CN110272612A - Protein-carbon nano-fiber/epoxy resin composite material and preparation method thereof - Google Patents
Protein-carbon nano-fiber/epoxy resin composite material and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/046—Carbon nanorods, nanowires, nanoplatelets or nanofibres
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Abstract
The invention discloses a kind of protein-carbon nano-fiber/epoxy resin composite materials and preparation method thereof, belong to modified nano composite material preparation and applied technical field, this method includes, quantitative protein is weighed to be put into acetic acid and the mixed solution of deionized water, carry out constant temperature stirring, quantitative carbon nano-fiber is then added, successively carries out protein denaturation and carbon nano-fiber is modified;Then it filtered, washed and is dried, obtain the carbon nano-fiber of protein graft modification;Quantitative protein-modified CNFs is weighed, is added in the epoxy resin of preheating, protein-carbon nano-fiber/epoxy resin composite material is prepared.The present invention realizes the protein grafting of carbon nano-fiber, protein-modified carbon nano-fiber in the epoxy evenly dispersed, and the stronger interaction between epoxy molecule, effectively improves the mechanical property of composite material.With simple process, environmentally protective and performance more preferably feature.
Description
Technical field
The invention belongs to modified nano composite material preparation and applied technical fields, more particularly, to a kind of albumen
Matter-carbon nano-fiber/epoxy resin composite material and preparation method thereof.
Background technique
Fibre reinforced epoxy composite material have excellent specific strength and specific stiffness, fatigue resistance, environmental suitability and
Cutting performance is widely used to aerospace industry.However, intensity and insulating property (properties) that epoxy resin-base is relatively poor
Hinder the realization of the high-mechanical property and multifunctional performance of composite material, such as potential anti-lightning and electromagnetic armouring structure
Material.Therefore, in order to develop its various application field, it is necessary to have the advanced Epoxy Resins of excellent mechanical and electric property.
Carbon nano-fiber has excellent mechanical property, electric property, thermal property and optical property.By carbon Nanowire
Dimension is compound with epoxy resin as nanofiller, and epoxy resin multifunctionality can be improved.However, if original carbon Nanowire
Dimension is directly mixed with epoxy resin, and strong Van der Waals interaction will drive carbon nano-fiber cluster and aggregation, this can
The performance of epoxy resin can be caused to decline.Therefore, carrying out surface treatment to carbon nano-fiber first seems and is highly desirable.
How carbon nano-fiber is surface-treated, avoids strong Van der Waals from interacting and drive carbon nanometer
Fiber cluster and aggregation improve carbon nano-fiber epoxy resin composite material performance, become the technical problem of this field.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of protein-carbon nano-fiber/
Epoxy resin composite material and preparation method thereof, it is intended that realizing the protein grafting of carbon nano-fiber, protein changes
Property carbon nano-fiber in the epoxy evenly dispersed, and the stronger interaction between epoxy molecule, thus solve
When certainly carbon nano-fiber is directly mixed with epoxy resin, strong Van der Waals interaction drives carbon nano-fiber cluster
And aggregation, cause epoxy resin performance decline the technical issues of.
To achieve the above object, according to one aspect of the present invention, a kind of protein-carbon nano-fiber/epoxy is provided
The preparation method of resin composite materials, which comprises the steps of:
(1) protein powder for weighing 2a parts of quality is dissolved in the deionized water of 1000a parts of quality or is by mass ratio
In the acetic acid solution that the anhydrous acetic acid and deionized water of 4:1 is configured to, the constant temperature stirring denaturation of protein is carried out;Wherein a is positive
Number;
(2) mixed liquor that step (1) obtains is cooled to room temperature, the carbon nano-fiber of a~8a parts of quality is then added,
Processing is modified to carbon nano-fiber;
(3) mixed liquor that step (2) obtains is separated by solid-liquid separation, isolated solid is adopted and is washed with deionized water
It washs to neutrality, is put into drying in vacuum oven, is then ground, obtain the carbon nano-fiber of protein grafting;
(4) carbon nano-fiber for the protein grafting that the step of weighing 1.3b parts of quality (3) obtains, is added to preheating
It in the epoxy resin of 400b~1000b parts of quality, is uniformly dispersed, obtains the first mixture;Wherein b is positive number;
(5) the first mixture that step (4) obtains is cooled to room temperature, being added with the quality proportioning of epoxy resin is 10:
3 curing agent, is dispersed with stirring, and bubble removing is gone to obtain the second mixture at room temperature;
(6) the second mixture that step (5) obtains is solidified, solidification carries out natural cooling after terminating, and obtains egg
White matter-carbon nano-fiber epoxy resin composite material.
Preferably, in step (1), the protein is Type A type animal skin gelatin Gelatin or soybean separation protein
White SPI;Temperature is 55~60 DEG C in the constant temperature stirring denaturation of the protein, 55~60min of mixing time.
Preferably, in step (2), the mode for being modified processing to carbon nano-fiber is cooler environment lower prong ultrasound
Processing then carries out the stirring of constant temperature constant speed.
Preferably, in step (2), cooler environment lower prong is ultrasonically treated 5-6min;The temperature of the constant temperature constant speed stirring
It is 55~60 DEG C, the time is 55~60min, and revolving speed is 1800~2000rpm.
Preferably, in step (3), drying temperature is 70~75 DEG C in vacuum oven, and the time is 10~12h.
Preferably, in step (4), finely dispersed mode is cooler environment lower prong ultrasonic disperse, then in room temperature
Lower water bath sonicator.
Preferably, it in step (4), is added in the epoxy resin of 400~1000 parts of quality of 35 DEG C~40 DEG C preheatings,
Cooler environment lower prong 5~6min of ultrasonic time, then 30~35min of water bath sonicator at room temperature, obtains the first mixture.
Preferably, in step (5), after the curing agent is added, 10~15min of mechanical stirring, vacuumize 50 at room temperature~
60min goes bubble removing to obtain the second mixture.
Preferably, the second mixture is poured slowly into mold in step (6), carries out 25 DEG C for 24 hours, 60 DEG C of 15h, 120 DEG C of 2h
Three sections solidification.
It is another aspect of this invention to provide that providing a kind of protein-being prepared by any of the above-described the method
Carbon nano-fiber/epoxy resin composite material.
Preferably, protein-carbon Nanowire in protein-carbon nano-fiber/epoxy resin composite material obtained above
The weight percent of dimension is 0.1wt%-0.25wt%.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) functional group abundant that the present invention is contained using protein, such as amino, carboxyl, hydroxyl, methyl, in its molecule
The multiple reaction sites provided in structure are grafted on its surface with CNFs interaction, form modified carbon nano tube fiber, then
Prepare protein-carbon nano-fiber/epoxy resin composite material;Protein is as a kind of effective environmentally protective surface-active
Agent can improve the dispersibility of carbon nano-fiber, avoid cluster and aggregation;Secondly, protein grafting carbon nano-fiber with
Interface performance between epoxy resin-base is effectively improved.
(2) the method for the present invention realizes the protein grafting of carbon nano-fiber, and protein-modified carbon nano-fiber is in epoxy
It is evenly dispersed in resin, and the stronger interaction between epoxy molecule, with the epoxy for not using the method for the present invention
Resin composite materials are compared, and the composite material bending strength and bending modulus that the method for the present invention obtains be respectively increased 28~
31% and 18~21%.
(3) method provided by the invention has a simple process, environmentally protective and performance more preferably feature, prepared
To composite material can be applied to the structural member and bonding agent of civil equipment, for preparing modified carbon nano tube fiber and changing
Property epoxy resin composite material has a wide range of applications meaning.
(4) experiment shows that the protein-carbon compared with existing epoxide resin material, being prepared through the invention is received
Rice fiber/epoxy resin composite material has obtained good promotion in mechanical property.
Detailed description of the invention
Fig. 1 is protein in the embodiment of the present invention-carbon nano-fiber/epoxy resin composite material preparation method process
Figure;
Fig. 2 (a) is that the first mixture optical microscopy that weight percent is 0.1wt% in the embodiment of the present invention 1 disperses
Figure;
Fig. 2 (b) is that the first mixture optical microscopy that weight percent is 0.1wt% in the embodiment of the present invention 4 disperses
Figure;
Fig. 3 is protein-carbon nano-fiber/epoxy resin composite material and control group obtained in the embodiment of the present invention
Sliding and bending deformation figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments,
The present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain this hair
It is bright, it is not intended to limit the present invention.In addition, technology involved in the various embodiments of the present invention described below is special
Sign can be combined with each other as long as they do not conflict with each other.
As shown in Figure 1, the present invention provides a kind of protein-carbon nano-fiber/epoxy resin composite material preparation sides
Method, which comprises the steps of:
(1) protein powder for weighing 2a parts of quality is dissolved in the deionized water of 1000a parts of quality or is by mass ratio
In the acetic acid solution that the anhydrous acetic acid and deionized water of 4:1 is configured to, the constant temperature stirring denaturation of protein is carried out;
(2) mixed liquor that step (1) obtains is cooled to room temperature, the carbon nano-fiber of a~8a parts of quality is then added,
Processing is modified to carbon nano-fiber;
(3) mixed liquor that step (2) obtains is separated by solid-liquid separation, isolated solid is adopted and is washed with deionized water
It washs to neutrality, is put into drying in vacuum oven, is then ground, obtain the carbon nano-fiber of protein grafting;
(4) carbon nano-fiber for the protein grafting that the step of weighing 1.3b parts of quality (3) obtains, is added to preheating
It in the epoxy resin of 400b~1000b parts of quality, is uniformly dispersed, obtains the first mixture;
(5) the first mixture that step (4) obtains is cooled to room temperature, being added with the quality proportioning of epoxy resin is 10:
3 curing agent, is dispersed with stirring, and bubble removing is gone to obtain the second mixture at room temperature;
(6) the second mixture that step (5) obtains is solidified, solidification carries out natural cooling after terminating, and obtains egg
White matter-carbon nano-fiber weight percent is that protein-carbon nano-fiber epoxy resin of 0.1wt%-0.25wt% is compound
Material.
As an alternative embodiment, the protein is Type A type animal skin gelatin in step (1)
Gelatin or soybean protein isolate SPI;Temperature is 55~60 DEG C in the constant temperature stirring denaturation of the protein, mixing time
55~60min.
As an alternative embodiment, the mode for being modified processing to carbon nano-fiber is, cold in step (2)
But environment lower prong is ultrasonically treated, and then carries out the stirring of constant temperature constant speed.
In step (2), cooler environment lower prong is ultrasonically treated 5-6min;The temperature of constant temperature constant speed stirring is 55~
60 DEG C, the time is 55~60min, and revolving speed is 1800~2000rpm.
As an alternative embodiment, drying temperature is 70~75 DEG C in vacuum oven in step (3), the time
For 10~12h.
As an alternative embodiment, finely dispersed mode is cooler environment lower prong ultrasound in step (4)
Dispersion, then water bath sonicator at room temperature.
It is added in the epoxy resin of 400~1000 parts of quality of 35 DEG C~40 DEG C preheatings, cooler environment lower prong ultrasound
5~6min of time, then 30~35min of water bath sonicator at room temperature, obtains the first mixture.
As an alternative embodiment, in step (5), after the curing agent is added, 10~15min of mechanical stirring,
Vacuumizing 50~60min at room temperature goes bubble removing to obtain the second mixture.
As an alternative embodiment, the second mixture is poured slowly into mold in step (6), 25 DEG C are carried out
For 24 hours, three sections of solidifications of 60 DEG C of 15h, 120 DEG C of 2h.
Below in conjunction with attached drawing and example to protein-carbon nano-fiber/epoxy resin composite material provided by the invention
Preparation method is described in further detail.
Embodiment 1:
Using the method for the present invention, a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method, including
Following steps:
1) it weighs 0.2g gelatin (Gelatin) powder and is dissolved in 100ml acetic acid solution (+1 part of deionized water of 4 parts of acetic acid)
In, it is placed in 60 DEG C of constant temperature oil bath magnetic stirring apparatus and stirs 60min;
2) it after the mixed liquor for obtaining step 1) is cooled to room temperature, is added 0.2g carbon nano-fiber (CNFs), water-bath cooling
Environment lower prong is ultrasonically treated 6min;Then solution is placed in 60 DEG C of constant temperature oil bath magnetic stirring apparatus, 2000rpm revolving speed stirs
Mix 12h;
3) mixed liquor for obtaining step 2) filters, and after deionized water is washed 5 times, it is dry to be put into 75 DEG C of vacuum
Dry 12h, is finally ground, obtains Gelatin-CNFs in dry case.
4) Gelatin-CNFs for weighing 39mg, is added in the 30g epoxy resin (epoxy) of 40 DEG C of preheatings, stirs manually
1min is mixed, then in water-bath (for example mixture of ice and water) cooler environment lower prong ultrasound 6min, power 100W, then in room
The lower water bath sonicator 35min of temperature, obtains the first evenly dispersed mixture;
5) the first mixture for obtaining step 4) is cooled to room temperature, and being added with the quality proportioning of epoxy resin is 10:3
Curing agent, mechanical stirring 15min vacuumizes bubble removing 60min at room temperature, obtains the second mixture Gelatin-CNFs/
epoxy;
6) Gelatin-CNFs/epoxy for obtaining step 5) is poured slowly into mold, carries out 25 DEG C for 24 hours, 60 DEG C of 15h,
Three sections of solidifications of 120 DEG C of 2h, natural cooling after solidification;Protein-carbon nano-fiber weight percent, which is prepared, is
The protein of 0.1wt%-carbon nano-fiber epoxy resin composite material, i.e. Gelatin-CNFs/epoxy sample coupon.
Using the method for the present invention, the protein-carbon nano-fiber epoxy resin composite wood for the 0.1wt% that embodiment 1 obtains
Expect that performance carries out experimental analysis, as shown in Fig. 2 (a), optical microscopy scatter diagram of the gelatin-CNFs in the first mixture
Show that control group Fig. 2 (b) relative to Pristine-CNFs, diameter range are mentioned in 0~5 μm of particle accounting from about 50%
84% is risen to, 20 μm of diameter or more of particle significantly reduces, this Dispersion on surface has good improvement;From Fig. 3 bending property
As can be seen that 31.47% He has been respectively increased in the bending strength and modulus of Gelatin-CNFs relative to pure epoxy group
21.72%, be superior to Pristine-CNFs/epoxy group (23.21% and 15.59%), show Gelatin-CNFs with
There is good interfacial interaction performance between epoxy.
Embodiment 2:
Using the method for the present invention, a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method, including
Following steps:
1) it weighs 0.2g gelatin (Gelatin) powder and is dissolved in 100ml acetic acid solution (+1 part of deionized water of 4 parts of acetic acid)
In, it is placed in 55 DEG C of constant temperature oil bath magnetic stirring apparatus and stirs 55min;
2) it after the mixed liquor for obtaining step 1) is cooled to room temperature, is added 0.8g carbon nano-fiber (CNFs), water-bath cooling
Environment lower prong is ultrasonically treated 5min;Then solution is placed in 55 DEG C of constant temperature oil bath magnetic stirring apparatus, 1800rpm revolving speed stirs
Mix 10h;
3) mixed liquor for obtaining step 2) filters, and after deionized water is washed 5 times, it is dry to be put into 70 DEG C of vacuum
Dry 10h, is finally ground, obtains gelatin-carbon nano-fiber (Gelatin-CNFs) in dry case.
4) Gelatin-CNFs for weighing 97.5mg, is added in the 30g epoxy resin of 35 DEG C of preheatings, hand operated mixing
1min, then in water-bath cooling environment lower prong ultrasound 5min, power 100W, then water bath sonicator 30min at room temperature,
Obtain the first evenly dispersed mixture;
5) the first mixture for obtaining step 4) is cooled to room temperature, and the quality proportioning with epoxy resin is consolidating for 10:3
Agent, mechanical stirring 10min vacuumize bubble removing 50min at room temperature, obtain the second mixture Gelatin-CNFs/
epoxy;
6) the Gelatin-CNFs/epoxy mixed liquor that step 5) obtains is poured slowly into mold, carries out 25 DEG C for 24 hours,
Three sections of solidifications of 60 DEG C of 15h, 120 DEG C of 2h, natural cooling after solidification;Protein-carbon nano-fiber weight hundred is prepared
Divide protein-carbon nano-fiber epoxy resin composite material than being 0.25wt%, i.e. Gelatin-CNFs/epoxy sample
Part.
Using the method for the present invention, 0.25% protein-carbon nano-fiber epoxy resin composite wood that embodiment 2 obtains
Material performance progress experimental analysis, optical microscopy dispersity of the gelatin-CNFs in the first mixture, relative to
The first mixture of 0.25wt%Pristine-CNFs is more excellent, and 20 μm of diameter or more of particle significantly reduces, this surface
Dispersibility has good improvement;It can be seen that from Fig. 3 bending property relative to pure epoxy group, Gelatin-CNFs's is curved
17.86% and 16.54% has been respectively increased in bent intensity and modulus, is superior to Pristine-CNFs/epoxy group (11.43% He
8.50%), show there is good interfacial interaction performance between Gelatin-CNFs and epoxy.
Embodiment 3:
Using the method for the present invention, a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method, including
Following steps:
1) it weighs 0.4g soybean protein isolate (SPI) powder to be dissolved in 100ml deionized water, is placed on 57 DEG C of constant temperature
57min is stirred in oil bath magnetic stirring apparatus;
2) it after the mixed liquor for obtaining step 1) is cooled to room temperature, is added 0.2g carbon nano-fiber (CNFs), water-bath cooling
Environment lower prong is ultrasonically treated 5min;Then solution is placed in 57 DEG C of constant temperature oil bath magnetic stirring apparatus, 1900rpm revolving speed stirs
Mix 11h;
3) mixed liquor for obtaining step 2) filters, and after deionized water is washed 5 times, it is dry to be put into 72 DEG C of vacuum
Dry 11h, is finally ground, obtains soybean protein isolate-carbon nano-fiber (SPI-CNFs) in dry case.
4) SPI-CNFs for weighing 78mg, is added in the 30g epoxy resin of 37 DEG C of preheatings, hand operated mixing 1min, then
In water-bath cooling environment lower prong ultrasound 5min, power 100W, then water bath sonicator 32min at room temperature, is uniformly divided
The first scattered mixture;
5) the first mixture for obtaining step 4) is cooled to room temperature, and the quality proportioning with epoxy resin is consolidating for 10:3
Agent, mechanical stirring 12min vacuumize bubble removing 57min at room temperature, obtain the second mixture Gelatin-CNFs/
epoxy;
6) Gelatin-CNFs/epoxy for obtaining step 5) is poured slowly into mold, carries out 25 DEG C for 24 hours, and 60 DEG C
Three sections of solidifications of 15h, 120 DEG C of 2h, natural cooling after solidification;Protein-carbon nano-fiber weight percent is prepared
For protein-carbon nano-fiber epoxy resin composite material of 0.2wt%, i.e. SPI-CNFs/epoxy sample coupon.
Using the method for the present invention, the protein-carbon nano-fiber epoxy resin for the 0.10wt% that embodiment 3 obtains is compound
Material property progress experimental analysis, optical microscopy dispersity of the SPI-CNFs in the first mixture, relative to
The first mixture of 0.2wt%Pristine-CNFs is more excellent, and 20 μm of diameter or more of particle significantly reduces, this surface point
Scattered property has good improvement;It can be seen that from Fig. 3 bending property relative to pure epoxy group, the bending strength of SPI-CNFs
28% and 22% has been respectively increased with modulus, has been superior to Pristine-CNFs/epoxy group (11.43% and 8.50%), shows
There is good interfacial interaction performance between SPI-CNFs and epoxy.
Embodiment 4:
It is prepared for epoxide resin nano composite material using the original Pristine-CNFs not dealt with as control,
The following steps are included:
1) Pristine-CNFs for weighing 39mg, is added in the 30g epoxy resin of 37 DEG C of preheatings, hand operated mixing
1min, then in water-bath cooling environment lower prong ultrasound 5min, power 100W, then water bath sonicator 32min at room temperature,
Obtain the first evenly dispersed mixture;
2) the first mixture for obtaining step 1) is cooled to room temperature, and the quality proportioning with epoxy resin is consolidating for 10:3
Agent, mechanical stirring 12min vacuumize bubble removing 57min at room temperature, obtain the second mixture Pristine-CNFs/
epoxy;
3) Gelatin-CNFs/epoxy for obtaining step 2) is poured slowly into mold, carries out 25 DEG C for 24 hours, and 60 DEG C
Three sections of solidifications of 15h, 120 DEG C of 2h, natural cooling after solidification;Original carbon nano-fiber weight percent, which is prepared, is
The carbon nano-fiber epoxy resin composite material of 0.1wt%, i.e. Pristine-CNFs/epoxy sample coupon.
The original carbon nano-fiber epoxy resin composite material performance for the 0.10wt% that embodiment 4 obtains is tested
Analysis, as shown in Fig. 2 (b), optical microscopy scatter diagram of the Pristine-CNFs in the first mixture shows
Pristine-CNFs, particle accounting about 50% of the diameter range at 0~5 μm, 20 μm of diameter or more of particle accounting are more than
15%, this Dispersion on surface is not good enough;It can be seen that from Fig. 3 bending property relative to pure epoxy group, Pristine-CNFs
Bending strength and modulus 23% and 15% has been respectively increased, show that Pristine-CNFs enhances the bending property of epoxy.
Cooler environment described in step 2) of the present invention and step 4) can be using water-bath coolings environment such as mixture of ice and water
Or the coolant cooler environment that salt adds trash ice to be equipped with, also can choose refrigeration machine etc. can provide setting cooling temperature
Cooler environment.
In the embodiment of the present invention, when the protein in step 1) uses gelatin (Gelatin), by Gelatin by matter
It is preferred embodiment in the acetic acid solution that amount is configured to than the anhydrous acetic acid for 4:1 with deionized water, obtained protein-carbon is received
Rice fibrous epoxy resin composite property is more preferably.
It is excellent in deionized water by Gelatin when protein in step 1) uses soybean protein isolate (SPI)
Scheme is selected, obtained protein-carbon nano-fiber epoxy resin composite material performance is more preferably.
Protein functional group rich in, such as amino, carboxyl, hydroxyl, methyl provide more on its molecular structure
A reaction site can interact with CNFs and be grafted on its surface, form modified carbon nano tube fiber;Protein has as one kind
The environmentally protective surfactant of effect, can improve the dispersibility of carbon nano-fiber, avoid cluster and aggregation;Secondly, albumen
Interface performance between the carbon nano-fiber and epoxy resin-base of matter grafting is effectively improved.Experiment shows albumen
Matter-carbon nano-fiber/epoxy resin composite material has obtained good promotion in mechanical property.This environmentally protective place
Science and engineering skill is for modified carbon nano tube fiber and prepares modified epoxy resin composite and has a wide range of applications meaning.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all wrap
Containing within protection scope of the present invention.
Claims (10)
1. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method, which is characterized in that including walking as follows
It is rapid:
(1) protein powder for weighing 2a parts of quality is dissolved in the deionized water of 1000a parts of quality or is 4:1's by mass ratio
In the acetic acid solution that anhydrous acetic acid and deionized water are configured to, the constant temperature stirring denaturation of protein is carried out;
(2) mixed liquor that step (1) obtains is cooled to room temperature, the carbon nano-fiber of a~8a parts of quality is then added, carbon is received
Rice fiber is modified processing;
(3) mixed liquor that step (2) obtains is separated by solid-liquid separation, isolated solid is adopted and is washed with deionized into
Property after, be put into vacuum oven dry, then ground, obtain the carbon nano-fiber of protein grafting;
(4) carbon nano-fiber that the step of weighing 1.3b part quality (3) obtained protein is grafted, be added to the 400b of preheating~
It in the epoxy resin of 1000b parts of quality, is uniformly dispersed, obtains the first mixture;
(5) the first mixture that step (4) obtains is cooled to room temperature, being added with the quality proportioning of epoxy resin is consolidating for 10:3
Agent is dispersed with stirring, and bubble removing is gone to obtain the second mixture at room temperature;
(6) the second mixture that step (5) obtains is solidified, solidification carries out natural cooling after terminating, and obtains protein-
Carbon nano-fiber epoxy resin composite material.
2. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method according to claim 1,
It is characterized in that, in step (1), the protein is Type A type animal skin gelatin Gelatin or soybean protein isolate SPI;
Temperature is 55~60 DEG C in the constant temperature stirring denaturation of the protein, 55~60min of mixing time.
3. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method according to claim 1,
It is characterized in that, in step (2), the mode for being modified processing to carbon nano-fiber is that cooler environment lower prong ultrasonic treatment connects
Carry out constant temperature constant speed stirring.
4. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method according to claim 3,
It is characterized in that, in step (2), cooler environment lower prong is ultrasonically treated 5-6min;The temperature of constant temperature constant speed stirring is 55~
60 DEG C, the time is 55~60min, and revolving speed is 1800~2000rpm.
5. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method according to claim 1,
It is characterized in that, in step (3), drying temperature is 70~75 DEG C in vacuum oven, and the time is 10~12h.
6. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method according to claim 1,
It is characterized in that, in step (4), finely dispersed mode is cooler environment lower prong ultrasonic disperse, and then water-bath is super at room temperature
Sound.
7. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method according to claim 6,
It is characterized in that, in step (4), is added in the epoxy resin of 400~1000 parts of quality of 35 DEG C~40 DEG C preheatings, cooler environment
Lower prong 5~6min of ultrasonic time, then 30~35min of water bath sonicator at room temperature, obtains the first mixture.
8. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method according to claim 1,
It is characterized in that, in step (5), after the curing agent is added, 10~15min of mechanical stirring vacuumizes 50~60min at room temperature and goes
Bubble removing obtains the second mixture.
9. a kind of protein-carbon nano-fiber/epoxy resin composite material preparation method according to claim 1,
It being characterized in that, the second mixture is poured slowly into mold in step (6), carry out 25 DEG C for 24 hours, three sections of 60 DEG C of 15h, 120 DEG C of 2h
Solidification.
10. a kind of protein-carbon nano-fiber/epoxy resin being prepared by any one of claim 1-9 the method is multiple
Condensation material.
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