film prevents from evaporating.The carbon nanotube that the present invention is deposited fiber and surface by ultrasonic treatment into
Row is physically activated.
When the carbon nanotube is attached to fiber surface by physical deposition, the surface modification of carbon nanotube fiber is not
Can using ultrasonic treatment, avoid ultrasonic treatment so that deposition carbon nanotube fall off from fiber surface, influence subsequent for fiber
The characterization of interface performance.
After ultrasonic treatment, the present invention dries fiber, then carries out exhibition silk processing again.
In the present invention, the exhibition silk preferably opens up silk manually or carries out exhibition silk using exhibition silk machine；The carbon nanotube table
Face modified fibre is fibre bundle, can reduce fiber stack thickness by opening up silk, increases tow surface area, be conducive to subsequent small molecule
The progress of Gas desorption.The present invention preferably passes through exhibition silk and the surface modification of carbon nanotube fiber is expanded to 0.5~1.0mm
Width, more preferably 0.6~0.7mm.
After the completion of opening up silk processing, the fibre bundle of Zhan Sihou is carried out gas desorption processing by the present invention.In the present invention, described
Gas desorption processing preferably carries out under vacuum conditions, and the temperature of the gas desorption processing is preferably 60~120 DEG C, more preferably
It is 80~100 DEG C, most preferably 85~95 DEG C；The time of the gas desorption processing is preferably 0.5h~3h, more preferably 1~
2h, most preferably 1.5h.The present invention carries out gas desorption processing preferably in vacuum drying oven, in specific embodiments of the present invention
In, preferably the fibre bundle both ends of Zhan Sihou are fixed on polytetrafluoroethylene film, is then placed in vacuum drying oven and carries out gas
Desorption processing.
After the completion of opening up silk processing, the fibre bundle of the Zhan Sihou is carried out monofilament processing by the present invention, obtains fibre single thread.?
In the present invention, the monofilament processing is preferred are as follows: fibre bundle is cut the length for being about 8~10cm, spreads over white polytetrafluoroethyl-ne
On alkene film, fibre bundle is driven out away dispersion using tip tweezers, and clamp single fiber.
After obtaining fibre single thread, the fibre single thread is straightened and pastes both ends horizontal on mold by the present invention, will stick
The mold for posting fibre single thread, which is vertically put into card slot, to be fixed.In the present invention, the mold is concave character type sheet metal, preferably
For concave character type stainless steel thin slice, the thickness of the concave character type sheet metal is preferably 0.1~0.3mm, and the present invention is to the mold
Size there is no particular/special requirement, can be according to the length and test equipment (microballon debonding interface device for evaluating performance) of fibre single thread
It is adjusted, as a specific embodiment of the invention, the structure snd size of the mold are as shown in Figure 1；Fibre single thread two
End is cohered on mold, and the interlude of fibre single thread is suspended on the concave indentation, there of mold；There are dentation aperture in the card slot two sides,
As shown in Figure 1, multiple concave character type sheet metals vertically can be fixed；The card slot is preferably metal material, more preferably not
Become rusty steel.
Present invention preferably uses adhesives to cohere at fibre single thread both ends on mold；The adhesive is preferably high temperature resistant
And at room temperature can quick-setting adhesive, such as 502, acrylate AB glue, R230.The present invention preferably takes adhesive with pin mark
It is applied to the contact position of fiber and mold, then coheres fibre single thread, after fibre single thread is cohered, the present invention will preferably cohere
Sample room temperature hangs 5~30min, solidifies adhesive, and then mold is put into card slot as shown in Figure 1 again.
The present invention preferably repeats aforesaid operations, and it is spare to be made 10~20 samples in total, to 10~20 samples when test
Surface property tested, be averaged, with improve test accuracy.
After mold is fixed in card slot, resin solution is added dropwise on fibre single thread the present invention, measures fiber after hanging
With the contact angle of resin liquid drop.In the present invention, the resin solution preferably includes resin, curing agent and diluent；The tree
Rouge is preferably that epoxy resin, bimaleimide resin, phenolic resin, polyester resin, cyanate resin or thermosetting property polyamides are sub-
Polyimide resin；The diluent is preferably acetone and/or methylene chloride；In the resin solution content of diluent be preferably 10~
40wt%, more preferably 20~30wt%, most preferably 25wt%；The present invention is to the type and dosage of the curing agent without spy
It is different to require, in a specific embodiment of the present invention, corresponding curing agent preferably is selected according to resin types, and according to solidification ratio
Determine the dosage of curing agent.
In the present invention, the viscosity of the resin solution is preferably 1Pas~10Pas, and more preferably 3Pas~
8Pas, further preferably 5Pas；The present invention within the above range, can make the concentration control of the resin solution solid
Resin bead after change is of uniform size to be distributed in 30~100 μm, reduces the stress on fiber and concentrates and be convenient for the test of microballon unsticking.
In a specific embodiment of the present invention, preferably resin, curing agent and diluent are stirred, the stirring when
Between preferably 5~15min, more preferably 10min, then use 1mL syringe receptive resin solution, dropped evenly dropwise in fibre
It ties up on monofilament, it will steadily slowly when paying attention to using and moving syringe needle；The present invention is preferably added dropwise on a fibre single thread
More drop resin solutions, to select the more suitable resin liquid drop of size to be tested, and a sample can test multiple numbers
According to keeping test result more accurate.
In the present invention, the time hung is preferably 0.5~3h, more preferably 1~2h, most preferably 1.5h；Institute
Stating and hanging environment temperature is preferably 10~30 DEG C, and more preferably 15~25 DEG C；The ambient humidity that hangs is preferably 40~60%
RH, more preferably 45~55%RH.The present invention makes the solvent in resin volatilize by hanging.
After hanging, the present invention will hang with the fiber global transfer of drop of resin to contact angle measurement in card slot and card slot
On, it is shot using contact image of the contact angle measurement to fiber/resin, by obtaining fiber/resin to image procossing
Contact angle, the present invention preferably test every kind of fiber sample to obtain 5 numerical value, take its average value, to improve the accuracy of detection.
After contact angle test, the fibre single thread for hanging with resin liquid drop is heat-treated by the present invention, makes resin
Drop is solidified into resin microbeads.The present invention preferably by the card slot, mold and coheres the fiber on mold and is integrally put into baking
It is heat-treated in case, the temperature of the heat treatment is preferably 80~200 DEG C, and the present invention is to the time of the heat treatment without spy
It is different to require, specific heat treatment time is preferably determined according to the curing process system of specific resin；The diameter of the resin microbeads
Preferably 30~100 μm, more preferably 40~80 μm.
After solidification, closing baking oven makes sample cooled to room temperature, then takes out sample and carries out the test of microballon unsticking,
Fiber/resin interface shear strength is obtained according to the diameter calculation of test result and the fibre single thread.The present invention is to described micro-
The specific method of pearl unsticking test does not have particular/special requirement, uses microballon debonding interface performance evaluation well known to those skilled in the art
Device is tested.In a specific embodiment of the present invention, when test, using in microballon debonding interface device for evaluating performance
Swaging clamp gripping fibers monofilament on resin microbeads, then apply certain tensile load to the left, as shown in Fig. 2, until by resin
Pearl pulls from fiber, obtains the maximum pull of the process for calculating interface shear strength.If occurring fiber in test process
Fracture, resin bead fragmentation are considered as invalid test result；The present invention 10~20 numerical value of preferably every group of sample testing take it average
Value, to improve the accuracy of detection；The present invention preferably retains the fibre single thread sample after resin bead and fiber separation, uses SEM
The fiber filament diameter of resin bead disengaged position is observed.
In the present invention, the fiber/resin interface shear strength calculation formula such as Formulas I institute that the microballon unsticking method measures
Show:
In Formulas I, FmaxMaximum, force (N) when slipping for resin, instrument directly gives after test；dfFor fiber filament diameter
(mm)；leIt is drop of resin to the embedding length (mm) of fiber, is amplified by optical microscopy when test soft using testing after sample
Measuring tool directly measures in part.
For fiber filament diameter dfMeasuring and calculating, unlike traditional fibre, the present invention in surface modification of carbon nanotube
Fiber is deposited with carbon nanotube in fiber surface, and it is apparent that the carbon nanotube with certain length can make fibre diameter present
Increase, but carbon nanotube layer has a large amount of apparent gaps, the fibre diameter before and after deposition of carbon nanotubes is as shown in Figure 3.And
Different situations, fibre diameter is presented in fiber surface state and diameter after different deposition methods and the test of different resins microballon unsticking
Selection will directly determine calculate gained interface shear strength accuracy.In this regard, the present invention provides following four fibre single thread
The advantage and disadvantage of every kind of acquisition modes are illustrated in the acquisition modes of diameter.
Mode one, the fibre single thread for taking 10~20 surface modification of carbon nanotube fibers to be measured, using SEM to the fiber
Monofilament is shot, diameter of the arithmetic average diameter as the fibre single thread.This kind of acquisition modes simple, intuitive, but due to micro-
The carbon nanotube deposited on fiber after the test of pearl unsticking is pulled together with resin mostly, thus the practical fiber for destroying interface is straight
Diameter can be less than the diameter that this kind of method measures, thereby increases and it is possible to have larger difference.
Mode two, according to the monofilament root of the line density of the surface modification of carbon nanotube fiber, volume density and every bundle fiber
Number is calculated, and the diameter of the fibre single thread is obtained.Between the carbon nanotube that this method can effectively avoid surface from depositing
Fibre diameter caused by gap it is apparent bigger than normal, but since the case where being likely to occur fibrous fracture in practical operation, leads to practical fibre
Dimension radical is relatively low, thus the fibre diameter that this method obtains is slightly bigger than normal.
Mode three retains the fibre single thread sample after the test of microballon unsticking, shoots resin bead by SEM and falls off the straight of place
Diameter, the diameter as the fibre single thread.It is broken that the diameter that such method obtains can the most accurately represent fiber/resin interface
The forced area situation of bad when, thus the interface shear strength being calculated is also the most accurate.But this kind of method needs more
Complicated later period test job, workload are maximum.
Mode four, the diameter for directly using the fibre single thread without surface modification of carbon nanotube.This method is suitable for carbon
When nanotube deposition combines insecure and fiber/resin interface interaction difference, fiber surface is smooth after microballon falls off at this time, no resin
It is remained with carbon nanotube, fibre diameter and the fibre diameter of non-deposition of carbon nanotubes are essentially identical.
The present invention is directed to the unique micron-nanometer composite construction feature of surface modification of carbon nanotube fiber, devises dedicated
Fiber pre-treatment and test sample preparation method, and test method provided by the invention can simultaneously to interface shear strength
It is tested with the important indicator of two fiber/resin interface performances of contact angle evaluation.Meanwhile the present invention is to interface shear strength
The selection details of fibre diameter is optimized in calculating, substantially increases the evaluation efficiency and standard of fiber/resin interface performance
True property.
Scheme provided by the invention is described in detail below with reference to embodiment, but they cannot be interpreted as pair
The restriction of the scope of the present invention.
Embodiment 1
Fiber to be measured are as follows: deposited the beautiful T700S carbon fiber in the east 12K of carbon nanotube on surface using chemical vapour deposition technique
Dimension；
Carbon fiber bundle to be measured is immersed in ethyl alcohol, is ultrasonically treated using supersonic cleaning machine, the supersonic frequency of ultrasonic treatment
Rate is 40kHz, ultrasonic power 400W, sonication treatment time 15min.After ultrasonic treatment, using exhibition silk machine by fiber
Tow is expanded to 0.6mm width.The fibre bundle both ends of Zhan Sihou are fixed on polytetrafluoroethylene film, are put into vacuum drying oven
Carry out Vacuum solutions adsorption treatment.Treatment temperature is 100 DEG C, time 2h.
By treated, fibre bundle cuts the length for being about 8cm, spreads on white polytetrafluoroethylpipe film, uses tweezers
It drives out carbon fiber bundle away dispersion, and clamps single fiber and be placed on stainless steel mould shown in FIG. 1.With pin mark R230 adhesive
It is applied to the contact position of fiber and mold, 25 DEG C of room temperatures hang 10min solidification.20 samples are made in total.Simultaneously measurement to
Survey fibre bundle line density is 0.907g/m, fiber volume density is 1.805g/cm3, and fibre single thread is taken to carry out SEM shooting to obtain
Intuitive diameter.
, will be fixed on mold card slot shown in Fig. 1 after fiber is pasted on mold, AG80 resin is weighed using beaker
3.08g acetone (the 20wt% of resin and curing agent quality, AG80 resin viscosity is added into resin by 10g, DDS curing agent 5.4g
It is larger) dilution.After weighing, resin, curing agent and acetone, mixing time 8min are stirred using glass bar.It uses
The 1mL syringe receptive resin solution of pinhole diameter 0.3mm, then drops evenly on carbon mono-filaments dropwise, and 25 DEG C/
2h is hung in the air environment of 50%RH makes the acetone in resin volatilize.
After hanging, card slot and the carbon fiber for hanging with drop of resin are transferred on contact angle measurement, shoot fiber/tree
The contact image of rouge is as shown in figure 4, and handle acquisition contact angular data.The contact angle that test obtains T700/AG80/DDS is average
Value is 81.1 °, 2.5 ° of standard deviation.And resin can be seen that according to Fig. 4 and fiber infiltrates good, internal tight appearance, this
Also ensure the accuracy of test.
After contact angle test, the carbon fiber for being put into card slot and hanging with drop of resin is integrally put into baking oven 180
DEG C heat preservation 3h solidified resin pearl, after solidification close baking oven make sample cooled to room temperature, after taking-up carry out microballon unsticking
Test, it is total to measure 20 data.
The surface of fiber and the SEM image of resin bead disengaged position are as shown in figure 5, wherein Fig. 5 (1) is fiber surface
SEM figure, Fig. 5 (2) are that the SEM of resin bead disengaged position schemes；It is 8.66 μm by the fibre diameter that SEM is directly obtained, passes through fibre
Tie up bunch density, fiber volume density obtain fibre diameter be 7.30 μm, fracture SEM resin bead fall off locate fibre diameter be 7.56
μm, the green diameter of the fiber of non-deposition of carbon nanotubes is 7.09 μm.The interface shear strength being calculated by respective diameters
As shown in Figure 6.
When the carbon nanotube of fiber surface to be measured is that chemical vapor deposition is this firm it can be seen from the result of Fig. 6
When method or stronger with the fibrous binding force epoxy resin of use, fiber surface has more resin residue to occur, and uses at this time
SEM shooting resin bead fall off place the interface shear strength that calculates of fibre diameter (mode three) it is the most accurate, by line density and
The interface shear strength that the fibre diameter (mode two) that volume density obtains calculates is not much different with upper person, and is directly obtained by SEM
Deposition of carbon nanotubes fiber apparent fibre diameter (mode one) and using non-deposition of carbon nanotubes fiber it is original
The interface shear strength accuracy that diameter (mode four) calculates is poor.
By the embodiment it is found that the method provided through the invention, it can efficiently and accurately obtain surface and deposited carbon and receive
The carbon fiber of mitron and the interface shear strength of epoxy resin and contact angle, conducive to the further development of correlative study.
Embodiment 2
Fiber to be measured is that deposited the T300 carbon fiber of the 12K of carbon nanotube on surface using electrophoretic deposition.
Carbon fiber bundle to be measured is expanded to by 0.7mm width using exhibition silk machine, the fibre bundle both ends of Zhan Sihou are fixed on poly-
On tetrafluoroethene film, it is put into vacuum drying oven and carries out Vacuum solutions adsorption treatment.Treatment temperature is 90 DEG C, time 3h.
By treated, carbon fiber bundle cuts the length for being about 10cm, spreads on white polytetrafluoroethylpipe film, wears rubber
Rubber gloves drive out fibre bundle away dispersion, and clamp single fiber and be placed on stainless steel mould shown in FIG. 1.It is taken with pin mark
Uniformly mixed two-component acrylicester AB glue adhesive is applied to the contact position of fiber and mold, and 30 DEG C of room temperatures are hung
30min solidification, is made 15 samples in total.Measure that fibre bundle line density is 1.02g/m, fiber volume density is 1.810g/ simultaneously
cm3, and fiber is taken to carry out SEM shooting to obtain intuitive diameter.
, will be fixed on mold card slot shown in Fig. 2 after fiber is pasted on mold, E51 resin is weighed using beaker
1.84g acetone (10wt% of resin and curing agent quality) dilution is added into resin by 10g, BC126 curing agent 8.4g.It weighs
After, resin, curing agent and acetone, mixing time 15min are stirred using glass bar.Use pinhole diameter 0.4mm
1mL syringe receptive resin solution, then drop evenly on carbon mono-filaments dropwise, and in the air of 30 DEG C/45%RH
1.5h is hung in environment makes the acetone in resin volatilize.
After hanging, card slot will be put into and hang with the carbon mono-filaments of drop of resin integrally it is put into baking oven at 120 DEG C
3h solidification is kept the temperature, baking oven is closed after solidification makes sample cooled to room temperature, and the test of microballon unsticking is carried out after taking-up, amounts to
Measure 20 data.
The surface of fiber and the SEM image at resin bead disengaging are as shown in fig. 7, wherein Fig. 7 (1) is the SEM of fiber surface
Figure, Fig. 7 (2) are the SEM figure at resin bead disengaging；It is 8.08 μm by the fibre diameter that SEM is directly obtained, passes through fiber bunch
Density, fiber volume density obtain fibre diameter be 7.75 μm, in fracture SEM resin bead fall off locate fibre diameter be 7.50 μm,
Incision position fiber surface is smooth, remains almost without resin and carbon nanotube, and the fiber of non-deposition of carbon nanotubes is original straight
Diameter is 7.45 μm.The interface shear strength being calculated by respective diameters is as shown in Figure 8.
When the carbon nanotube of fiber surface to be measured is physical deposition (carbon nanotube and fiber it can be seen from the result of Fig. 8
Surface combines insecure) and when using the resin weaker with fibrous binding force, fiber surface is almost without resin and carbon nanotube
Residual.At this time using SEM shooting resin bead fall off place fibre diameter (mode three) calculate interface shear strength it is the most accurate,
The interface shear strength calculated by the fibre diameter (mode four) of non-deposition of carbon nanotubes is essentially identical with the former, and passes through
The apparent diameter (mode one) and use tow line density/fiber volume density of the fiber for the deposition of carbon nanotubes that SEM is directly obtained/
The interface shear strength accuracy that the average diameter (mode two) that number of fiber obtains calculates is poor.
By the embodiment it is found that the method provided through the invention, selects according to different deposition methods and resin-bonded power
Different fibre diameter acquisition methods, can the more efficient and accurate surface that obtains deposited the carbon fiber and asphalt mixtures modified by epoxy resin of carbon nanotube
The interface shear strength of rouge, conducive to the further development of research.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of interface performance test method of surface modification of carbon nanotube fiber, which comprises the following steps:
(1) surface modification of carbon nanotube fiber Zhan Sihou is successively subjected to gas desorption processing and monofilament is handled, obtain fiber list
Silk；The surface modification of carbon nanotube fiber includes fiber and the carbon nanotube for being deposited on fiber surface；
(2) fibre single thread is straightened and pastes both ends horizontal on mold, the mold for being adhesive with fibre single thread is vertical
It is put into card slot fixed；The mold is concave character type sheet metal；The interlude of the fibre single thread is suspended on the concave of mold
Indentation, there；
(3) resin solution is added dropwise on fibre single thread, the contact angle of fiber and resin liquid drop is measured after hanging；
(4) fibre single thread for hanging with resin liquid drop is heat-treated, resin liquid drop is made to be solidified into resin microbeads, then carried out micro-
The test of pearl unsticking, obtains fiber/resin interface shear strength according to the diameter calculation of test result and the fibre single thread.
2. test method according to claim 1, which is characterized in that deposition method of the carbon nanotube in fiber surface
Including chemical deposition or physical deposition.
3. test method according to claim 2, which is characterized in that when the carbon nanotube is in the deposition side of fiber surface
When method is chemical deposition, the Zhan Siqian further include:
The surface modification of carbon nanotube fiber is placed in liquid and is ultrasonically treated.
4. test method according to claim 3, which is characterized in that the liquid includes one in water, ethyl alcohol and acetone
Kind is several；The frequency of the ultrasonic treatment is 20kHz~60kHz, and power is 100W~500W, and the time is 5min~30min.
5. test method according to claim 1, which is characterized in that gas desorption processing is in vacuum in the step (1)
Under the conditions of carry out, the temperature of gas desorption processing is 60~120 DEG C, and the time is 0.5h~3h.
6. test method according to claim 1, which is characterized in that resin solution includes resin, consolidates in the step (3)
Agent and diluent；The diluent is acetone and/or methylene chloride；The viscosity of the resin solution is 1Pas~10Pa
s。
7. test method according to claim 1, which is characterized in that the time hung in the step (3) be 0.5~
3h, the environment temperature hung are 10~30 DEG C, and the ambient humidity hung is 40~60RH.
8. test method according to claim 1, which is characterized in that the temperature being heat-treated in the step (4) is 80~
200℃。
9. test method according to claim 1, which is characterized in that the diameter of the resin microbeads is 30~100 μm.
10. test method according to claim 1, which is characterized in that the diameter of fibre single thread passes through in the step (4)
Following methods obtain:
The fibre single thread for taking 10~20 surface modification of carbon nanotube fibers to be measured claps the fibre single thread using SEM
It takes the photograph, diameter of the arithmetic average diameter as the fibre single thread；
Or, according to the monofilament radical of the line density of surface modification of carbon nanotube fiber to be measured, fiber volume density and every bundle fiber into
Row calculates, and obtains the diameter of the fibre single thread；
Or, retain the fibre single thread sample after the test of microballon unsticking, resin bead is shot by SEM and is fallen off the diameter at place, as institute
State the diameter of fibre single thread；
Or, directly using the diameter of the fibre single thread without surface modification of carbon nanotube.
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