CN101314664A - Preparation method for rare earth modified carbon nano-tube/epoxy resin composite material - Google Patents
Preparation method for rare earth modified carbon nano-tube/epoxy resin composite material Download PDFInfo
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- CN101314664A CN101314664A CNA2008100407116A CN200810040711A CN101314664A CN 101314664 A CN101314664 A CN 101314664A CN A2008100407116 A CNA2008100407116 A CN A2008100407116A CN 200810040711 A CN200810040711 A CN 200810040711A CN 101314664 A CN101314664 A CN 101314664A
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Abstract
The invention relates to a method for preparing rear earth-modified carbon nanotube/epoxy resin composite material, which comprises the following steps: subjecting a carbon nanotube to surface modification treatment at room temperature by using a rear earth modifier, ball-milling the processed carbon nanotube in a ball miller, mechanically blending the carbon nanotube, epoxy resin and curing agent to control the mass percentage of the carbon nanotube of 1 to 10 percent of the mixed material, adding the mixed material in a vacuum oven for degassing, and injecting the mixed material into a mold to obtain the composite material, wherein the rear earth modifier contains a rear earth compound, ethanol, ethylenediaminetetraacetic acid, ammonium chloride, nitric acid and urea. The method has the advantages of simple process, low cost and environment-friendliness, and the prepared composite material has excellent mechanical properties and tribological properties.
Description
Technical field
The present invention relates to a kind of preparation method of matrix material, relate in particular to a kind of preparation method of rare earth modified carbon nanotube pipe/epoxy resin composite material, adopt through rare earth surface-treated carbon nanotube reinforced epoxy matrix material, obtaining, and then improve the mechanical property and the abrasion resistance properties of matrix material than higher interface binding power.
Background technology
Resins, epoxy is the oligopolymer that is formed by the molecule aggregation that contains 2 above epoxy group(ing), can form three-dimensional netted thermosetting resin with the solidifying agent reaction.Resins, epoxy has performances such as good bonding, corrosion-resistant, insulation, is widely used in tackiness agent, coating, insulating material and the matrix material.Because epoxy resin composite material has higher, the low density characteristics of intensity, can substitute materials such as timber, iron and steel in many occasions, thereby Resins, epoxy has become one of indispensable base mateiral of industrial circle gradually.But the shortcoming of epoxy resin composite material is more crisp, and its resistance to fatigue, thermotolerance, shock-resistance etc. are also poor, make its application be subjected to very big restriction.The normal method of modification that adopts gives epoxy resin composite material new performance in actual production.
Carbon nanotube is the seamless hollow tube that is rolled into by the graphite flake that carbon atom forms, and has peculiar electric property, superpower mechanical property, good adsorption property, thereby has caused very big attention in the material field.But carbon nanotube radial nano-grade size and high surface energy cause it to reunite easily in polymkeric substance, and be dispersed relatively poor, not only reduced the effective L D ratio of carbon nanotube.And cause slippage between the tube and tube easily, make the reinforced effects variation of carbon nanotube.In addition, the carbon nano tube surface feature is similar to graphite, and insoluble in most solvents, wet performance is poor, is difficult to be formed with effective adhesive with polymeric matrix.In order to improve the dispersed of carbon nanotube and to increase it and the bonding force of polymer interface, must be by to methods such as the physics of the surface modification of carbon nanotube and matrix, chemical modifications, improve the wetting property between carbon nanotube and the matrix, even between carbon nanotube and matrix, form Chemical bond, to improve the interface combination degree between carbon nanotube and the matrix, obtain the high matrix material of interlaminar shear strength.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of rare earth modified carbon nanotube pipe/epoxy resin composite material is provided, it is simple to have technology, the characteristics that reinforced effects is good, can well improve the interface binding power of carbon nanotube and epoxy resin-base, thereby improve the over-all properties of matrix material.
For realizing such purpose, in the technical scheme of the present invention, earlier at room temperature adopt rare-earth modifier that carbon nanotube is carried out surface modification treatment, carbon nanotube after will handling is again put into the ball mill ball milling, carbon nanotube after will handling then is compound with Resins, epoxy, is cast to that curing molding obtains rare earth modified carbon nanotube pipe/epoxy resin composite material in the mould.Wherein, the component of rare-earth modifier comprises rare earth compound, ethanol, ethylenediamine tetraacetic acid (EDTA), ammonium chloride, nitric acid and urea.
Method concrete steps of the present invention are:
Earlier carbon nanotube is immersed and soak 2～4 hours in the rare-earth modifier, filter the back oven dry; The carbon nanotube that obtains is handled in modification immersed in the distilled water, be made into the solution of carbon nanotubes 1～18wt%, solution is put into planetary ball mill ball milling 3～75min, rotating speed is 100～500r/min, the solution behind the ball milling is put into baking oven fully dry; Then carbon nanotube and Resins, epoxy are carried out mechanical blending, add solidifying agent again and stir, obtain mixture, by weight percentage, carbon nanotube is 1～10% in the mixture, and Resins, epoxy is 80～89%, and solidifying agent is 10%; Then mixture is put into the vacuum drying oven degassing 0.5～3 hour, the mixture after the degassing is injected mould,, be warming up to 120 ℃ of after fixing again 4 hours in 80 ℃ of curing 2 hours; The curing molding postcooling obtains rare earth modified carbon nanotube pipe/epoxy resin composite material.
Can be as required, with the gained matrix material again through being machined into carbon nano tube/epoxy resin matrix material sample or part.
The weight percentages of components of wherein said rare-earth modifier is: rare earth compound 0.1～2%, alcohol 95～99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05～0.5%, ammonium chloride 0.1～1%, nitric acid 0.02～0.5%, urea 0.03～1%.
Rare earth compound described in the present invention is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
Carbon nanotube described in the present invention is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes.
Resins, epoxy described in the present invention is E-51, E-44 or E-42 Resins, epoxy.
The present invention can solve the problem of carbon nano tube epoxy resin composite material interface bonding force difference, improves the mechanical property and the tribological property of matrix material, and processing method is simple, and cost is low.Adopt the matrix material of making through the carbon nano-tube filled Resins, epoxy of rare earth surface-treated to compare, have better mechanical property and tribological property with common same type of material.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described, following examples do not constitute limitation of the invention.
Embodiment 1
Used starting material comprise: E-51 Resins, epoxy, 5769 aliphatics amine solidifying agent are produced by Shanghai Resin Factory.Carbon nanotube: the Single Walled Carbon Nanotube that Nanometer Port Co., Ltd., Shenzhen produces.The weight percentages of components of the rare-earth modifier that is adopted is: Cerium II Chloride 0.1%, ethanol 99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05%, ammonium chloride 0.1%, nitric acid 0.02%, urea 0.03%.
Each weight percentages of components of starting material is as follows:
Resins, epoxy: 89%
Carbon nanotube: 1%
Solidifying agent: 10%
At room temperature carbon nanotube is immersed earlier in the rare-earth modifier and soaked 2 hours, filter the back oven dry.The carbon nanotube that obtains is handled in modification immersed in the distilled water, be made into the solution of carbon nanotubes 2wt%, solution is put into planetary ball mill ball milling 30min, rotating speed is 100r/min.The baking oven of solution behind the ball milling being put into 100 ℃ is fully dried.
Then Resins, epoxy is mixed according to aforementioned proportion with carbon nanotube, carry out the powerful 30min of stirring of machinery, make Resins, epoxy and carbon nanotube thorough mixing, add solidifying agent again, obtain mixture after stirring.Mixture is put into the vacuum drying oven degassing 0.5 hour, and the CNT (carbon nano-tube) after will outgasing again, Resins, epoxy and curing agent mixture material inject mould, in 80 ℃ of curing 2 hours, are warming up to 120 ℃ of after fixing again 4 hours.Matrix material behind the curing molding is taken out,, obtain rare earth modified carbon nanotube pipe/epoxy resin composite material with the room temperature cooling.
It is 40MPa that the matrix material that makes according to above-mentioned steps records its tensile strength according to standard.
Routine in contrast, under identical content of carbon nanotubes and composite material preparation process condition, the carbon nanotube reinforced epoxy matrix material tensile strength that non-modified is handled is 30MPa, and as can be seen, rare-earth modifier for treatment is significantly improved for the matrix material tensile property.
Embodiment 2
Used starting material comprise: E-51 Resins, epoxy, 5769 aliphatics amine solidifying agent are produced by Shanghai Resin Factory.Carbon nanotube: the double-walled carbon nano-tube that Nanometer Port Co., Ltd., Shenzhen produces.The weight percentages of components of the rare-earth modifier that is adopted is: lanthanum trioxide 1.5%, ethanol 96%, ethylenediamine tetraacetic acid (EDTA) 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, urea 1%.
Each weight percentages of components of starting material is as follows:
Resins, epoxy: 85%
Carbon nanotube: 5%
Solidifying agent: 10%
At room temperature carbon nanotube is immersed earlier in the rare-earth modifier and soaked 3 hours, filter the back oven dry.The carbon nanotube that obtains is handled in modification immersed in the distilled water, be made into the solution of carbon nanotubes 6wt%, solution is put into planetary ball mill ball milling 15min, rotating speed is 500r/min.The baking oven of solution behind the ball milling being put into 100 ℃ is fully dried.
Then Resins, epoxy is mixed according to aforementioned proportion with carbon nanotube, carry out the powerful stirring of machinery 1 hour, make Resins, epoxy and carbon nanotube thorough mixing, add solidifying agent again, obtain mixture after stirring.Mixture is put into the vacuum drying oven degassing 2 hours, and the CNT (carbon nano-tube) after will outgasing again, Resins, epoxy and curing agent mixture material inject mould, in 80 ℃ of curing 2 hours, are warming up to 120 ℃ of after fixing again 4 hours.Matrix material behind the curing molding is taken out,, obtain rare earth modified carbon nanotube pipe/epoxy resin composite material with the room temperature cooling.
Above-mentioned gained material mechanical is processed into shock test sample and rub(bing)test sample.
Utilize MMD-10 type metope wear testing machine, matrix material is carried out the friction and wear behavior test, and compare with undressed carbon nano tube/epoxy resin matrix material, experimental result shows: the friction and wear behavior through the carbon nano tube/epoxy resin matrix material of rare earth modified processing is better than the carbon nano tube/epoxy resin matrix material that non-modified is handled.
Embodiment 3
Used starting material comprise: E-51 Resins, epoxy, 5769 aliphatics amine solidifying agent are produced by Shanghai Resin Factory.Carbon nanotube: the multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.The weight percentages of components of the rare-earth modifier that is adopted is: Lanthanum trichloride 2%, alcohol 95 %, ethylenediamine tetraacetic acid (EDTA) 0.5%, ammonium chloride 1%, nitric acid 0.5%, urea 1%.
Each weight percentages of components of starting material is as follows:
Resins, epoxy: 80%
Carbon nanotube: 10%
Solidifying agent: 10%
At room temperature carbon nanotube is immersed earlier in the rare-earth modifier and soaked 4 hours, filter the back oven dry.The carbon nanotube that obtains is handled in modification immersed in the distilled water, be made into the solution of carbon nanotubes 2wt%, solution is put into planetary ball mill ball milling 60min, rotating speed is 400r/min.The baking oven of solution behind the ball milling being put into 100 ℃ is fully dried.
Then Resins, epoxy is mixed according to aforementioned proportion with carbon nanotube, carry out the powerful stirring of machinery 2 hours, make Resins, epoxy and carbon nanotube thorough mixing, add solidifying agent again, obtain mixture after stirring.Mixture is put into the vacuum drying oven degassing 3 hours, and the CNT (carbon nano-tube) after will outgasing again, Resins, epoxy and curing agent mixture material inject mould, in 80 ℃ of curing 2 hours, are warming up to 120 ℃ of after fixing again 4 hours.Matrix material behind the curing molding is taken out,, obtain rare earth modified carbon nanotube pipe/epoxy resin composite material with the room temperature cooling.
It is 42MPa that the matrix material that makes according to above-mentioned steps records its tensile strength according to standard.
Carry out composite material impact test by GB GB1415-83 regulation, the XCJ-40 type charpy impact test machine that adopts Chengde trier factory to produce, obtaining material impact toughness is 38.8kJ/m
2Routine in contrast, under identical fibre content and composite material preparation process condition, untreated matrix material impelling strength is 30.7kJ/m
2Matrix material impelling strength through rare-earth modifier for treatment of the present invention as can be seen is good.
Claims (3)
1. the preparation method of a rare earth modified carbon nanotube pipe/epoxy resin composite material is characterized in that earlier carbon nanotube being immersed soaking 2～4 hours in the rare-earth modifier, filters the back oven dry; The carbon nanotube that obtains is handled in modification immersed in the distilled water, be made into the solution of carbon nanotubes 1～18wt%, solution is put into planetary ball mill ball milling 3～75min, rotating speed is 100～500r/min, the solution behind the ball milling is put into baking oven fully dry; Then carbon nanotube and Resins, epoxy are carried out mechanical blending, add solidifying agent again and stir, obtain mixture, by weight percentage, carbon nanotube is 1～10% in the mixture, and Resins, epoxy is 80～89%, and solidifying agent is 10%; Then mixture is put into the vacuum drying oven degassing 0.5～3 hour, the mixture after the degassing is injected mould,, be warming up to 120 ℃ of after fixing again 4 hours in 80 ℃ of curing 2 hours; The curing molding postcooling obtains rare earth modified carbon nanotube pipe/epoxy resin composite material;
The weight percentages of components of wherein said rare-earth modifier is: rare earth compound 0.1～2%, alcohol 95～99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05～0.5%, ammonium chloride 0.1～1%, nitric acid 0.02～0.5%, urea 0.03～1%.
2, according to the preparation method of the rare earth modified carbon nanotube pipe/epoxy resin composite material of claim 1, it is characterized in that described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
3, according to the preparation method of the rare earth modified carbon nanotube pipe/epoxy resin composite material of claim 1, it is characterized in that described carbon nanotube is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described Resins, epoxy is E-51, E-44 or E-42 Resins, epoxy.
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| CNA2008100407116A CN101314664A (en) | 2008-07-17 | 2008-07-17 | Preparation method for rare earth modified carbon nano-tube/epoxy resin composite material |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781444A (en) * | 2010-03-31 | 2010-07-21 | 上海交通大学 | Method for preparing rare-earth-modified glass-fiber epoxy-resin composite materials |
| CN101831232A (en) * | 2010-04-29 | 2010-09-15 | 哈尔滨工程大学 | Rare earth compound epoxy zinc-rich paint for preventing microorganism attachment and preparation method thereof |
| CN102533190A (en) * | 2010-12-10 | 2012-07-04 | 张士钦 | Carbon nano-tube compound epoxy resin adhesive and application method thereof |
| RU2471829C1 (en) * | 2011-05-11 | 2013-01-10 | Российская Федерация в лице Министерства промышленности и торговли Российской Федерации (Минпромторг России) | Epoxy binder, prepreg based thereon and article made therefrom |
| CN103073847A (en) * | 2013-01-23 | 2013-05-01 | 苏州大学 | Modified carbon nano tube/thermosetting resin composite material and preparation method thereof |
| CN103726399A (en) * | 2013-12-19 | 2014-04-16 | 陕西科技大学 | Blend fiber-reinforced paper-based friction material and preparation method thereof |
| CN104558659A (en) * | 2013-10-11 | 2015-04-29 | 北京化工大学 | Preparation of carbon fiber/epoxy resin prepreg sprayed with aminated carbon nanotubes |
| CN108690488A (en) * | 2018-05-02 | 2018-10-23 | 苏州捷德瑞精密机械有限公司 | A kind of electronic circuit board three proofings coating material and preparation method thereof |
| CN113122186A (en) * | 2021-04-21 | 2021-07-16 | 广东工业大学 | Nano-metal composite phase-change material and preparation method thereof |
| CN115286895A (en) * | 2022-02-09 | 2022-11-04 | 青岛大学 | Rare earth complex modified epoxy resin composite material and preparation method thereof |
| CN115926586A (en) * | 2023-02-01 | 2023-04-07 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
| CN116178894A (en) * | 2023-02-03 | 2023-05-30 | 安徽恒泰新材料科技股份有限公司 | Epoxy resin composite material and processing device thereof |
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2008
- 2008-07-17 CN CNA2008100407116A patent/CN101314664A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781444A (en) * | 2010-03-31 | 2010-07-21 | 上海交通大学 | Method for preparing rare-earth-modified glass-fiber epoxy-resin composite materials |
| CN101831232A (en) * | 2010-04-29 | 2010-09-15 | 哈尔滨工程大学 | Rare earth compound epoxy zinc-rich paint for preventing microorganism attachment and preparation method thereof |
| CN101831232B (en) * | 2010-04-29 | 2012-05-09 | 哈尔滨工程大学 | Rare earth compound epoxy zinc-rich paint for preventing microorganism attachment and preparation method thereof |
| CN102533190A (en) * | 2010-12-10 | 2012-07-04 | 张士钦 | Carbon nano-tube compound epoxy resin adhesive and application method thereof |
| RU2471829C1 (en) * | 2011-05-11 | 2013-01-10 | Российская Федерация в лице Министерства промышленности и торговли Российской Федерации (Минпромторг России) | Epoxy binder, prepreg based thereon and article made therefrom |
| CN103073847A (en) * | 2013-01-23 | 2013-05-01 | 苏州大学 | Modified carbon nano tube/thermosetting resin composite material and preparation method thereof |
| CN104558659A (en) * | 2013-10-11 | 2015-04-29 | 北京化工大学 | Preparation of carbon fiber/epoxy resin prepreg sprayed with aminated carbon nanotubes |
| CN103726399A (en) * | 2013-12-19 | 2014-04-16 | 陕西科技大学 | Blend fiber-reinforced paper-based friction material and preparation method thereof |
| CN108690488A (en) * | 2018-05-02 | 2018-10-23 | 苏州捷德瑞精密机械有限公司 | A kind of electronic circuit board three proofings coating material and preparation method thereof |
| CN113122186A (en) * | 2021-04-21 | 2021-07-16 | 广东工业大学 | Nano-metal composite phase-change material and preparation method thereof |
| CN115286895A (en) * | 2022-02-09 | 2022-11-04 | 青岛大学 | Rare earth complex modified epoxy resin composite material and preparation method thereof |
| CN115286895B (en) * | 2022-02-09 | 2023-07-07 | 青岛大学 | Rare earth complex modified epoxy resin composite material and preparation method thereof |
| CN115926586A (en) * | 2023-02-01 | 2023-04-07 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
| CN115926586B (en) * | 2023-02-01 | 2023-08-18 | 天津大学 | Epoxy heat-conducting anticorrosive paint and preparation method thereof |
| CN116178894A (en) * | 2023-02-03 | 2023-05-30 | 安徽恒泰新材料科技股份有限公司 | Epoxy resin composite material and processing device thereof |
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Open date: 20081203 |