CN104356598B - Modified graphene, preparation method thereof and composite material comprising epoxy resin enhanced by modified graphene - Google Patents
Modified graphene, preparation method thereof and composite material comprising epoxy resin enhanced by modified graphene Download PDFInfo
- Publication number
- CN104356598B CN104356598B CN201410611914.1A CN201410611914A CN104356598B CN 104356598 B CN104356598 B CN 104356598B CN 201410611914 A CN201410611914 A CN 201410611914A CN 104356598 B CN104356598 B CN 104356598B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- graphene
- firming agent
- accelerator
- modified graphene
- 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
Links
Abstract
The invention aims to provide an alkali modified graphene and a method for preparing a composite epoxy resin material with the graphene. The method comprises the following steps: the graphene is processed by using a mixed solution of a hydrogen peroxide solution and an ammonia solution, and the surface grafting modification of the graphene is realized, so that the modified graphene is homogeneously dispersed in an epoxy resin matrix, and the composite epoxy resin material enhanced by the graphene, with excellent mechanical property, can be prepared.
Description
Technical field
The present invention relates to Graphene modification field, more particularly, to a kind of method of alkali compoundss modified graphene, and its
Enhanced epoxy resin composite material.
Background technology
Since Graphene (graphene) this material in 2004 is found, just it be not interrupted about research and news.
Graphene is a kind of carbonaceous new material of carbon atom tightly packed one-tenth monolayer bi-dimensional cellular shape lattice structure, this Graphene crystal
The thickness of thin film only has 0.335nm, only the 200000 of hair diameter/, be to be currently known intensity highest material in the world
Material, is the elementary cell building other dimension carbonaceous materials (as zero dimension fullerene, one-dimensional CNT, three-dimensional graphite), has
Fabulous crystallinity and electric property.This material not only can be used for developing producing thin ultra light aircraft material as the scraps of paper
The tough and tensile flak jackets of material, manufacture excess of export, or even 2.3 ten thousand miles that scientist dreams of long space elevators can be allowed to become a reality.
Similar with SWCN (SWCNT), Graphene has the excellent performance such as heat, power, electricity.
Prepare the key point of high performance Graphene/epoxy resin composite material with how when filling Graphene
It is uniformly dispersed in epoxy resin-base.Scattered method mainly improves filling in the base to improve now obturator
Interface binding power between body and matrix.Report with regard to improving interface binding power with acid modification Graphene has a lot at present,
But seldom it is related to the report with alkali modification Graphene.
Content of the invention
The technical problem to be solved there is provided a kind of alkali modification Graphene and prepares Graphene epoxy resin
The method of composite it is achieved that homogeneous dispersion in epoxy resin-base for the modified graphene, thus can prepare have excellent
The Graphene epoxy resin composite material of different mechanical property.
The present invention is achieved by the following technical solutions, and the present invention comprises the following steps：
Step one, Graphene is added in the mixed solution that hydrogen peroxide is with ammonia, supersound process at a certain temperature, uses
Appropriate deionized water dilution, is then filtered with sand core funnel and washs to neutrality, product is placed in vacuum drying oven and dries, be obtained
The Graphene of surface treatment.
Step 2, during preparing composite, epoxy resin, firming agent and accelerator are according to certain mass ratio
Mixing.First, weigh 49.0g firming agent, 70g epoxy resin (E-51), then according to epoxy resin, firming agent and rush
Enter agent gross mass certain proportion and weigh modified graphene, Graphene is added to the mixing of the firming agent having weighed and epoxy resin
In solution, it is then placed in 60 DEG C of permanent stirred in water bath uniformly, be then that 600W ultrasound wave separating apparatus are carried out with power more ultrasonic
Process 3h.
After supersound process terminates, 0.7g accelerator is added in mixed liquor, with after Glass rod stirring 10min more ultrasonic half
Individual hour.Put it under 60 DEG C, -0.1MPa, in vacuum drying oven, exclude bubble 0.5h.After exclusion bubble, it is drawn off pouring into a mould
To coating in releasing agent warmed-up mould, the size of stretching and bend specimen mould respectively with GB2568-81 and
GB2570-81 standard is consistent, puts into baking oven and is heating and curing, and the condition of solidification is 90 DEG C of insulations 1h, 130 DEG C of constant temperature 2h, 160
DEG C constant temperature 2h, then natural cooling in an oven.
The further preferred version of the present invention is：The ratio of described ammonia and hydrogen peroxide is 1～4: 1.
The further preferred version of the present invention is：The ratio of described Graphene and alkali mixed solution is 0.001～0.01g/
ml.
The further preferred version of the present invention is：Described ultrasonic time is 2～8 hours.
The further preferred version of the present invention is：Described ultrasonic temperature is 30～60 DEG C.
The further preferred version of the present invention is：Described epoxy resin, firming agent and accelerator are 100 according to mass ratio:
The mass mixing of 50～80: 1 proportioning
The further preferred version of the present invention is：The ratio that the quality that described Graphene adds accounts for gross mass is 0.05%～
1%.
The method that the present invention adopts only just need to can obtain modified graphene through mixing, ultrasonic, washing process, has technique
Simply, material preparation cost low, free from environmental pollution the features such as, easily realize extensive preparation.
The present invention has higher stretching strong due to using modified graphene as the standby composite of filling system
Degree and bending strength.By Mechanics Performance Testing, when Graphene addition is 1%, the tensile strength of composite reaches
67.28Mpa, bending strength has reached 135.58Mpa.
Brief description
Infrared spectrogram (FTIR) figure of accompanying drawing 1 modified graphene.
The composite tensile strength figure of the different modified graphene addition of accompanying drawing 2.
The composite bending strength figure of the different modified graphene addition of accompanying drawing 3.
Accompanying drawing 4 fracture of composite materials Surface scan Electronic Speculum (SEM) photo.
Specific embodiment
The present invention will be described in more detail with reference to the accompanying drawings and examples
Embodiment 1
Step one, 0.4g Graphene is added in the mixed solution that 400ml hydrogen peroxide is formed with ammonia 1: 1, at 30 DEG C
Lower supersound process 2h, with appropriate deionized water dilution, is then filtered with sand core funnel and washs to neutrality, product is placed in very
Empty oven for drying, is obtained the Graphene of surface treatment.
Step 2, during preparing composite, epoxy resin, firming agent and accelerator are 100 according to mass ratio:
The mass mixing of 50: 1 proportioning.First, weigh 49.0g firming agent, 70g epoxy resin (E-51), then according to ring
The 0.05% of oxygen tree fat, firming agent and accelerator gross mass weighs modified graphene, Graphene is added to the solidification having weighed
In the mixed solution of agent and epoxy resin, it is then placed in 60 DEG C of permanent stirred in water bath uniformly, be then that 600W surpasses with power again
Sound wave separating apparatus carry out supersound process 3h.
After supersound process terminates, 0.7g accelerator is added in mixed liquor, with after Glass rod stirring 10min more ultrasonic half
Individual hour.Put it under 60 DEG C, -0.1MPa, in vacuum drying oven, exclude bubble 0.5h.After exclusion bubble, it is drawn off pouring into a mould
To coating in releasing agent warmed-up mould, the size of stretching and bend specimen mould respectively with GB2568-81 and
GB2570-81 standard is consistent, puts into baking oven and is heating and curing, and the condition of solidification is 90 DEG C of insulations 1h, 130 DEG C of constant temperature 2h, 160
DEG C constant temperature 2h, then natural cooling in an oven.
Embodiment 2
Step one, 0.6g Graphene is added in the mixed solution that 400ml hydrogen peroxide is formed with ammonia 2: 1, at 40 DEG C
Lower supersound process 4h, with appropriate deionized water dilution, is then filtered with sand core funnel and washs to neutrality, product is placed in very
Empty oven for drying, is obtained the Graphene of surface treatment.
Step 2, during preparing composite, epoxy resin, firming agent and accelerator are 100 according to mass ratio:
The mass mixing of 60: 1 proportioning.First, weigh 49.0g firming agent, 70g epoxy resin (E-51), then according to ring
The 0.1% of oxygen tree fat, firming agent and accelerator gross mass weighs modified graphene, Graphene is added to the firming agent having weighed
In the mixed solution of epoxy resin, it is then placed in 60 DEG C of permanent stirred in water bath uniformly, be then that 600W is ultrasonic with power again
Ripple separating apparatus carry out supersound process 3h.
After supersound process terminates, 0.7g accelerator is added in mixed liquor, with after Glass rod stirring 10min more ultrasonic half
Individual hour.Put it under 60 DEG C, -0.1MPa, in vacuum drying oven, exclude bubble 0.5h.After exclusion bubble, it is drawn off pouring into a mould
To coating in releasing agent warmed-up mould, the size of stretching and bend specimen mould respectively with GB2568-81 and
GB2570-81 standard is consistent, puts into baking oven and is heating and curing, and the condition of solidification is 90 DEG C of insulations 1h, 130 DEG C of constant temperature 2h, 160
DEG C constant temperature 2h, then natural cooling in an oven.
Embodiment 3
Step one, 0.8g Graphene is added in the mixed solution that 400ml hydrogen peroxide is formed with ammonia 3: 1, at 50 DEG C
Lower supersound process 6h, with appropriate deionized water dilution, is then filtered with sand core funnel and washs to neutrality, product is placed in very
Empty oven for drying, is obtained the Graphene of surface treatment.
Step 2, during preparing composite, epoxy resin, firming agent and accelerator are 100 according to mass ratio:
The mass mixing of 70: 1 proportioning.First, weigh 49.0g firming agent, 70g epoxy resin (E-51), then according to ring
The 0.5% of oxygen tree fat, firming agent and accelerator gross mass weighs modified graphene, Graphene is added to the firming agent having weighed
In the mixed solution of epoxy resin, it is then placed in 60 DEG C of permanent stirred in water bath uniformly, be then that 600W is ultrasonic with power again
Ripple separating apparatus carry out supersound process 3h.
After supersound process terminates, 0.7g accelerator is added in mixed liquor, with after Glass rod stirring 10min more ultrasonic half
Individual hour.Put it under 60 DEG C, -0.1MPa, in vacuum drying oven, exclude bubble 0.5h.After exclusion bubble, it is drawn off pouring into a mould
To coating in releasing agent warmed-up mould, the size of stretching and bend specimen mould respectively with GB2568-81 and
GB2570-81 standard is consistent, puts into baking oven and is heating and curing, and the condition of solidification is 90 DEG C of insulations 1h, 130 DEG C of constant temperature 2h, 160
DEG C constant temperature 2h, then natural cooling in an oven.
Embodiment 4
Step one, 1g Graphene is added in the mixed solution that 400ml hydrogen peroxide is formed with ammonia 4: 1, at 60 DEG C
Supersound process 8h, with appropriate deionized water dilution, is then filtered with sand core funnel and washs to neutrality, product is placed in vacuum
Oven for drying, is obtained the Graphene of surface treatment.
Step 2, during preparing composite, epoxy resin, firming agent and accelerator are 100 according to mass ratio:
The mass mixing of 80: 1 proportioning.First, weigh 49.0g firming agent, 70g epoxy resin (E-51), then according to ring
The 1% of oxygen tree fat, firming agent and accelerator gross mass weighs modified graphene, Graphene is added to the firming agent having weighed and
In the mixed solution of epoxy resin, it is then placed in 60 DEG C of permanent stirred in water bath uniformly, be then 600W ultrasound wave with power again
Separating apparatus carry out supersound process 3h.
After supersound process terminates, 0.7g accelerator is added in mixed liquor, with after Glass rod stirring 10min more ultrasonic half
Individual hour.Put it under 60 DEG C, -0.1MPa, in vacuum drying oven, exclude bubble 0.5h.After exclusion bubble, it is drawn off pouring into a mould
To coating in releasing agent warmed-up mould, the size of stretching and bend specimen mould respectively with GB2568-81 and
GB2570-81 standard is consistent, puts into baking oven and is heating and curing, and the condition of solidification is 90 DEG C of insulations 1h, 130 DEG C of constant temperature 2h, 160
DEG C constant temperature 2h, then natural cooling in an oven.
Below the preferred embodiments of the present invention are illustrated, but the present invention are not limited to described embodiment,
Those of ordinary skill in the art also can make a variety of equivalent modifications or replacement on the premise of spiritual without prejudice to the present invention,
These equivalent modifications or replacement are all contained in the application claim limited range.
Claims (2)
1. a kind of method preparing modified graphene epoxy resin composite material is it is characterised in that be obtained as follows：
Step one, Graphene is added in the mixed solution of hydrogen peroxide and ammonia, supersound process at a certain temperature, with appropriate
Deionized water dilution, then filtered with sand core funnel and wash to neutrality, product is placed in vacuum drying oven and dries, prepared surface
The Graphene processing, wherein, the ratio of described ammonia and hydrogen peroxide is 1～4: 1；
Step 2, during preparing composite, epoxy resin, firming agent and accelerator are mixed according to certain mass ratio
Close；First, weigh firming agent, epoxy resin E-51, then according to epoxy resin, firming agent and accelerator gross mass one
Certainty ratio weighs modified graphene, Graphene is added in the firming agent having weighed and the mixed solution of epoxy resin, then
Put into 60 DEG C of permanent stirred in water bath uniformly, be then that 600W ultrasound wave separating apparatus carry out supersound process 3h with power again, wherein,
The ratio of the gross mass that the quality that described modified graphene adds accounts for epoxy resin, firming agent and accelerator is 0.05%～1%；
After supersound process terminates, accelerator is added in mixed liquor, with ultrasonic half an hour again after Glass rod stirring 10min；
Put it under 60 DEG C, -0.1MPa, in vacuum drying oven, exclude bubble 0.5h；After exclusion bubble, it is drawn off being poured into and applies
In good releasing agent warmed-up mould, the size of stretching and bend specimen mould is marked with GB2568-81 and GB2570-81 respectively
Accurate consistent, put into baking oven and be heating and curing, the condition of solidification is 90 DEG C of insulations 1h, 130 DEG C of constant temperature 2h, 160 DEG C of constant temperature 2h, so
Natural cooling in an oven afterwards.
2. according to claim 1 preparation method it is characterised in that described epoxy resin, firming agent and accelerator are according to matter
Amount is than the mass mixing of the proportioning for 100: 50～80: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410611914.1A CN104356598B (en) | 2014-11-05 | 2014-11-05 | Modified graphene, preparation method thereof and composite material comprising epoxy resin enhanced by modified graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410611914.1A CN104356598B (en) | 2014-11-05 | 2014-11-05 | Modified graphene, preparation method thereof and composite material comprising epoxy resin enhanced by modified graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104356598A CN104356598A (en) | 2015-02-18 |
| CN104356598B true CN104356598B (en) | 2017-02-15 |
Family
ID=52523920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410611914.1A Active CN104356598B (en) | 2014-11-05 | 2014-11-05 | Modified graphene, preparation method thereof and composite material comprising epoxy resin enhanced by modified graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104356598B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861910B (en) * | 2015-05-20 | 2017-04-05 | 北京化工大学 | A kind of graphene coated inorganic filler epoxy resin compound adhesive and preparation method thereof |
| CN104830027A (en) * | 2015-05-20 | 2015-08-12 | 叶芳 | Method for preparing novel epoxy resin laminated composite material for sports equipment |
| CN107129660A (en) * | 2017-05-12 | 2017-09-05 | 深圳市华星光电技术有限公司 | LED encapsulation material and preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153835B (en) * | 2011-03-15 | 2012-12-19 | 北京航空航天大学 | Modified graphene/epoxy resin composite material and preparation method thereof |
| CN102286189B (en) * | 2011-06-24 | 2012-11-21 | 中国科学院理化技术研究所 | Method for preparing graphene oxide/epoxide resin nano composite material |
-
2014
- 2014-11-05 CN CN201410611914.1A patent/CN104356598B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104356598A (en) | 2015-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6915887B2 (en) | Polypyrrole film graphene oxide cement-based composite material and its preparation method | |
| CN105968717A (en) | Preparation of carbon fiber/graphene/carbon nanotube/epoxy resin prepreg and carbon fiber composite material | |
| CN104356598B (en) | Modified graphene, preparation method thereof and composite material comprising epoxy resin enhanced by modified graphene | |
| CN105860143A (en) | Flexible nanocellulose-graphene composite membrane and preparation method thereof | |
| CN109627689B (en) | Preparation method of graphene-epoxy resin composite material | |
| CN102732037A (en) | Graphene foam/polymer high-conductivity composite material preparation method and application thereof | |
| CN108570212A (en) | A kind of manufacturing method of carbon fiber bulk moulding material | |
| Xiao et al. | 3D printed SiC nanowire reinforced composites for broadband electromagnetic absorption | |
| CN107459774A (en) | A kind of graphene/nanometer silica/epoxy resin composite material and preparation method thereof | |
| CN110408083A (en) | It is a kind of using bacteria cellulose as high-heat-conductive composite material of matrix and preparation method thereof | |
| CN108285612A (en) | A kind of high heat conductive insulating thermosetting polymer and preparation method | |
| CN107474354A (en) | A kind of high dispersive graphene heat-conducting plastic preparation method and products thereof and application | |
| CN110818927A (en) | Heat-conducting gelatin composite film and preparation method thereof | |
| Fan et al. | Effect of carbon nanotube and styrene-acrylic emulsion additives on microstructure and mechanical characteristics of cement paste | |
| WO2021000551A1 (en) | Graft-modified aluminum oxide and preparation method therefor, epoxy composite material and application thereof | |
| Raza et al. | A study on mechanical characteristics of cement composites fabricated with nano-silica and carbon nanotube | |
| CN104194264B (en) | PCB high heat resistance POSS base epoxy nanocomposite and preparation method thereof | |
| CN109593331A (en) | A kind of preparation method and product of graphene oxide tannic acid compound enhancing polylactic acid 3D printing material | |
| CN104894869A (en) | Fast preparation method of carbon fiber reinforcement | |
| Ji et al. | Quantitative evaluation of carbon fiber dispersion in amorphous calcium silicate hydrate-based contact-hardening composites | |
| Yang et al. | Synergistic Enhanced Thermal Conductivity and Crack Resistance of Reactor Epoxy Insulation with Boron Nitride Nanosheets and Multiwalled Carbon Nanotubes | |
| CN107936273A (en) | A kind of high-performance light composite material of carbon fiber enhancement resin base and preparation method thereof | |
| CN103602847A (en) | Method for preparing carbon-nanotube-modified aluminum material from boride-coated single-walled carbon nanotubes | |
| CN109294501A (en) | A kind of graphite oxide alkenyl waterproof insulation glue | |
| CN109608881A (en) | A kind of preparation method of rubber neutron shielding material |
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 |